mgcj2015 Green Chem Journal

The McGill Green Chemistry Journal
Vol.1 – December 2015

Table of Contents
A Note from the Editors
Carbon Dioxide
Critical Essay: Supercritical CO2 dyeing, a key to textile dyeing’s sustainable future
Irene Carrasco, Editor-in-Chief p. 6
A super-critical review of supercritical fluids: can SCFs replace traditional solvents?

Charles Cole p. 10
Carbon dioxide copolymerization: how green is it?

Rebecca O’Leary p. 15
Methane
Making something from nothing: qualifying the potential of biogas from organic waste in Canada
Joanna Vinden p. 21
Strategies for the reduction of methane emissions and harnessing for use as an alternative energy
resource: a review
Alyssa Fu p. 26
Environmental decay, incommensurate methane emission, and feasible future solutions for the
treatment of a greenhouse gas
Angel Castaneda Ruiz p. 31
Chemical Processes
Critical Essay: On selectivity and stability: can metal organic frameworks be a green industrial
catalyst?
John Hsu p. 35
Synthesis of polyurethane using castor oil based and kraft lignin based polyols: a review
Hyun June Jun p. 39
Green alternatives for the synthesis of metal nanoparticles

Philippe Green p. 44
Current developments in green chemical extraction techniques of lignocellulosic materials:

implications to next-generation biorefineries
Bryan Lee p. 52
Endangered Element: A Review on Palladium

Luca Poli p. 56
McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 2

Consumer Products
Critical Essay: Visibly green chemistry: in favour of polyhydroxyalkanoates to replace
conventional petroleum-based polymers
Allen Li, Associate Editor p. 61
The ugliness of the personal care industry

Sokina Joseph p. 65
Green Energy
Sustainable water-splitting methods to produce hydrogen
Nora Abbassi-Mohadjel p. 72
How current hydrogen producing fuel cells show promise of a green, zero-emission energy
generation
Richard von Celsing p.81
A methanol economy based on renewable resources

Thomas Garrow p.87
On the effectiveness and sustainability of large-scale CdTe photovoltaic cell use

Sebastian Drake p. 91
Waste Reduction and Repurposing

Chemical valorization of coffee bean waste
Ross Koby, Associate Editor p. 95
How green is green? A critical analysis of chemical processes that utilize citrus waste by
employing the principles of green chemistry
Andrew Brebner p. 99
Development in the commercial methods of recycling poly(ethylene terephthalate)

Corey Braun p. 105
Remediation
Review of polychlorinated biphenyls treatments in water and soils: from supercritical fluid
extraction to rhizotemediation
Sheena Louisia, Associate Editor p. 109

About the McGill Green Chemistry Journal
The McGill Green Chemistry Journal consists of articles written by McGill students, which report and
critique issues related to the 12 Principles of Green Chemistry. The journal broadens the definition of
green chemistry by accepting the perspectives offered by the authors. The published articles highlight
different ways for sustainable chemistry to directly and indirectly improve people’s lives. The articles
cover the following subjects:
•Design of more sustainable reactions and chemicals
•Chemistry to reduce waste production
•Analytical techniques for hazardous chemicals
•The societal effects of green chemistry
•Evaluation of the sustainability of current chemical processes and methods

A Letter from the Editors
The world we live in is in a precarious state; one that will require technological advances and a shift to
sustainable practices to ensure the prosperity of current and future generations. As chemists, we have
the ability to greatly impact the world and help society make informed decisions. Current pressing issues
including climate change, resource scarcity, access to energy and pollution can be ameliorated by
advances in green chemistry. Green chemistry is the philosophy and practice of reducing the negative
impact and increasing the sustainability of chemistry. It is for this reason that we have chosen to focus
on this quickly developing field in this journal.
There is a distinct lack of focus on green chemistry in core chemistry undergraduate classes, meaning all
learning must be done independently if the student’s specific chemistry department does not value
sustainability enough to offer courses in it. This peer-reviewed journal will hopefully act as a beacon for
students trying to develop their own sense of sustainability and interest in green chemistry.
This student-run journal is designed to give McGill students a platform to publish work on the scientific
advances in green chemistry and to develop writing skills and interest in the topic.
In our first year, the making of this journal has been a learning experience for all of those involved. We
hope our work will enable future student interest in publishing in this field. Furthermore, we hope to
inspire students graduating from the McGill University Chemistry Department to pursue research and
careers that employ green chemistry.
Thank you,
Irene Carrasco
Editor-In-Chief
Sheena Louisia
Allen Li
Ross Koby
Associate Editors

A Critical Essay: Supercritical CO2 Dyeing, a Key to Textile Dyeing’s
Sustainable Future
Irene Carrasco
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, Canada, H3A 0B8.
KEYWORDS: Supercritical CO2, Textile Industry, Polyester, Waterless, Sustainable
ABSTRACT: Energy is scarce.1 Water is scarce.2 Carbon dioxide is plentiful.3 With this in mind, an efficient process that reduces
both energy and water consumption4 at the expense of carbon dioxide in the textile industry – the most water polluting of the
industrial sectors5 - must be applied at once. In this critical essay strong regulations and strategic subsidies are proposed as the
remaining factors needed for the successful widespread implementation of supercritical carbon dioxide (scCO2) polyester dyeing
technology in the textile industry. The technology has been developed4, pilot plants have been tested successfully6 and large
companies have taken up the technology7. However, the technology is still considered to be in the pilot stage.7 Thus, what remains
to successfully commercialize the technology is to combine regulation on wastewater discharge that will force the industry to change
their processes with strategic subsidies. This essay demonstrates that the chemistry and technology required for this
commercialization is available and it is time to use it to solve the grave problem that is textile dyeing water pollution.
THE TEXTILE INDUSTRY’S PROBLEM plants are not equipped to deal with these resistant effluents
and with variation in effluent chemical composition for
The textile industry’s high water consumption in its dyeing different dyeing plants, a large portion of these dyes escape into
processes8 and lack of effluent discharge legislation5 have made the environment.5 Once in the environment, these dyes persist
it one of manufacturing’s largest water consumers7. The as a result of their high stability and resistance to biological
conventional wet textile dyeing process is inefficient, with an degradation.5 This stability is due in large part to 70% of the
estimated 200 000 tons of unused dye emitted by the industry world’s organic dyes being comprised of azo dyes.5 The
in its wastewater each year.5 As many wastewater treatment

problem arises in that these dyes contain azo groups of general Not only does this switch increase productivity, it also
formula: reduces energy consumption. A 2013 study by the Department
of Apparel Manufacturing Management and technology at
R-N=N-R’, with the R’s pertaining to arenes. Shanto Mariam Univeristy in Dhaka, Bangladesh compared the
These arenes destabilize the molecule’s system and in turn wet and dry methods and found the dry process to require only
stabilize the azo dye greatly. Unfortunately, it is this stability 20% of the wet method’s energy.10 Energy savings are primarily
that leads to both the longevity of these dyes in the a result of eliminating the wet dyeing’s drying step4 and the
environment and their success in the textile industry. The water pre and post dyeing steps (notably washing, scouring,
industry requires its dyes to withstand harsh conditions, bleaching and finishing steps10). These steps account for 100-
namely soap, bleach, water, high temperatures and light5, 145L of water on average per 1kg of textile material dyed. 10
making azo dyes an ideal option, as long as their toxicity and Energy use would also be reduced in terms of cleaning the
persistence are overlooked. Overlooking these two effects water of impurities at the beginning of the wet process and
however has shown great disruption in aquatic ecosystems. treating the wastewater at the end of it. The aforementioned
Primarily through the impediment of photosynthesis and process time reduction would also reduce the energy input per
oxygenation from the reduction of water transparency and the kg of dyed textile. This energy reduction would have an
negative health impacts from the carcinogenic, mutagenic and economic benefit for the dyer. A 2005 economic analysis of a
synergistic properties of certain dye components (i.e. azo dyes, 1000-L supercritical dyeing machine by the University of Delft
chlorine, heavy metals).5 in the Netherlands found that although an scCO2 machine
required an initial investment five times greater than that of an
aqueous machine, the scCO2 dyed 1 kg of polyester for 0.35€
while the aqueous dyed it for 0.9€.12 Over time, this difference
Considering the harmful environmental effects of this was found to have a 50% reduction in process costs for the
effluent, the textile industry must be held accountable for its scCO2 method compared to the wet process12. This supports
waste. One form of accountability has been seen in countries the viability of scCO2 textile dyeing as the initial investment in
that charge companies for their water supply and discharge. 7 the new technology can be offset by the significant energy
This has motivated them to modify their processes to reduce reduction as compared to the wet process.
their costs.7 However, this pricing does not encompass all of the
effects that the wastewater has on the environment and is
limited to certain countries. Based on this trend from putting a
price on the water and discharge, regulation on wastewater Economic benefits aside, this energy reduction has the added
discharged must be implemented in each country to push effect of reducing pollutant emissions from fossil fuel
industry to adopt waterless technology to remain competitive. dependent textile dyeing mills.10 Thus, a company that adopts
this technology will pay less to fuel its process as well as reduce
its CO2, nitrous oxide, and sulfurous dioxide emissions.7
THE WATERLESS SOLUTION
The textile industry’s problem of high water consumption The most notable way that this technology reduces the
and contamination can be eliminated with the elimination of textile industry’s environmental impact however is through the
water from the dyeing process. Switching from wet dyeing to removal of water from the process. A waterless process
dyeing with supercritical CO2 leads to an increase in both eliminates both the sector’s demand for clean water and its
productivity and energy savings4 and a reduced environmental discharge of wastewater into the environment. This
impact9 for the textile industry. contributes to ease the global strain for clean water as well as
prevent water pollution that intensifies this strain and harms
aquatic ecosystems. The use of scCO2 prevents pollution as a
result of successful dye separation from CO2 through
The increase in productivity is a result of scCO2’s chemical
depressurization at the end of the process.12This allows for easy
properties. Above critical point, CO2 has both liquid and gas
collection of the dye at the end of the process, as opposed to the
properties, allowing for hydrophobic dyes to dissolve into it. 10
wet process where dye separation from the wastewater is very
Paired with a low-viscosity and gas-like diffusion, dyeing with
difficult5. Further, it allows for CO2 recycling12, a process that
scCO2 has been shown to produce shorter dyeing times than
has been optimized to 90% recyclability7. Finally, the use of
wet dyeing.10 Additionally, chemicals and auxiliaries are
CO2 as the solvent for this process is environmentally
reduced4 as there is better dye diffusion in scCO2 and a more
favourable as it is nontoxic and nonflammable and its linear
even spreading of the dye than in water. This reduction is
structure and non-polarity classify it as an inert gas in many
further enhanced through the possible optimization11 of dye
conditions.4 With CO2 being a stable and well-studied
and CO2 compatibility. Stains from salts, notably calcium and
molecule, it is easier to work with than the hazardous and
magnesium, would be eliminated10 with the use of scCO2
variable wastewater from wet processes.
dyeing, once again increasing the productivity of the process by
eliminating the need of stain removal. There are also
temperature controllable dyes and density controllable dyes4
which increase productivity as they allow for the control on the
dye outcome through temperature and pressure changes.

THE PILOT PLANTS However, I argue that the first can be solved with strategic
price subsidies17 and the second is already in its developmental
Over the past 15 years successful pilot plants have emerged stage.7 First, the subsidies would make scCO2 dyeing
for supercritical CO2 textile dyeing across the globe. In 2000 technology available to the textile industry sooner than would
the North Carolina State University College of textiles started be possible without the program. Through the use of a strategic
up a pilot-plant machine that concluded that the scCO2 dyeing price subsidy program, the technology’s feasibility would be
process of polyester was technologically and economically taken into account and there would be a continuous
feasible.4 In 2008, an Italian pilot plant at the Polytechnic adjustment to competitive pricing.17 The combination of these
University of Turin produced scCO2 dyed polyester yarn two requirements would ensure the subsidy’s contribution to
bobbins with low crocking, high reproducibility and dye the new technology’s longevity in the industry. The second
evenness.6 It recorded an impressive dye process time of 1.5hrs, problem that of natural fibers not being compatible with
(compared to the conventional wet process’s 3-4hours) which scCO2 is only a temporary problem. Research is being
provided strong support for scCO2 dyeing’s potential to conducted at many sites that has improved natural fibers’
increase the textile industry’s productivity. Soon after, a dyeability. One notable example is the 100% dye fixation of
technical scale machine at the Delft University of Technology cotton using scCO2 dyeing technology in combination with
in the Netherlands reproduced short dye times (2hrs) as well fluorotriazine reactive dyes18. A further example is that of the
as even dyeing.12 This machine also showed final product fiber Delft University of Technology’s development of pretreatment
strength comparable to wet dyeing and 95% efficient recycling methods using methanol and modification of cosolvents that
of CO2.12 More recently, in 2014, the Soochow University also demonstrated an increase in dye fixation. Even though
College of Textile and Clothing Engineering developed a scCO2 dyeing of natural fibers is not yet ready to be
scCO2 rope dyeing pilot plant which produced commercially commercialized, it will benefit greatly from the
viable products with low crocking and high colour diffusivity.11 implementation of scCO2 dyeing infrastructure for polyester,
These successful plants are all indicators of scCo2 dyeing’s as the latter will facilitate the former’s entrance into the
commercial potential and realization of this technology’s pilot market. Thus, although these two problems are valid concerns
state. It is now time for regulation and subsidies to step in. for the adoption of the technology, neither is an irresolvable
impediment to its commercialization.
THE CURRENT COMMERCIALIZATION
The commercialization of scCO2 polyester dyeing has begun, CONCLUSION

and there is evidence of companies that have successfully To conclude, now is the time for supercritical CO2 polyester
upscaled this technology and introduced it into the textile dyeing technology to be upscaled and commercialized in the
dyeing market. The current spearheading company in this textile industry. Regulation and subsidies are critical to this
commercialization is DyeCoo Textile Systems7. The Dutch commercialization as the technology has been developed and
company has patented its method of scCO2 dyeing13, and the pilot and large scale plants implemented with successful
signed contracts with major companies such as Nike and results. The current rate of textile wastewater discharge is
Adidas14. Further, it boasts the ability to bring dyeing to water hazardous for both the environment and society as clean water
scarce environments14, which could open up the world becomes increasingly scarce. If the textile industry is truly
geographically to the dyeing industry. In collaboration with focused on sustainable manufacturing, as stated in their goals
DyeCoo, the Yeh Group - a Thai textile company specializing for this year’s World Textile Summit19, it is crucial that it
in performance polyester - has now implemented commercial- implements supercritical CO2 polyester dyeing at once.
scale scCO2 machine in its mills7. As a result, it is now branding
AUTHOR INFORMATION
its fabrics as DryDye™ fabrics15, which are consequently
distributed around the world with the DryDye™ certification. Irene Carrasco
These two companies are examples of the feasibility of
commercializing scCO2 technology in the textile industry. In [email protected]
addition to these companies, there are also manufacturers that
wish to shift to scCO2 technology with alternative options. ABBREVIATIONS
Applied Separations, a US manufacturer of supercritical scCO2, supercritical carbon dioxide
systems works together with companies that wish to develop
their own scCO2 equipment. It has developed scCO2 polyester REFERENCES
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scCO2 polyester dyeing technology; subsequently supporting major problems of the 21st century? . Ecological Engineering
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Agricultural Water Management 2006, 80 (1-3), 18; (b) Taylor,
R., Hydrology: When wells run dry. Nature 2014, 516
THE CRITICS
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Maria Boldrin, Danielle Palma de Oliveira Textile Dyes: Geert-Jan Witkamp. Design and Performance of a
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of Textiles - From the Laboratory Apparatus to the Pilot Dyeing a Substrate with a Reactive Dyestuff in
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A Super-Critical Review of Supercritical Fluids: Can SCF’s Replace
Traditional Solvents?
Charles J. F. Cole
KEYWORDS: Supercritical Fluids, Analytical techniques, Pharmaceuticals, Waste Treatment, Traditional Solvents, Organic Solvents
ABSTRACT: Recently, a great deal of attention has been directed towards finding alternatives to traditional solvents. The chemical
industry, as a whole, relies heavily on solvents, which has contributed to the large volume of solvent related waste produced to date.
This waste is not only toxic to humans but can cause adverse effects to the surrounding environment and ecosystems and as such a
substitute is required. Some of the proposed ideas include solid state reactions, greener solvents and alternative solvent systems.
This article focuses on supercritical fluids (SCF’s) as an alternative solvent system. The applications and advantages of these solvents
are analyzed to determine whether or not SCF’s are a viable replacement to the traditional solvents. SCF’s are extremely versatile
and have great environmental benefits relative to traditional organic solvents, however the use of these solvents is not widespread
nor are they sufficiently developed to feasibly replace solvents used today. Regardless, SCF’s present an area into which certain
solvent uses can be diverted in order to mitigate the environmental effects of the current situation while searching for a more
practical replacement.
INTRODUCTION necessary and in some cases may hinder optimal reaction

conditions. In addition, the replacement of these traditional
Presently, solvents occupy most of the focus in the realm of systems can eliminate the vast amount of solvent related waste.
green chemistry, whether it be optimizing solid-state For example, in pharmaceutical manufacturing alone, solvents
reactions, investigating ways to recycle solvent waste or make up 80 % of the raw materials used in the process and this
conducting research on greener solvent systems. Motivating is only expected to increase [1]. Solvents are commonly
this work is the realization that while solvents play crucial employed for their benefits such as mass transfer, heat transfer,
roles in various chemical reactions they are not always

dilution of reagents to ensure selectivity and potential characteristics [3 – 5]. This property is well known and
stabilization of transition states. successive extractions of different compounds using the same
SCF have been reported previously. One such example is VOC’s
The environmental impact from solvent waste of chemical found within urban air particulates. When the extraction
industries underscores the current need to find “greener” and process is performed using ScCO2 at constant temperature,
more sustainable alternatives. Supercritical fluids (SCF’s) are alkanes can be extracted at 75 atm while polyaromatic
one of the many green solvents which have received a fair hydrocarbons (PAH’s) remain in the sample matrix until the
amount of attention in the past 20 – 30 years. As a result, several pressure is increased to 300 atm [6]. Further examples of
published works have investigated the properties and uses of tunable solvating character are present in ScCO2 which, at low
these solvents. Supercritical fluid is a term that refers to a pressure favours less polar analytes and at higher pressure will
substance exposed to temperatures and pressures above the favour more polar and higher molecular weight analytes [5].
corresponding critical point. There are a number of commonly Therefore, as opposed to traditional extractions in which
studied SCF’s including: carbon dioxide (ScCO2), water multiple solvents must be employed in order to extract all
(ScH2O), propane (ScC3H8), methanol (ScCH3OH) and nitrous desired products, SCF’s present a convenient way to remove
oxide (ScN2O) among others. Of these, ScCO2, is the most multiple products without changing the solvent but rather
commonly used, this is because of its critical pressure (73 atm) changing the physical conditions [3]. Once the analyte has been
and critical temperature (approximately 31˚C) [2]. Most SCF’s extracted, the SCF is removed by simply bringing the sample to
have very little environmental impact and are non-toxic, non- ambient pressure. On the other hand, with liquid-liquid
flammable and relatively cheap, making these solvents a great extractions, the analyte would then have to be concentrated,
potential alternative to the systems already in place. This resulting in increased energy usage and labour to obtain the
review seeks to present some of the applications of SCF’s in desired product as well as potential degradation of the product,
order to assess their efficacy as replacements to traditional which could take place in cases of lengthy concentration steps
solvents. [3]. In the case of thermally sensitive products, SCF’s are a good
alternative to traditional solvents as some of them have critical
temperatures below 40˚C [3].
ANALYTICAL APPLICATIONS
Most of the advantages previously discussed carry over to
SCF’s are used in two main analytical techniques Supercritical Fluid Chromatography (SFC), since
Supercritical Fluid Extraction (SFE) and Supercritical Fluid chromatography generally relies on the partitioning of the
Chromatography (SFC). SCF’s offer great benefits to the desired analyte between the mobile phase (SCF) and the
aforementioned techniques as a result of their tuneable solvent stationary phase. Hence, the ability to alter the solvating
properties. The process of liquid extraction can be adapted to properties of SCF’s with changes in temperature and pressure
accommodate SCF’s and is relatively simple to perform. A offers numerous advantages to SFC. ScCO2, is a commonly used
pump is used to produce a given pressure of extraction fluid supercritical fluid for SFC because of its low critical
that is transferred to a temperature-controlled container which temperature, which allows for the separation of thermally
remains above the critical temperature of the solvent of interest labile compounds [7], [8]. However, a challenge arises when
[3], [4]. The analyte of interest is then added to the SCF. trying to separate polar analytes since at lower pressures
Following this the extracted product and residual SCF are ScCO2 shows minimal solvating power for polar compounds.
removed and sent to a collection vessel that is held at ambient This is overcome by adding a small amount of modifier to the
pressure. Once the mixture is transferred the SCF then quickly sample, such as methanol (5 – 30 %), which increases the
converts to its gaseous form leaving only the desired products. polarity of the SCF. Therefore, it works best with compounds
The use of SCF’s offers multiple benefits, one being that above of low polarity but can be adapted to those of moderately high
the critical point a solvent will exhibit characteristics of both a polarity if necessary. In addition, the mild operating conditions
gas and a liquid [5]. For instance, the gaseous nature of SCF’s used in SFC, with ScCO2 as the mobile phase, allows it to be
leads to an increase in mass transfer of the solvent. This easily adapted to liquid chromatography (LC) and Gas
increase is due to the lower viscosity and larger diffusivity Chromatography (GC) instrumentation [8]. There has even
observed in SCF’s [3]. As a result of the reduction in mass been reported coupling of SFC to spectroscopic methods
transfer limitations, extractions performed using SCF’s often including UV/Vis, FTIR, MS and 1H NMR [8 - 13]. Although the
result in less time required to complete the process as use of SFC might seem limited due to the restricted solvating
compared to liquid extractions. For instance, common SFE’s characteristics of ScCO2, it has already been employed for the
can take place in 10 – 60 minutes while, a traditional liquid separation of many different compounds such as highly polar
extraction can take up to several days [3], [5]. A comparative antibiotics, natural products such as sterols, terpenes, fatty
study was performed in which PAH’s were extracted from an acids and cannabinoids and is even used in chiral separations
adsorbent material using both SFE and a traditional extraction of enantiomeric compounds [7], [8], [14]. Furthermore, this
method. The results indicated that both methods offered the method can offer advantages over traditional chromatographic
same extraction efficiencies, but SFE showed a decreased techniques like the ability to separate mixtures at lower
extraction time [5]. Furthermore, the solvent properties of temperatures than GC and in shorter periods of time than LC
SCF’s can be varied greatly by small changes in temperature [8]. Moreover, the methods associated with SFC are quite
and pressure allowing multiple extractions to be performed diverse with both capillary SFC (cSFC) and packed column
using one given solvent. Above the critical point of a given SFC (pSFC) having already been developed [14].
substance, small changes in the pressure cause significant
changes in the density, accounting for the adjustable solvent

The examples presented above are not the only analytical solvent that is miscible with most gases such as O2 and
applications of SCF’s. Research has shown that SCF’s can be promotes the rapid oxidation of the waste water [22]. Other
used in tandem with electrochemical and gravimetric methods materials contained in the waste stream, like inorganic salts,
among others [3]. Unfortunately, the implementation of many remain insoluble and can be precipitated out of the solution
of these techniques is limited by the high costs required for and collected separately [23]. The efficiency of this process can
slightly modified equipment [15]. However, the examples reach values of up to 99 % with a process time of under 10
outlined present the versatile nature of this solvent and seconds. Furthermore, this pathway offers the additional
highlights both the benefits and drawbacks of replacing advantage of destroying hazardous waste and separating
traditional solvents in analytical applications with SCF’s. inorganics in a single reactor [23]. Additionally, this process
does not allow for the production of other common air
pollutants, such as NOx and SO2, which would otherwise be
PHARMACEUTICAL APPLICATIONS formed in the incineration of such waste [22], [23]. The
configuration commonly used is a pipe reactor however this
As previously indicated, supercritical fluid chromatography type of reactor has the disadvantage of plugging if the waste
is a widely studied technique. Moreover, it has been used in stream, once treated, produces a large amount of inorganic salts
pharmaceutical research in order to separate a wide variety of [23]. However, there have been patents put forward to handle
compounds, including enantiomers, where research has shown this problem, wherein the reactor contains two zones, one in
that through the use of SFC, better resolution of chiral which the SCF is contained and a second zone containing cold
compounds can be obtained as opposed to other HPLC water at the same pressure as the ScH2O. The reactor operates
methodologies [15]. Besides the use of SCF’s to purify as follows; as the organic waste is oxidized the corresponding
compounds, these solvents can also be used in the synthesis of gaseous products are vented from the top of the reactor, while
certain drugs in order to improve the delivery of the compound. the solid materials produced will sink into the cold water layer.
The most common methods are Solution Enhanced Dispersion Constant stirring is maintained in this layer to form a slurry
by Supercritical fluids (SEDS) and Rapid Expansion of that can then be easily removed [23]. Yet there have been
Supercritical Solutions (RESS). The former uses an SCF to act difficulties in fully optimizing this process due to the corrosive
as an antisolvent to precipitate the material, while the in the nature of ScH2O and the by products of SCWO which
latter the SCF rapidly expands, due to a pressure difference eventually lead to the degradation of the reactor vessel.
which causes the dissolved material to precipitate out of Nevertheless, active research is being conducted to bring
solution very quickly as small particles. In both of these SCWO to an industrial scale [22], [23].
techniques, the material of interest is introduced to the SCF,
commonly ScCO2, at a high pressure in order to produce SCF’s also show promise in the production of chemically
ultrafine particles. This is mostly used to increase the recycled plastics. Recently, significant focus has been placed on
bioavailability of such drugs by reducing the particle size and plastic recycling due to the realization that the degradation of
increasing the surface area [17 - 20]. Additional advantages such plastics is almost impossible under normal biotic and
include; high purity product, control over particle morphism abiotic conditions. This has lead to problems such as landfill
and ability to process thermally sensitive compounds. overflow and the Great Gyre Problem. There have been some
Furthermore, for this process, the use of ScCO2 in place of attempts to find alternatives to the current products used, such
traditional organic solvents offers fundamental environmental as PLA a polymer which is biodegradable under certain
benefits [18]. Like the previous methods described, the use of conditions. However, no definite solution has been found.
ScCO2 allows this process to be conducted under mild Another area of research within this field is the chemical
conditions while producing crystals that are solvent free and degradation of plastics by SCF’s. By combining certain
require no added surfactants [16]. Additionally, traditional polymers with SCF’s it is possible to depolymerize them to the
methods of crystal formation such as spray drying, milling, corresponding monomers quicker and in a more selective
lyophilisation and controlled precipitation can cause particle manner than traditional methods. The monomers obtained are
size inhomogeneity, low yields and temperature induced of decent quality such that they can be recycled [24], [25].
protein inactivation, all of which are undesirable Condensation polymers can be depolymerized by solvolysis
characteristics in sustainable processing methods [16]. Thus, using supercritical water or alcohol. Previous research has
SCF’s can offer more than a medium in which one can conduct shown that complete depolymerization of PET to monomer
reactions, they can also aid in particle size alteration in order to sized units can take place in ScCH3OH in a short time span of
increase bioavailability of a given drug. 1200 seconds without a catalyst, [24 - 28]. Addition polymers,
like resins commonly found in electronics, are constructed out
of materials such as phenols which have a high thermal
WASTE TREATMENT stability. When combined with ScH2O and a slight Na2CO3
SCF’s can also be applied in the field of waste treatment. modifier, these materials can be decomposed into the
ScH2O can be used to treat organic waste by oxidizing it to corresponding monomers in as short a period of time as 30
produce CO2, H2O and N2 in a process referred to as minutes with yields reaching 90 % [24], [25].
Supercritical Water Oxidation (SCWO) [21]. The process is
carried out at 600 ˚C and 23 MPa, at which point most organic
compounds become soluble in ScH2O. This change in solubility ROLES OF SCF’S IN CHEMICAL REACTIONS
is due to the decrease in dielectric constant and ionic product
of the solvent [22]. As a result, ScH2O acts as a non-polar SCF’s, because of their versatile nature, have been studied in
various reactions either as the solvent medium or as actively

participating in the reaction. By altering certain properties, hydrogenation reaction, the reaction rate for hydroformylation
such as the density, pressure, dielectric constant etc., it is is not greatly altered when carried out in SCF’s since the
possible to increase the reaction rate, yield and selectivity [28]. reaction is homogeneous when carried out in organic solvents.
In fact, previous literature presents the study of SCF’s in many However, there have been observed increases in catalytic
well-known chemical reactions [29]. Hence, the ability to tune selectivity when conducting the reaction in SCF’s such that the
the chemical properties of these solvents by altering the desired product is obtained in higher yields [29], [30], [32].
physical conditions presents certain experimental
consideration that should be taken into account. Changes in Oxidation: There have also been many studies where SCF’s are
the pressure under which the SCF is contained can impact the used in oxidation reactions, some of which have yielded certain
density of the fluid immensely and consequently, the solvating heterogeneous catalyzed reactions such as the steel catalyzed
ability of said fluid. Through the use of SCF’s it may be possible oxidation of cumene, the CoO catalyzed oxidation of toluene
to carry out traditionally heterogeneous reactions in the or supercritical water oxidation as previously discussed [30].
homogeneous state. One example of this is reactions which The benefit here, similar to the previous examples, is the
involve polymeric substrates that experience rate limitations miscibility of O2 with most SCF’s allowing for greater mass
when conducted heterogeneously. In addition, it is necessary transfer [29], [33]. Some studies have been performed on
to consider the temperature under which the reaction will be homogeneous oxidation reactions with SCF’s such as
carried out. For instance, lower temperatures will cause the epoxidation reactions that can afford enantioselective
reaction rates to decrease while higher temperatures may cause products in the presence of specific catalysts, sulfoxidation
catalytic decomposition [30]. In the case of pyrolysis, it is reactions where the use of an SCF promotes
observed that conducting the reaction at lower temperatures diastereoselectivity and even oxidation of alkanes to produce
can reduce unwanted by-products and has been shown to functionalized molecules, such as the conversion of
increase yield, selectivity and product separation [28]. cyclohexane to cyclohexanone albeit in lower yields [29], [30],
Furthermore, it is necessary to consider the reactive nature of [32]. Another interesting application of SCF’s, with respect to
the SCF being employed. One consequence of using SCF’s in oxidation, is the use of partial oxidation. Methane has been
chemical synthesis is that these solvents ca partake in the studied as a potential fuel source, however there are challenges
reaction under certain conditions. However, this property is associated with the storage and transport of this material.
actually utilized in certain reactions such as the hydrogenation Partial oxidation of methane yields methanol and other higher
of CO2 to produce common organic molecules, such as order hydrocarbons, which are easier to transport and store.
formaldehyde. Of the many reactions that have been studied in Unfortunately, this reaction is yet to be optimized and shows
SCF’s, three of the most well-known are presented below. very poor yields [31]. In addition to the synthetic pathways
These are: hydrogenation, hydroformylation and oxidation. described above, there has also been research invested into the
use of SCF’s to increase total aerobic oxidation of organics [29].
Hydrogenation: The rate of many hydrogenation reactions is
dependent on the concentration of hydrogen in solution as well Although not explicitly discussed herein, there are a vast
as the diffusion of H2 once dissolved. However, this is limited number of reactions in which SCF’s have been substituted in
by the immiscibility of H2 in many organic solvents [31]. order to observe the impact on reaction rates, selectivity, yield
Because of the miscible nature of SCF’s with certain gases, it is etc. As presented, it is clear that in some cases it is largely
possible to significantly increase the concentration of hydrogen beneficial to employ SCF’s in place of the traditional solvents
in solution. Furthermore, the increased diffusivity present in not only for their environmental benefits, but also for their
most SCF’s allows the reaction to proceed at significantly potential to improve the metrics associated with the reaction
increased rates [30 - 32]. Previous studies have shown that this of interest.
increase in rate lies exclusively with the increase in hydrogen CONCLUSION
concentration as catalytic activity is not shown to increase
when the reaction is carried out in SCF’s [32]. Moreover, SCF’s Solvent use contributes tremendously to the environmental
have been advantageous in the production of many impact of most chemical industries. Solvents are used in the
hydrogenation products including, fats and oils, small organic pharmaceutical industry, automotive industry, textiles, dry
compounds and enantioselective products. Considering that cleaning, paints, plastics, rubbers etc. However, it is clear that
the conversion of vegetable oils into saturated fats is a huge simply halting the production of solvents would do more harm
industry, using SCF’s would be greatly advantageous. The than good. Therefore, it is necessary to find some alternatives
widespread use of SCF’s would initially result in the to the traditional methods used, whether greener solvents are
replacement of traditional solvents and ultimately a large introduced, solvents are removed from the process altogether
reduction in the environmental impact caused by such solvents or alternative solvent systems are adopted. The many
[31]. Hence, the ability to replace the current solvents with applications previously presented indicate that there is a
ScCO2, which is non-flammable, non-toxic and possibility for SCF’s to replace traditional solvents in some
environmentally benign would present many “green” benefits aspects. More specifically, the use of SCF’s as the mobile phase
[31], [33]. in some common analytic techniques, the potential use of SCF’s
in the pharmaceutical industry, the ability to treat waste using
Hydroformylation: This process is very similar to SCF’s or substituting SCF’s in well-known reactions all in an
hydrogenation in that it traditionally uses liquid solvents, attempt to replace the solvents traditionally used.
gaseous reagents and a solid catalyst and presents great Unfortunately, there are several applications where it is not
industrial importance as the products of this reaction go onto feasible to simply replace the solvent with a SCF. Therefore,
many secondary applications [30], [33]. Unlike the SCF’s can clearly offer a replacement to traditional solvents in

many aspects and in these cases it would be greatly beneficial 12. Fischer, H.; Gyllenhaal, O.; Vessman, J.; Albert, K.,
to replace the solvents. However, SCF’s cannot completely Reaction monitoring of aliphatic amines in supercritical
substitute the solvents used today and solve the current crises. carbon dioxide by proton nuclear magnetic resonance
spectroscopy and implications for supercritical fluid
SCF’s offer an environmentally friendly transition state, during
chromatography. Analytical chemistry 2003, 75 (3), 622-626.
which a greener and more viable alternative can be sought.
13. Lang, Q.; Wai, C. M., Supercritical fluid extraction in
herbal and natural product studies—a practical review.
AUTHOR INFORMATION Talanta 2001, 53 (4), 771-782.
Corresponding Author 14. Yaku, K.; Morishita, F., Separation of drugs by packed-
column supercritical fluid chromatography. Journal of
Charles J. F. Cole, Department of Chemistry, McGill University
biochemical and biophysical methods 2000, 43 (1), 59-76.
ACKNOWLEDGMENT 15. Maftouh, M.; Granier-Loyaux, C.; Chavana, E.; Marini, J.;
Pradines, A.; Vander Heyden, Y.; Picard, C., Screening
The author wishes to thank Prof. Robin D. Rodgers and Prof. approach for chiral separation of pharmaceuticals: Part III.
Audrey Moores for their extensive help in the construction of this Supercritical fluid chromatography for analysis and
article as well as the McGill Green Chemistry Journal Editorial purification in drug discovery. Journal of Chromatography A
Board for assistance in the layout and publishing of this article.
2005, 1088 (1), 67-81.
16. Debenedetti, P. G.; Tom, J. W.; Sang-Do, Y.; Gio-Bin, L.,
ABBREVIATIONS Application of supercritical fluids for the production of
SCF, Supercritical Fluid; ScH2O, Supercritical Water; ScCO2, sustained delivery devices. Journal of Controlled Release 1993,
Supercritical Carbon Dioxide; SCWO, Supercritical Water 24 (1), 27-44.
Oxidation; Polyaromatic Hydrocarbons, PAH; Supercritical Fluid 17. Blagden, N.; De Matas, M.; Gavan, P.; York, P., Crystal
Extraction, SFE; Supercritical Fluid Chromatography, SFC; engineering of active pharmaceutical ingredients to
Volatile Organic Compounds, VOC’s; Mass Spectrometry, MS; improve solubility and dissolution rates. Advanced drug
Fourier Transform Infrared Spectroscopy, FTIR; Proton Nuclear
delivery reviews 2007, 59 (7), 617-630.
Magnetic Resonance, 1H NMR; Solution Enhanced Dispersion 18. Fages, J.; Lochard, H.; Letourneau, J.-J.; Sauceau, M.;
by Supercritical fluids, SEDS; Rapid Expansion of Supercritical Rodier, E., Particle generation for pharmaceutical
Solutions, RESS; High Performance Liquid Chromatography, applications using supercritical fluid technology. Powder
HPLC; Polylactic Acid, PLA. Technology 2004, 141 (3), 219-226.
19. Soppimath, K. S.; Aminabhavi, T. M.; Kulkarni, A. R.;
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Carbon Dioxide Copolymerization: How Green Is It?

Rebecca O’Leary
KEYWORDS Copolymerization; Carbon Dioxide; Epoxides; Catalysts; Polycarbonates; Organometallic Complexes
ABSTRACT: Carbon dioxide is one of the most abundant carbon resources available, however its activation and subsequent
utilization, is a difficult process. In recent years, this field has been of great interest since carbon dioxide is one greenhouse gas
contributing to climate change. The intent of this article is to present 3 case studies of specific methods of catalysis used in carbon
dioxide copolymerization, in order to evaluate the “greenness” of each method. The various catalysts are synthesized with slightly
different priorities in mind, so each method will be evaluated to see if these priorities align with the principles of green chemistry.
The chosen catalytic systems presented in each case study are a β-diiminate zinc catalyst, an Iron catalyst, and a Palladium catalyst.
Not only will the characteristics of the products be examined, but also the renewability of the starting materials and the catalyst.
The need to find alternative feedstocks for creating copolymers, as well as catalysts with high activity at mild conditions, is of great
concern if the field wants to reach a green standard. Highlighted overall is the need to be conscious of all aspects of a process in
order to achieve sustainable methods.
INTRODUCTION

Carbon Dioxide (CO2) copolymerization was originally Looking at the source of the starting material will assess the
designed to be a green technique due to its use of the renewability of the reagents. If the production of the reagents
greenhouse gas, CO2, as a reactant. CO2 is a cost effective, non- requires large amounts of energy, or is a long process that
toxic, and abundant reagent.2 Using it to create polycarbonates produces other wastes, this does not embody the ideas of green
has been a process of great interest, since polycarbonate-based chemistry.13 Energy efficiency, waste prevention and use of
plastics can have many desirable properties, such as high renewable feedstocks are green chemistry principles13 that
transparency and UV stability3 and polycarbonates have many should be considered when choosing reagents.
lucrative applications in food and drink containers, household The same factors will influence the factor of the renewability
appliance parts, components of electronic devices, reusable of the catalyst. If the catalyst is made from abundant starting
bottles, and many other products.3 Polymers provide a method materials and its synthesis is not an energy intensive process,
of recycling the carbon dioxide into products we need. green standards are likely to be met.
The general pathway shown in scheme 1 depicts the two Finally, the biodegradability of final product will be taken
possible products that can be obtained. The top product, a into account. Biodegradable polymers are designed to degrade
cyclic carbonate is the kinetic product, while the bottom in the presence of the action of living organisms. 14 A common
product, an aliphatic polycarbonate is the thermodynamic example of a biodegradable polymer is poly(lactic) acid.14
product.4 Pioneering work on this process was performed by S.
Inoue and colleagues who, in 1969, discovered that CO2 and Methods to be analyzed will include the use of β-diiminate
propylene oxide can copolymerize in the presence of diethyl zinc catalysts to produce biodegradable polymers,15 catalysts
Zinc in water to produce polycarbonates.5 Since this discovery, using iron, a more sustainable metal,16 and a novel palladium
there have been numerous catalysts synthesized for the catalyst that employs butadiene instead of epoxides in the
copolymerization of carbon dioxide. The majority of these copolymerization process.1 Each method was chosen based on
catalysts are organometallic compounds.6 The ligands have a different “green” factor specific to each process.
been varied over the years to examine how sterics or chirality7 β-diiminate (BDI) zinc catalysts were chosen for this case
of the catalyst can influence copolymerization. More recently, study due to the ability to produce biodegradable polymers.15
the “greenness” of the process has been called into question. Approximately 150 million tons of plastics are produced every
The amount of carbon dioxide actually consumed can trivial.6 year, and the majority of those are non-biodegradable and are
The impact the copolymerization of atmospheric CO2 would manufactured using energy intensive processes, often using
have on global emissions is minimal.8 However CO2 is a waste petroleum-based starting materials.8 Thus to reduce the
product of many processes,9 thus utilization of emitted CO2 amount of waste plastics, the biodegradability of the
would be a way to valorize this waste. copolymer is of great importance. The zinc catalyst chosen
There are several obstacles in the entire process that need to embodied this trait.
be solved. The source of this carbon dioxide is not necessarily An iron catalyst was considered since Iron is one of the most
green either. Existing processes are very energy intensive.10 abundant metals in Earth’s upper crust.17 This catalyst also
Thus the capture of waste CO2 is an active field of research shows activity at atmospheric pressure, which has a lower
currently. There are pilot projects in the works, however it is energy demand than those processes requiring elevated
by no means a simple process.10 Carbon dioxide waste needs to pressures.17 Iron’s accessibility and potential to reduce energy
be scrubbed (or stripped out), purified, and concentrated costs makes it a green option for this process
before it can be stored for use.11 So depending on the reactants, Finally, the use of conjugated dienes with a palladium
the final polymer product may not be a particularly green or a catalyst was chosen to contrast the other methods of catalysis
sustainable product. since it uses a precious metal, as well as a diene as a starting
material.1 The use of a precious metal is not a green choice.
However, the use of a conjugated diene allows the elimination
of the epoxidation step. With the elimination of a step, energy
is saved and the waste from that particular step can be
reduced.8 Both the pros and cons of this method are to be
evaluated, in order to decide how green this catalysis really is.
Β-diiminate Zinc Catalysts. Since the first catalyst discovered

for copolymerization was a zinc diethyl complex,5 the most
traditional of the catalysis methods analyzed is the use of a β-
diiminate zinc catalyst, (Figure 1). In particular D. Moore and
co-workers, synthesized highly active zinc catalysts to produce
Scheme 1. General Copolymerization Reaction4 to yield biodegradable polymers, specifically heterotactic and
either a cyclic carbonate (top product) or a polycarbonate syndiotactic poly(lactic) acid.18 Using bulky β-diiminate
with possible ether linkages. ligands, each containing two nitrogen atoms, and a zinc atom,
In order to illustrate the vast differences of catalysis in this these compounds have achieved narrow polydispersity indices
field, three current methods will be evaluated using four (PDI) where PDI = 1.10 – 1.16. The rate of reaction can be
different qualities. The first will be the amount of CO2 manipulated via ligand choice and configuration.15 The
incorporated into the final copolymer by analysis of carbonate polydispersity of a polymer corresponds to the uniformity of
linkage % The carbonate linkage percentage will be calculated the polymer length, this is important for the commercial or
using the following equation.12 industrial processes downstream from the production. The
(copolymer carbonate linkages) narrower the polydispersity index, the more desirable the
% Carbonate= (copolymer (1) product for consumers and the more likely this process could
carbonate + ether linkages)
eventually be commercialized. Interestingly, this catalyst
seems to be the most effective when it forms a loosely

associated dimer complex.15 This mechanistic aspect has
influenced more recent research of M. Kember and colleagues
to synthesize dizinc catalysts, that have been found to be highly
active at atmospheric pressure19 and maintained a high
percentage (>99%) of carbonate linkages at lower pressure. 19
Figure 2. Comparison of epoxides used, (2a) Cyclohexene

Oxide. (2b) Propylene Oxide. (2c) Limonene Oxide.
This is an advantageous alternative since limonene is one of
the most common terpenes, and is produced by over 300
different plants.23 Limonene and carbon dioxide copolymers are
biodegradable and can be synthesized under mild conditions.23
In comparison with the β-diiminate zinc catalysts made by D.
Moore and co-workers18, the dizinc catalysts synthesized by M.
Kember and colleagues19 embody the previously mentioned
green qualities but remain active at lower pressures, with
comparable turnover numbers (TON) and turnover
frequencies (TOF).19 This is advantageous due to the reduced
energy input of the reaction.19 The copolymers of Kember’s
dimetallic catalyst maintain the high percentages (>99 %) of
Figure 1. Loosely associated dimer of the β-diiminate zinc carbonate linkages, and ether linkages were not detected.19
catalyst.15 This is the most active form of the catalyst. Ether linkages would indicate polymerization without the
incorporation of carbon dioxide so it is important that these are
If this process were to be commercialized, the process would minimized to have maximal CO2 consumption.6
need to be reevaluated from a green perspective. As mentioned
before, carbon dioxide copolymerization is often labeled green Iron Catalysis, a Sustainable Metal Choice. Iron is one of the
on the sole basis that carbon dioxide is consumed. A carbonate most abundant metals on Earth. It has a low toxicity, and is
linkage in the polymer signifies the incorporation of a carbon necessary for metabolic processes in many animals, plants, and
dioxide molecule since the epoxide itself will not create a microorganisms.24 Its abundance in nature makes for a cost-
carbonyl moiety in the polymer chain. In the absence of carbon effective, environmentally friendly green choice.17 With these
dioxide, the catalyst may catalyze the formation of an ether qualities known, somehow Iron seemed to slip under the radar
bond between subsequent epoxide molecules.12 For β- of the majority of research in copolymerization catalysts until
diiminate zinc catalysts, the copolymerization with relatively recent years. The first report of a highly active Iron
cyclohexane oxide (CHO), Coates and co-workers reported a catalyst for carbon dioxide copolymerization was in 2011 by A.
high percentage of carbonate linkages.15 Most of the BDI zinc Buchard and colleagues.12 This group created a bimetallic iron
complexes produced polymers with 94 % – 99 % carbonate (III) catalyst that showed notable activity with CHO at
linkages.15 Zinc is an abundant, cost-effective and sustainable atmospheric pressure.12 Creating an active catalyst at lower
metal.20 Therefore, this choice abides by the green principle CO2 pressures reduces the energy consumption of the entire
stating to use renewable feedstocks.13 Also to be considered is process.12 This bi-metallic catalyst demonstrated a narrow
the renewability of the reagents. As previously described, polydispersity index of 1.13.12 Two years later, the first iron
carbon dioxide is abundant, cheap, and in excess on our planet catalyst able to effectively copolymerize CO2 and propylene
although issues are presented in its capture and storage.10 oxide (PO) was reported by K. Nakano and co-workers,16 using
However, the epoxide, cyclohexene oxide (CHO) or propylene iron-corrole complexes (figure 3). Using this complex,
oxide (PO), with which the CO2 copolymerizes, is much less crystalline copolymers were observed.16 Varying the degree of
sustainable. These traditional choices are derived from crystallinity can change the mechanical properties of the
petrochemicals, such as cyclohexene and propylene, which polymer, although too high crystallinity will cause the polymer
undergo industrial epoxidation using heterogeneous to become brittle.25 It is important to be able to control this
catalysis.21 While technically petrochemicals are renewable, it factor in order to obtain the desired final product. The fact that
is estimated that they will be depleted or become uneconomical this catalyst can increase the crystallinity is significant because
within the next century.12 The development of an it allows for manipulation of mechanical qualities in the final
environmentally benign catalytic system for olefin epoxidation product, which would be appealing for commercial use.26
is still a challenging endeavor in the field.22 Crystalline polymers are desirable for use as gas-barrier films in
However, there has been successful work using BDI zinc food, medicine, and electronics packaging.26 While quite
catalysts to copolymerize limonene, a naturally occurring effective at 10 atm pressure, this bimetallic iron (III) catalyst
cyclic monoterpene, with similarities to CHO.23 (Figure 2) was not as effective at lower CO2 pressures.12

CO2,1 thus comparable to the 94 – 99 % carbonate linkages
reported in copolymerization reactions with CHO and PO.12, 15-
16, 19 It also boasts a narrow polydispersity index of 1.6, along
with a high yield and high selectivity.
Figure 3. Example of a Simple Iron-Corrole Catalyst.16

For iron catalysts, a major green aspect is the availability,
abundance, and low cost16 of the catalytic metal centre. It is also
environmentally benign16 in the case of contamination or
industrial accident. The diiron catalyst has demonstrated Figure 4. Polymer created via lactone polymerization.1
activity at atmospheric pressure, however this copolymer was
of sub-optimal standards with only 66% carbonate linkages.12. However, the metal catalyst used to activate the carbon
If the pressure was increased to 10 atm, the result was a dioxide to react with the butadiene is made of palladium.
dramatic improvement on the quality of the polymer with Palladium is a precious metal, so it is expensive and not a
greater than 99% carbonate linkages, and only trace amounts renewable resource.29 The catalyst loading of palladium/diene
of a cyclic carbonate by-product.12 This indicates that quality is 1:750 in effective experiments.1 While organometallic
polymers can be synthesized using a diiron catalyst, however catalysts, such as the dizinc catalyst discussed, obtained
changes need to be made before atmospheric pressure successful results with a lower catalyst loading of dizinc
copolymerization will be effective. The iron-corrole catalyst catalyst/CHO of 1:1000.19 It should also be noted that short
for CO2 copolymerization with PO did not incorporate notable alkenes used in this process, such as butadiene and isoprene,
amounts of CO2, the greatest carbonate linkage % found to be are petroleum based and generally derived from by-products in
62%, at increased pressure.16 Although, the iron-corrole oil refining.30 Butadiene is produced specifically from steam
catalyst reported by K. Nakano and colleagues was the first to cracking, an energy intensive oil-refining process.30 Therefore,
be able to catalyze the copolymerization reaction with these unsaturated alkenes are not a sustainable alternative to
propylene oxide,16 there are still improvements to be made epoxides.30 Although, this method produced polymers with
before this catalyst can be active at atmospheric pressure. comparable carbon dioxide incorporation to the zinc and iron
methods, the high price and rarity of Palladium, along with the
extra step in the copolymerization process, are not green
Use of Alkenes in Place of Epoxides via Palladium Catalysis. choices. In addition to the non-renewable sources of
The majority of copolymerization reactions involve carbon conjugated dienes, the starting material, and the non-
dioxide and an epoxide, a fairly reactive species due to ring biodegradability of the final copolymer, one cannot justify
strain.23 Starting with an alkene eliminates the synthetic step deeming this process ‘green.’
of adding the epoxide across the double bond.8 In 1975,
attempts at copolymerization reactions with butadiene and
carbon dioxide were reported.27 However, only oligomers with
low molecular weight could be achieved.27 In 1983, the
activation of carbon dioxide to create lactones was studied, 28
but this process was not expanded past the synthesis of
lactones. These results left each method relatively untouched
for decades. Neither the CO2 copolymerization of butadiene, or
the CO2 utilization to create lactones were connected until R.
Nakano and co-workers, developed the novel idea of creating a
metastable lactone for subsequent copolymerization.1
Scheme 2. First reaction in the process to obtain the lactone

intermediate before subsequent copolymerization.1
Although the copolymerization reaction between carbon
dioxide and butadiene has finally created polymers of desirable
qualities, is this process actually green? One major pro for this
process is that it incorporates up to 33 mol% of CO2, which is
comparable to the theoretical maximum.1 Since this process
incorporates carbon dioxide into the lactone intermediate
(scheme 2), the carbonate linkages of the final polymer are not
reported like the previous catalysts.1 However, it is stated that
33 mol% is near the theoretical maximum incorporation of

Table 1. Comparison of Catalysts using discussed Qualities:
Catalyst Carbon Pressure needed Renewability Renewability Biodegradability

Dioxide for of Starting of Catalyst of the Copolymer
Incorporated copolymerization Material
(%)a, b (atm)
BDI Zinc 94 – 99a 1.36 Yes, if using Yes Yes
Limonene Oxide
DiZinc >99a 1 No Yes No
Bimetallic 99a 10 No Yes No
Iron(III)
Iron-Corrole 62 19.7 No Yes No
Palladium 33 mol%b 1 No No No
aCarbonatelinkages were the measurement used to assess the amount of carbon dioxide incorporated. bMole percent was the
measurement of to assess the amount of carbon dioxide incorporated. Note that 33 mol% is near the theoretical maximum,1
comparable to 95-99 % carbonate linkages.
Future Research. Currently, a variety of chemical techniques standards has not yet been realized. The BDI zinc catalyst is
are being employed to approach this process. To grasp a better able to synthesize biodegradable polymers,15 while the dizinc
understanding of the mechanism of polymerization using these catalyst shows high activity at atmospheric pressure. 19 The
catalysts, the reaction can be computationally modeled.31 For bimetallic iron (III) catalyst can create polymers of high
example, the BDI Zinc catalyst previously described has been crystallinity.12 While the palladium catalyst is able to
modeled by Morokuma et al32 who mapped out a plausible incorporate CO2 into a polymer starting with a conjugated
sequence of reactions for the CO2-epoxide copolymerization, diene.1 In this critique of three example methods, it is clear that
using ethylene oxide. They predicted carbon dioxide would different catalysts have certain advantages but also
weakly coordinate to the coordinatively unsaturated zinc- disadvantages. Both zinc and iron routes of catalysis use CHO
bound polymeric alkoxide. 32 They identified the transition and PO, which are not yet sourced from renewable
state of this mechanism as the breaking epoxide bond, and the feedstocks.22 Thus, the process also needs to be adjusted to
following ring-opening step by the polymeric carbonate to be favour renewable starting materials. Using petrochemical
the rate-determining step. This modeling can be applied to derived hydrocarbons and epoxides30 on an industrial scale
other similar catalysts for this process, and the transition state would not be a green option. For that reason, research into the
and rate-determining steps of the reaction will provide insight copolymerization of renewable, naturally occurring or derived
into future catalyst design.32 Using different models and basis starting material also needs to be a priority. However, BDI zinc
sets, the enthalpies and free energies of copolymerization with catalysis of limonene oxide, produces a biodegradable
different reagents can also be analyzed to aid in design of better copolymer from a renewable feedstock using mild conditions.23
catalysts.31 Of the results chronicled in this article, this process best
There has also been research into metal free catalysis. A embodies the principles of green chemistry.13
notable example of this was put forward by N. Aoyagi and Also included in this critique was the novel technique to
colleagues,33 who used secondary and primary ammonium copolymerize carbon dioxide with conjugated dienes via a
iodides to activate carbon dioxide and synthesize cyclic lactone intermediate. As discussed previously, the use of
carbonates.33 However, this catalysis has yet to report palladium, an intermediary step, and use of non-renewable
applications in the creation of copolymers. The fact that this feedstocks13, is not indicative of a green process. This
catalyst is able to activate carbon dioxide is an important emphasizes the fact that there is research currently done in the
advancement to demonstrate that metal-free catalysts are field that hardly embodies any principles of green chemistry.
viable alternatives. It is still important to analyze the One cannot generalize an entire field since some of the ways to
renewability of these catalysts, because they are metal free does perform this reaction are green. It is dangerous to make
not automatically make them green. Conscious choices will assumptions, the reader needs to be aware of this, and critically
have to be made in sourcing the starting material of the catalyst. evaluate the information given before deciding if a process is
One type of catalysis that seems to be missing in this field is the green or not.
use of nanoparticles. Immobilized catalysts have been used for Unfortunately, all of this research field cannot be considered
carbon dioxide copolymerization,34 so the heterogeneity of green until a viable method of carbon dioxide capture and
nanoparticles may be suitable for the copolymerization storage is available.10-11 In order to maximize the valorization of
process. Nanoparticles also provide many tunable qualities the waste product, CO2, this method needs to be energy
such as size, shape, and composition.35 Due to the small size but efficient, to ensure the green standards of the CO2
high surface area of nanoparticles, the cost per function is copolymerization process are not negated by the effort of
minimized.3 This makes nanocatalysis attractive for industrial obtaining the starting material. As of 2014, there were pilot
processes.36 Since there has been significant development in the projects under way to optimize carbon capture and storage on
research of nanoparticles in recent years, it could be an idea a large scale.10 With the world focused on limiting CO2
worth exploring. emissions,11 this technology will be in focus over the next few
CONCLUSIONS years. Hopefully, this will mean the realization of a completely
green CO2 copolymerization process.
It is clear that there is still a lot of work to be done in this
field. A commercializable catalyst that upholds green

AUTHOR INFORMATION 17. Pinaka, A.; Vougioukalakis, G. C., Using sustainable metals
to carry out “green” transformations: Fe- and Cu-catalyzed CO2
Corresponding Author monetization. Coordination Chemistry Reviews 2015, 288, 69-97.
* E-mail [email protected] 18. Cheng, M.; Lobkovsky, E. B.; Coates, G. W., Catalytic
reactions involving C1 feedstocks: new high-activity Zn (II)-based
ACKNOWLEDGMENT catalysts for the alternating copolymerization of carbon dioxide and
epoxides. Journal of the American Chemical Society 1998, 120 (42), 11018-
I gratefully acknowledge the Green Chemistry class of Prof. A. 11019.
Moores, and Prof. R. Rogers at McGill University for support in 19. Kember, M. R.; Knight, P. D.; Reung, P. T.; Williams, C. K.,
the writing of this article. Highly active dizinc catalyst for the copolymerization of carbon
dioxide and cyclohexene oxide at one atmosphere pressure. Angewandte
ABBREVIATIONS Chemie International Edition 2009, 48 (5), 931-933.
CO2, Carbon Dioxide. CHO, cyclohexene oxide. PO, propylene 20. Broadley, M. R.; White, P. J.; Hammond, J. P.; Zelko, I.; Lux,
oxide. PDI, Polydispersity Index. BDI, β-diiminate. A., Zinc in plants. New Phytologist 2007, 173 (4), 677-702.
21. Sherrington, D. C.; Simpson, S., Polymer-supported Mo and
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Making Something From Nothing: Quantifying the potential of
biogas from organic waste in Canada
Joanna R. Vinden
KEYWORDS: Biogas, organic waste, Canada, biomethane, green chemistry.
ABSTRACT: The use of organic waste materials as a biogas feedstock presents multifaceted environmental benefits. In addition to
reducing dependence on fossil fuel sources for energy, diversion of organic waste material to biogas plants will reduce greenhouse
gas emissions and pollution caused by the current prevailing disposal methods of organic waste materials. Canada is a country rich
in biomass with large argicuture and forestry sectors producing large amounts of organic waste, creating potential for organic waste
as an energy renewable energy resource. This study quantifies the possible energy produced if all sources of organic waste were
wholly converted to biogas.
1. INTRODUCTION hydrocarbon, methane is also a fuel. Natural gas is a commonly

used fuel source that is comprised predominantly of methane,
Increased global awareness of climate change has created an
highlighting the usability of methane as a fuel source. This
impetus for the research and development of renewable sources
presents an intriguing strategy for the mitigation of methane
of energy, including biogas. Biogas is the product of anaerobic
emissions from organic waste: if it were possible to collect all
digestion of biomass, including energy crops and organic waste
of the organic waste material and deliver it to an anaerobic
materials, that can be used for electricity and heat, or converted
digester, the methane produced by its decomposition would
to biomethane for use in the natural gas network.1 Production
not be released to the atmosphere, but used for energy.
of biogas specifically from organic waste materials, such as
agriculture and forestry residue, livestock waste, municipal Biogas plants exist around the world today, using anaerobic
waste, and wastewater sludge, has the added environmental digesters to convert biomass into biogas—a gas mixture that is
advantages of diverting waste from landfills, reducing landfill primarily composed of methane. In addition to reducing
methane and carbon dioxide emissions, and preventing methane emissions and creating energy out of what was once
toxification of soil and groundwater (see Figure 1). In Canada, garbage, this strategy would divert volume from landfills and
unused organic waste materials are responsible for 10% of prevent other harmful effects of unregulated anaerobic
greenhouse gas emissions each year.2 Thus introduction of digestion of organic matter, such as eutrophication and air and
centralized biogas plants in Canada could directly reduce groundwater pollution.4 Further, in addition to methane,
greenhouse gas emissions in addition to reducing dependence biogas production produces a nutrient-rich digestate that can
on fossil fuels. be used as a fertilizer.5 Produced on a large-scale, this could
displace a significant amount of chemical fertilizers used in the
Organic waste material, especially municipal solid waste and
agricultural industry, which are produced by the highly energy
livestock waste, is a significant source of methane emissions.
intensive haber-bosch process.
Methane is a greenhouse gas 21 times more potent than carbon
dioxide in terms of global warming potential.3 Mitigation of Biogas produced from waste materials in Canada is currently
this greenhouse gas is thus a crucial concern in climate change an untapped hydrocarbon resource that, unlike petroleum-
efforts. Unlike other greenhouse gases however, as a based hydrocarbon resources, is more environmentally
detrimental if left unused. This paper serves to quantify the

potential for large-scale biogas production from waste livestock manure was estimated based on a study by Levin et al
materials in Canada. to be 14.3%, 25.5%, and 10.1% for cows, poultry, and swine
respectively.2 The amount of dry matter in the wastewater
sludge was estimated to be 4% based on a study by Berlgund et
2. METHODS al.7 The organic fraction
Data on the feedstock inventories in Canada was obtained from
a study by Wood and Layzell.6 The amount of dry matter in
CO2+ CH4+
GHG*Emission*
Forestry/Farm+
Residue+ Burn+Off+
a POWER*
Livestock+Waste+
Open+Air/Lagoon+
Municipal+Waste+
Fer( lizer*
Toxific( o n*
Landfill+
Wastewater++
Sludge+
Figure 1. Schematic diagram of the benefits of diverting organic waste to biogas production.
of dry municipal solid waste was taken to be 40% based on a convert the macromolecules present in the feedstock material
study by Chornet et al.8 The conversion factors of dry matter to into compounds suitable for use as food by microorganisms.10
biogas yield were adapted from the study by Berglund et al. 7 Proteins, carbohydrates, and lipids are metabolised into amino
The published conversion factor for manure was 7 GJ/dry tonne acids, monosaccharides, and long chain fatty acids.
for swine manure and 6.2 GJ/dry tonne for cow manure.7 In this In the second stage, called acidogenesis, the monomers
study, the conversion factor the manure from cows, pigs, and produced in hydrolysis are further digested by acidogenic
poultry combined was taken to be 5.5 GJ/dry tonne to account bacteria into short chain organic acids (such as acetic, formic,
for the lower biogas yield of poultry manure. 9 The conversion and butyric acid) and alcohols (methanol, ethanol). Some
factor for agricultural and forestry waste was approximated to hydrogen and carbon dioxide is also produced during this
be 7 GJ/dry tonne, based on the published conversion factor for stage.11
straw.7
The short chain acids and alcohols (except methanol)
produced resulting from acidogenesis are further degraded by
acetogenic bacteria into carbon dioxide, hydrogen and acetic
3. HOW IT WORKS acid in the third stage of anaerobic digestion, acetogenesis. This
Anaerobic digestion of organic material is a process involving a stage is acutely sensitive to the partial pressure of hydrogen. As
variety of microbial communities. There are four stages of hydrogen is a major product of acetogenesis, an elevated
anaerobic digestion: hydrolysis, acidogenesis, acetogenesis, hydrogen partial pressure will render the conversion processes
and methanogenesis, each one making use of a different type of thermodynamically unfavourable.12 Hydrogen scavenging
microorganism.10 A schematic of the entire process can be bacteria are thus another critical bacterial family in the
found in Figure 2. anaerobic digestion process, as they act to keep the partial
The first step in anaerobic digestion is hydrolysis. During this pressure of hydrogen low in the reaction vessel.11
process, the feedstock material is broken down into its basic The fourth and final stage of anaerobic digestion is
substituents via enzyme-mediated digestion. Extracellular methanogenesis. During this stage, the acetic acid, hydrogen,
enzymes secreted by bacteria, such as proteases and amylases, and carbon dioxide formed in the acidogenesis and

acetogenesis stages, as well as the methanol formed during the
acidogenesis stage, are converted into methane
Hydrolysis)
Acidogenesis)
Acetogenesis)
Methanogenesis) Methanogenesis)
Figure 2: Schematic diagram of anaerobic digestion processes.
by acetotrophic methanogenesis, hydrogenotrophic Organic waste materials used for biogas production include
methanogenesis, or methylotrophic methanogenesis. The agriculture and forestry residues, livestock residue, municipal
stoichiometric equations for these conversions are found in solid waste, and wastewater sludge. Unlike energy crops, the
Equation 1, 2, and 3 respectively.13 production of biogas from organic waste material does not
require the manufacture of feedstock material and thus the
only energy input is that involved with the collection of
𝐶𝐻3 𝐶𝑂𝑂𝐻 → 𝐶𝐻4 + 𝐶𝑂2 (1) waste.14 Additionally, as the prevailing disposal methods of
organic waste are environmentally detrimental, diversion of
𝐶𝑂2 + 4𝐻2 → 𝐶𝐻4 + 2𝐻2 𝑂 (2) these waste materials to biogas production presents additional
environmental benefits of greenhouse gas emissions (see Figure
4𝐶𝐻3 𝑂𝐻 + 6𝐻2 → 3𝐶𝐻4 + 2𝐻2 𝑂 (3) 1).
This paper outlines four major sources of organic waste that
The amounts of hydrogen, acetic acid, and methanol produced have potential to be used for biogas production in Canada, and
in the first three stages of anaerobic digestion will depend on quantifies the potential energy production if these materials
the composition of the feedstock.11 Thus, different feedstocks were wholly converted to biogas (see Table 1).
vary widely in the relative amounts of methane and carbon
dioxide in the biogas they produce. Typically the methane
4.1 LIVESTOCK WASTE
content of biogas falls between 50-75%. The biogas can be
converted to electricity and heat, or upgraded to pure methane Livestock manure is an organic waste material that is
(called biomethane) using a biogas upgrader facility, which can extremely hazardous to the environment if left unused. In the
then be supplied to the natural gas grid. United States in 2005, 50.8 million metric tonnes of carbon
dioxide equivalent resulted from methane and nitrous oxide
emissions solely due to livestock manure.15 Normally, manure
4. ORGANIC WASTE POTENTIAL IN CANADA is stored either in lagoons (i.e. buried under ground) or in open-
air and left to decompose. In addition to the foul odour,
Typical feedstocks for biogas production include energy crops decomposition in these conditions leads to many problems,
and organic waste residues. Energy crops, such as maize and namely the production of methane and nitrous oxide, as well as
clover, are crops grown specifically for the purpose of biogas air pollutants such as hydrogen sulphide and ammonia.15 The
production. While biogas from energy crops is renewable ammonia produced has the additional issues of groundwater
source of energy, there are several drawbacks to this approach. contamination and eutrophication of the soil.16 In short, when
Production of energy crops on a large scale requires a treated as waste, manure is highly problematic and
substantial energy input for the cultivation and harvest of the environmentally volatile. However, as an organic material,
crops. Tractors and machinery used in these steps often rely on manure has an alternate destiny as a feedstock for biogas.
petroleum-based fuels, further limiting the benefits of biogas
from energy crops.

Table 1: Quantities of dry manure produced by agricultural livestock in Canada.
Manure Produced Total Dry Matter

Livestock Number of Animals17 (Mt/year)6 % Dry Matter2 (Mt/year)
Cows 7,594,465 100 14.3 14.3
Poultry 126,159,529 2 25.5 0.51
Swine 13,913,001 26 13 3.38
Total 147,666,995 128 -- 18.19
Table 2: Overview of biogas potential by feedstock source.
Biogas Potential per Total Biogas Potential Total Biogas potential

Organic Material Dry Matter (Mt) dry tonne (GJ) (PJ) (TWh)
Livestock Waste 18.19 5.5 100.045 27.79
MSW 6.016 12.4 186.4660788 75.12
Wastewater Sludge 15486.64 22 0.34070608 51.80
Agriculture Residue 38.632 7 270.424 156.99
Forestry Residue 80.74088 7 565.18616 0.09464
Total 1122.461945 311.79
In Canada, 128 million tonnes of manure are produced each year With heightened water treatment standards being introduced,
from cows, swine and poultry.6 Table 1 shows the dry matter the amount wastewater sludge collected around the world is
content of manure by Livestock species in Canada. If instead of ever increasing. In Canada, 390,000 tonnes of wastewater
decomposing on site, this manure were collected and brought sludge is created each year, presenting a significant source for
to an anaerobic digester, it could be converted into biogas production.
approximately 100 PJ of energy (see Table 2). In addition to
mitigating methane and nitrous oxide emission, conversion to
biogas could solve manure’s waste management problems and 4.4 FORESTRY AND AGRICULTURE RESIDUE
turn manure into a renewable energy resource. Agricultural residue is what is left in a field after the harvest:
stalks, stems, leaves—the non-food portions of agricultural
production. While it is beneficial to leave part of the residue
4.2 MUNICIPAL SOLID WASTE (MSW) after harvest to protect soil, the amount of sustainably
There are three categories of municipal solid waste: urban removable residue is still a significant source for biogas
residential waste; industrial, commercial, and institutional production at 40 million dry tonnes. Current disposal methods
waste; and landscaping and construction waste. About 40% of for harvest residue often include burn-off, which results in
the dry weight of municipal solid waste is organic, and significant carbon dioxide emissions. The use of harvest
therefore usable as a biogas feedstock. Unused, these waste residue for biogas production could prevent this source of
materials end up in landfills, where they are degraded to form emissions in addition to creating 270 PJ of energy each year in
methane that is released to the atmosphere. Landfill emissions Canada.
are the largest source of anthropomorphic methane in the Forestry waste includes the non-stem portions of the trees—
United States.18 Much of the organic material in landfills is a i.e. the branches and leaves. The forestry industry in Canada is
result of food waste. In North America, 300 kg of food per immense, with an annual harvest of over 1 million hectares
capita is wasted annually by consumers and production to every year, the residue amounts to 90 million dry tonnes.
retailing.19 In the U.S., 40% of food that reaches the consumer
is thrown away—the equivalent of 20 pounds per person per
month.20 The total municipal solid waste production in Canada 4.5 SUMMARY OF ORGANIC WASTE POTENTIAL
is nearly 23 million tonnes (wet). If the organic fraction was IN CANADA
diverted into biogas production, it would result in Table 2 illustrates the potential energy from biogas if each
approximately 186 PJ of energy. source of organic waste were wholly diverted to a biogas plant.
4.3 WASTEWATER SLUDGE The total amount of energy created from organic wastes was
Another waste form that has potential as a biogas feedstock is found to be over 300 GWh, the equivalent of 190 million barrels
wastewater sludge: the material filtered out of wastewater, of oil.21 The organic waste from forestry and agricultural sectors
including sewage. This sludge is mostly organic material and are the largest sources of energy, accounting for 230 GWh
can produce the most methane per dry kg out of all of the combined. The total biogas potential from all organic wastes
feedstocks mentioned in this paper. Wastewater sludge is could power over 50% of Canada for a year.
another troublesome waste that is major source of marine
pollution. Its high capacity for conversion to methane as well
as the sheer quantity produced in developed countries makes
wastewater sludge an ideal candidate as a biogas feedstock.

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wastes in centralized biogas plants. Applied biochemistry and biotechnology
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anaerobic digestion submodels. Swedish University of Agricultural Agricultural biomass residue inventories and conversion systems for
Sciences., 1999. energy production in Eastern Canada. Prepared for Natural Resources-
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Biogas Slurry on Vegetables and Soil [J]. China Biogas 2009, 1, 014; (b)
inventory-final. pdf 2002.
Liu, W. K.; Yang, Q.-C.; Du, L., Soilless cultivation for high-quality
18. Czepiel, P. M.; Mosher, B.; Crill, P. M.; Harriss, R. C., Quantifying
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a Bio-based Economy; BIOCAP Canada Foundation: 2003.
Alexandre Maybeck Global food losses and food waste: Extent, causes and
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prevention; Food and Agriculture Organization of the United Nations:
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Strategies for the Reduction of Methane Emissions and Harnessing
for Use as an Alternative Energy Resource: A Review.
Alyssa Fu
KEYWORDS: Methane, methane emissions, greenhouse gases, environment, alternative energy

resource
ABSTRACT: Methane gas is a greenhouse gas over 20 times more potent than carbon dioxide and is produced in four principal
sectors: the oil and gas industry, the agricultural industry, from landfill waste, and as a byproduct of coal mining. Apart from being
detrimental to the environment, the emission of methane into the atmosphere is also a waste of an energy resource. In this review,
the sources of methane emission and current methods used to mitigate emissions or to harness them for use are presented and
evaluated. It was found that the harnessing and use of emitted methane for an alternative fuel source has been explored to varying
degrees depending on the sector: in the oil and gas industry the detection of emitted methane is still a challenge, whereas in the
agricultural, landfill, and coal mining sectors the harnessing of methane gas for use is becoming more popular, though flaring is still
an option in these sectors.
1. INTRODUCTION emissions.1 Greenhouse gases (GHGs) include: carbon dioxide

In the past several decades, societal attention has shifted (82%), methane (10%), nitrous oxide (5%), and fluorinated
increasingly toward greenhouse gas emissions and the gases (3%).1
problems they pose, as well as the solutions presented to solve Greenhouse gases play an important role in trapping heat in the
these problems. Emission sources as reported by the United atmosphere and maintaining global temperatures necessary for
States Environmental Protection Agency (EPA) include: life on Earth. Trapping too much heat, however, can lead to a
electricity (31%), transportation (27%), industry (21%), global rise in temperature, a phenomenon known as global
commercial and residential (12%), and agricultural (9%) warming. Climate change that results from global warming is

of significant importance as it directly affects the survival of the anaerobic decomposition of its organic matter in storage.
many lifeforms on Earth2 by impacting the habitats in which Storage conditions such as temperature, oxygen level
they live. To combat global warming, much research has been (aeration), moisture, and sources of nutrients greatly affect
conducted on the matter of reducing greenhouse gas emissions. emissions.9
Carbon dioxide has been a main concern as emissions are found
to account for 80% of all GHG contributions to global 2.1.1. Agricultural methane emission reduction and
warming3. The second most prevalent GHG is methane, which harnessing strategies
accounts for 10% of GHG contributions to global warming3.
Although CO2 is the primary GHG emitted through human Methane emitted as part of livestock digestion is difficult,
activities (there is 200 times as much CO2 in the atmosphere though not impossible, to mitigate. Cattle diet plays a huge part
as there is methane4), methane is more potent, with a global in emissions, so feeding strategies naturally play a part as well.
warming potential (GWP) 3.7 times that of CO2 on a molar Experiments done by Agriculture and Agri-Food Canada
basis3. Therefore, while methane does not linger in the (AAFC), for example, have shown that an increase in dietary
atmosphere for as long as CO2 does, its higher GWP means fat by feeding crushed oilseeds such as sunflower, canola, and
that it is far more effective than CO2 at absorbing and trapping flaxseeds, reduce methane emissions from livestock by up to as
heat in the atmosphere, and it is initially far more devastating much as 20%.10 The use of a methane inhibitor (3-
to the climate. nitrooxypropanol, or 3NOP, outside the scope of this paper)11
Methane emissions have many sources, including: natural gas was found to persistently decrease methane emissions by
and petroleum systems (29%), enteric fermentation (26%), enteric fermentation by 30%, without negatively affecting
landfills (18%), coal mining (10%), and manure management animal productivity. Other methods for the mitigation of
(10%).1 Global warming is also causing the release of methane enteric emissions include management practices that reduce
hydrates frozen in permafrost.
animal numbers on beef and dairy farms10, as well as vaccines
Recently, studies have been conducted on the harnessing and that target the methanogens present in animal rumen12.
reduction of methane emissions. The EPA proposed the first-
ever rule to directly limit methane emissions from oil and gas For the remaining emissions emitted by livestock, recent
operations in 2015.5 This would instill regulations to reduce methane harnessing strategies have been developed, including
wasteful methane emissions in the near future. Studies have a backpack for cows for the collection of methane gas
also been conducted on the harnessing and use of emitted emissions13. This method extracts 300 L of methane a day from
methane gas in the environment, including methane hydrates the animals’ digestive tracts and converts the gas into enough
as a fuel source6 and the use of methane emissions from
energy to run a car for 24 hours.13
livestock, landfills, and coal mining for an alternative fuel
source through a combustion reaction. Enteric fermentation is not the only factor for agricultural
In this review, methods for the harnessing, use, and reduction emissions, however, and livestock manure should also be
of methane emissions will be explored. addressed. Its value as an excellent soil amendment, as
mentioned above, prompts storage at various farming locations
2. METHANE EMISSION SOURCES AND worldwide. In storage, the
RECYCLING PROCESSES
In order to better understand the recycling processes of
methane, it is important to first understand the sources from
which methane is emitted. Globally, over 60% of total methane
emissions come from human activities.1 By understanding how
methane is emitted from each source, it becomes possible to
devise methods for the reduction and recycling of methane
emissions.
2.1. Agriculture
The agricultural sector is the primary source of methane

emissions from human activities globally1. Enteric fermentation
is responsible for 26% of methane emissions, while manure
management is responsible for 10%.1 These emission sources are
considered human-related because humans farm the animals
responsible for the emissions and raise them for food.
Enteric fermentation is the digestive process whereby

microorganisms break down carbohydrates for absorption into
the bloodstream of an animal. Methane is produced in the
rumen as part of this process, and it is emitted through belching
by the animal or passed out as flatulence.
Livestock manure is a valuable resource for nutrients and an

excellent soil amendment that improves soil quality, tilth, and
productivity.9 It is also a source of methane production during

Figure 1. The anaerobic decomposition of manure in a lagoon forming methane biogas, to be used as an
alternative energy source or flared to the environment. Remaining manure can be used as fertilizer.
amount of methane emitted depends upon: the amount of 2.2.1. Industry methane emission reduction strategies
manure, the animal type, the manure handling method, and the
environmental conditions.9 Liquid manure storage, such as in As mentioned above, the EPA has proposed national
ponds, lagoons, and holding tanks, leads to anaerobic standards to directly regulate methane emissions from the oil
conditions; the decomposition of manure in these conditions and gas industry just recently. Although currently unfinalized,
can emit up to 80% of manure-based methane emissions.9 Solid the rule is expected to have an impact on methane pollution for
storage, on the other hand, comprises a more aerobic new and modified sources in the industry.5 Regulation of
environment, and emits little to no methane. emissions is an important step for mitigation of leakage, due to
the variety of ways in which leakage can occur: loose screws,
Waste management methods for manure include covered leaky storage tanks, corroded pipes, outdated compressors,
lagoons, whereby a cover is placed on the surface of the tank or inefficient pneumatic systems, condenser valves stuck open. 8
lagoon used for storage; the trapped gases are subsequently
flared and exhausted to the atmosphere as the less potent CO2, Replacement of outdated equipment prone to leakage could
or burned inside a generator for an alternative energy source. 9 aid in stopping leakages, as well as the installation of new
Covers can reduce methane emissions by 80% 9 and provide technology to capture leaks where they occur. Unfortunately,
good odor control as well. Digesters are also used to process it is difficult to determine when and where a certain pipe will
waste for the production of methane gas under anaerobic leak in hundreds of miles of pipelines, or when a certain valve
conditions.9 The gas can be used as an alternative energy source or storage tank will suddenly burst open 8. Therefore, the
and the remaining manure can be used as fertilizer. A typical current approach to dealing with fugitive emissions has been to
lagoon is shown in Figure 1 below. impose regulations (as noted above) and to investigate
methods for the better detection of leakages. Thus far, infrared
cameras have been put to use for the purpose of leakage
detection, however, better detection systems are needed, as
2.2. Oil and gas industry they are too labor-intensive and fail to find many leaks 8.
The second biggest source of methane emissions as denoted Cameras mounted on drones have been explored8, but they do
by the EPA stems from the natural gas and petroleum industry, not last long and the development of lighter sensors is required
better known as the oil and gas industry. This sector is to prolong flight time.
responsible for 29%1 of emissions from human activities in the 2.3. Landfills
US. Emission sources from the oil and gas industry include
leaks in natural gas transmission facilities such as pipelines and Landfills account for 18%1 of human activity-related methane
compressor stations, as well as leaks in upstream oil and gas emissions in the US. Much like manure, methane is produced
production facilities, especially from solution gas.7 For both in landfills during the anaerobic decomposition of the organic
safety and climate change reasons, the elimination of methane matter present. As such, emission levels differ from landfill to
emissions from these sources can only be beneficial. In addition, landfill depending on site-specific characteristics such as the
these emissions are a source of wasted energy, which, if kind of waste present and its composition, as well as the
captured, can be used as fuel for useful energy.7 climate of the landfill in question.

2.3.1. Landfill emission reduction and harnessing strategies generation.21 In the US, some mines even sell the gas to natural
gas distributors.21
Landfill waste can be mitigated first and foremost by limiting
waste production not only in the industrial setting but the Methane emissions from ventilation air shafts used during
office and household settings as well. This can be achieved by mining can be lowered in several ways: by using the ventilation
reusing objects before subjecting them to the waste bin and air as the combustion air in surface installations at the mine
simple tasks such as composting organic waste instead of site, by the oxidation of methane to carbon dioxide, or by
throwing it out. In fact, increased recycling and alternative thermal incineration.20 The use of ventilation air as combustion
waste disposal methods are contributing to a forecasted decline air has been noted to be unlikely to use more than a small
in landfill methane emissions, by reducing the rate of waste portion of the total available air20, making this an unlikely one-
going into the landfills.15 shot solution to the problem. Both thermal incineration and
oxidation of methane produce carbon dioxide (the primary
For waste that does end up in landfills emitting methane gas, greenhouse gas, although less potent), so this is not the best
rules such as the Emission Guidelines set by the EPA 16 ensure solution either, unless coupled to an energy recovery system.
that methane emission is controlled by setting an emissions
threshold at which a landfill must install controls. Landfill gas The use of boreholes, or narrow shafts bored into the ground,
recovery plants exist to capture and use emitted methane as a for methane drainage provide an effective way of reducing the
renewable energy source in many countries including: Canada, risk of gas outbursts by decreasing the pressure of the coal bed
Germany, Sweden, Finland, and the United States, to name a near the mine workings23.
few.17 The world’s largest biogas plant has a 140 megawatt
(MW) capacity and is expected to cut coal use by up to 40% in Once a mine is abandoned, the methane emission decreases
Vaasa, central Finland, where it was built.18 Current landfill but does not completely stop. Abandoned mines can liberate
methane emission mitigation strategies appear optimistic for methane at a near-steady rate for an extended period of time.23
the short term: Northern European countries such as Sweden Flooding of the mines can inhibit gas emissions and buildups in
and Norway burn waste as a major source of energy.19 Recently, the empty spaces; this would also help to mitigate the danger
they have even had to import garbage as they had run out of level of working in active mines nearby23. Methane emissions
waste to burn. In the event that demand far exceeds supply for from abandoned mines can also be reduced by properly sealing
trash worldwide, this would mean no more methane emissions the mine, eliminating unintentional venting of methane23.
from landfill sources, and attention would then be drawn to Finally, it should be noted that, with the advancement of
harnessing from other sources as mentioned in this article. technology and various other methods for electricity and
2.4. Coal mines energy generation (hydroelectricity, wind turbines, solar
generators), perhaps the method of coal mining should take a
Coal mines are the fourth-largest source of methane backseat. After all, the only way to ensure 0% methane
emissions from human activities, and are responsible for 10%1 emissions from coal mining would be to stop mining activities
of emissions in the US. Methane gas and coal are formed altogether, but this is beyond the scope of this paper.
together during coalification, and methane is stored within coal
seams and the rock strata surrounding the seams.20 It is 3. SUMMARY AND FUTURE PROSPECTS
released when natural erosion, faulting, or mining causes the
Methane is a greenhouse gas over 20 times more potent than
pressure within the coal bed to drop.20 Underground mines
carbon dioxide on a pound-for-pound basis over a 100 year time
tend to release more methane than surface mines, because
period.1 It is emitted primarily from four major sectors: the
storage capacity is increased with pressure, which increases
agricultural industry, the oil and gas industry, from landfill
with depth. According to the EPA, underground coal mines
waste, and from the coal mining industry. The emission of
liberate 29 to 40 x 109 m3 of methane annually, of which less
methane gas from these sectors into the atmosphere not only
than 2.3 x 109 m3 is used for fuel.21 Abandoned mines also play a
has a negative impact on the environment, but also represents
part in methane emissions, and a study done by the EPA
a wasted energy resource. Across each sector, various methods
concludes that, along with coal handling and surface mines,
have been applied to limit the amount of emissions; in the oil
they represent approximately 26% of total emissions from the
and gas industry, however, efforts are still being made for the
coal mining industry.22
proper detection of leakages. The theme behind the methods
2.4.1. Coal mine methane emission reduction and harnessing applied to each sector follows roughly the same format: a rule
strategies or regulation is implanted, and measures are taken to follow
that rule. Energy harnessing has been explored in the
As mentioned above, underground coal mines liberate 29 to agricultural, landfill, and coal mining sectors, with exceptional
40 x 109 m3 of methane annually, of which less than 2.3 x 109 m3 results using landfill waste in particular. This is usually
is used for fuel.21 The remaining methane is emitted to the achieved through a combustion process, whereby methane is
atmosphere and represents the loss of a valuable energy converted to CO2 and water. The expulsion of this CO2 into the
source21; methane is also detrimental to the environment as a atmosphere is justified by noting that, if methane were not to
major greenhouse gas. Thus, methods for the capture and use of be used as an alternative fuel source, it would be expelled into
methane emitted from coal mines have been developed.20-21 As the atmosphere anyway, and cause more than 20 times the
methane is the primary constituent of natural gas, current uses damage than would CO2. In addition, another fuel source
for coal mine methane include: heating and cooking at mine would be used, adding to the greenhouse gas emissions.
facilities and nearby residences, boiler fuel, and electricity

For future research, better methane detection technologies S., An inhibitor persistently decreased enteric methane
must be developed for the oil and gas industry, as this would emission from dairy cows with no negative effect on milk
allow for the better pinpointing of leak locations and thus more production. Proc. Natl. Acad. Sci. U. S. A. 2015, 112 (34), 10663-
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to maximize the full potential of emissions. livestock wind. Nature (London, U. K.) 2004, 429 (6988), 119.
13. Zolfagharifard, E. Now THAT'S wind power! Cows
AUTHOR INFORMATION wear BACKPACKS to capture their "emissions" and become
miniature power stations.
Corresponding Author http://www.dailymail.co.uk/sciencetech/article-
Alyssa Fu ([email protected]) 2606956/Now-THATS-wind-power-Cows-wear-
BACKPACKS-capture-emissions-miniature-power-
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Deighton, M. H.; O. Williams, S. R.; Kindermann, M.; Duval,

Environmental decay, incommensurate methane emission and
feasible future solutions for the treatment of a greenhouse gas
Angel J. Castañeda
KEYWORDS: Absorption, greenhouse gasses, framework, ionic, nanofibers
ABSTRACT: The human growth in the last decades has required the supply of food, energy and fuel in a high demand. These three
necessities are related with one issue: green house gas emission. This may not appear directly related to the supply of goods, but
secondary activities are responsible for this problem such as organic waste disposals, natural gas extraction and combustion of fossil
fuels. These and other similar activities have raised methane concentration in the environment, causing an increase in temperature
and natural disaster frequency. For this reason, methane emissions have been chosen as a target problem to be solved. Some
opportunities to reduce this greenhouse gas are the implementation of physical chemical and spectroscopic methods such as: time
correlation tracer systems, sorption modeling for coal-bed methane production, use of ionic liquids for methane capture and methane
decomposition by catalyst to create carbon nanofibers. Several of these small-scale applications have shown significant results for
methane reduction. This paper reviews the significant results for methane reduction of the aforementioned physical, chemical and
spectroscopic methods.
INTRODUCTION instance hurricanes, tornadoes, floods, typhoons, droughts,

Over the pass of the years, the chemical composition of the wildfires, etc.1 Methane is one cause of many of environmental
atmosphere has been altered producing a change in deterioration, producing a growth in the greenhouse effect 2.
environmental conditions, such as the increment of Global activities such as fossil fuel production, distribution and
temperature. This has led to an increase in natural disasters, for use; intensive livestock farming; and the creation of abounding

landfill and waste disposals, generate the exponential emission through a transparent medium, but the emitting radiation from
of this gas 3. With the well-known consequences of the the Earth to the space (infrared radiation) is blocked by it. This
preceding activities, humans must propose alternatives to trapped radiation causes the heating of the Earth's surface,
reduce the inherent global warming created by the greenhouse increasing its temperature. The primary cause for this effect is
effect. attributed to carbon dioxide (CO2) which has increased 30%
since industrial times, 5 and is still increasing with a rate of
Scientists may be doing research for creating a new branch of 0.4% per year according to the records and documentation of
chemistry, for example: innovating low-cost and Mauna Loa Observatory7 as illustrated in Figure 2.
environmentally friendly processes, namely methods for
recycling and purifying water and technologies for storing
ATMOSPHERIC CO2 AT MAUNA LOA
energy coming from renewable sources. However, a small
OBSERVATORY
portion is proposing solutions to improve climate conditions 480
that are damaged and getting worse. 460
PARTS PER MILLION

440
The purpose of this paper is to give a review of the
420
environmental situation as well as to provide ideas and
400
proposals of what can be done for the environmental concern
380
and the treatment of immeasurable methane emission by using
360
technologies and processes already developed by scientists. 340
Many possible options to solve this current global condition 320
are convenient, for example: the employment of methane 300
1955 1965 1975 1985 1995 2005
sorption models, the decomposition of methane to heavier
hydrocarbons and its conversion to reusable goods. With the YEAR
prior proposals to improve the environmental situation, a slight
reduction of catastrophic side effects in the near future may be Figure 2.7 Graphic of carbon dioxide increase in ppm reported by
possible the Institution of Oceanography. Scripps Institution of
Oceanography NOAA Earth System Research Laboratory.
DISCUSSION
The composition of the atmosphere is 78% nitrogen, 21% However, CO2 is not the only greenhouse gas resulting from
oxygen, 0.9% argon, 0.0375% carbon dioxide and 0.003% as anthropogenic activities, methane and nitrous oxide must also
trace elements. This composition has remained the same for the be taken into consideration.
past 200 million years 4. However, it wasn't until the beginning The main characteristic of these gases is the increment on
of the industrial revolution in the mid-18th century when the Earth’s temperature that consequently generates an impact on
impact of human activities began to grow, especially the use of climate change and natural disasters. According to the IPCC,
fossil fuels and their combustion5. This led to the creation of an increase in greenhouse gasses in the atmosphere will
greenhouse gases and aerosols that modify the atmosphere
probably increment temperatures, which will lead to the
composition. Hydrocarbons were not uniquely responsible for emergence of droughts, intense storms, tropical cyclones and
the initiation of ambient impact effects, the emission of mid- latitude storms8. In Figure 3, the graphs demonstrate that
chlorofluorocarbons, chlorine and bromine compounds were the change in climate, besides affecting temperatures, produces
also a cause of the ozone layer depletion. an increase of weather-related natural disasters. An example of
As Figure 1 illustrates, the increase in temperature over the this is: the formation of storms by decreasing the temperature
years since the first half of 18th century due to the industrial difference between the poles and the equator. The warmer
revolution 6. temperatures at latitude 0 will increase the water vapor in the
atmosphere generating a humid and hotter environment. From
the convection currents, the poles will receive warmer air
drafts taking these regions out of temperature equilibria.
Subsequently, as the temperature increases, concentration of
water vapor in the atmosphere increases, as well as the
probabilities of storm formation with greater potential. The
increase of temperature over land, change of temperature
difference between equator and poles and humidity increase
could provoke intense cycles of droughts and floods 9.
Figure 1.6 Graphics for Northern and Southern Hemisphere
According to the Climate Analysis Indicator Tool, China and
average temperature along the past 150 years. Graphics plotting
temperature versus years. the U.S are the main countries for greenhouse gas emissions,
and methane is the second highest emitted gas in the U.S. 10.
Moreover, the greenhouse effect is the phenomena that Although CH4 emissions are small compared to those of carbon
permits the solar radiation (visible radiation) absorption

dioxide (CO2), the lifetime in atmosphere of CH4 is 12 years. decades because of the large growth of livestock populations
The global warming potential (it refers worldwide producing an increase of 90 million tonnes of
methane annually 13. Landfills and waste dumps generate
methane due to the decomposition of biodegradable organic
material, and it produces 55 million tonnes annually.
Human Sources of Methane
Fossil fuel production
Livestock farming
As population grows every year, as does human waste,
Landfill and waste increasing the number of landfills. As more organic waste is
9% 5%
11% Biomass burning produced, anaerobic degradation increases the methane
32%
Rice Agriculture production. But not only solid material wastes enhance this
16% 27%
problem, but also wastewater from residential and industrial
Figure 39. Different graphs to illustrate divergent temperature sources can be a problem 3.
behavior in distinct cases.
Biomass burning, rice agriculture and biofuels represent a
to how much energy the emissions of one ton of a gas will minimum percentage of methane emission, but they contribute
absorb over a given period of time11) is 28-36 compared to CO2 69 million tonnes annually 3.
that it is 1, and the most hazardous property of CH4 is that it is
can absorb CO2 in much higher concentrations which, in turn, As it was reviewed, production of methane is inherent in all
will lead to greater impacts on climate change. human daily activities and as long as we continue inhabiting
this planet, greenhouse gasses will continue existing. For the
There exist two types of methane emissions. The natural prevalence of an equilibria between our wellbeing and the
emissions correspond to a 36% of the total emissions, while continuity of quotidian activities, standards or mitigation
human emissions account the 64% total including landfills, opportunities should be applied to achieve better
livestock farming and fossil fuel use (see Figure 4)3. environmental conditions. An example of this is illustrated in
the graph of Figure 5, where U.S reduced a by 15% the CH 4
emissions in a period of 23 years 11.
Figure 5. U.S. Methane Emissions, 1990-2013
Some reduction opportunities for methane have been set by

the U.S Department of State such as the renewal of extraction,
handling and transportation equipment for natural gas which
will reduce the number of gas leaks 14. Another proposal is that
of manure management strategies at livestock operations15 and
the implementation of methods to capture methane in landfills
as a reduction strategy16.
On 1 October 2010, 37 government partners and the European
U.S. Methane Emissions, 1990-2013
800
(Million Metric TonsCO2
600
Methane Emissions
Figure 412. Pie chart for the human sources of methane

400
Equivalent)
The methane concentration in the atmosphere has increased in

the last two centuries because of the population growth and 200
the increase in human activities. In the past, the methane
0
concentration was between 350-800 ppb but after the 1850’s,
1990 1995 2000 2005 2010
the concentration levels have raised 2.5 times larger 12.
Year
Fossil fuels production and use occupies the 32% of the
Commission launched The Global Methane Initiative (GMI) to face
overall emissions and they are mainly produced when fuels are
extracted from the earth (natural gas, petroleum, and coal) but the climate change developing new technologies for cleaner
also during their handling, transportation and refinement. It energies 17. An example of this is the implementation of bio
has been calculated that 110 million tonnes of methane are digesters in local farms in the U.S region. At the moment, this
produced due to these activities 3. has been a great step for society to deal with climate problems
and the decrease of greenhouse gasses production. However,
Livestock farming is also a big contributor of methane by the more than establishing initiatives can be done.
enteric fermentation in animals proportioning the 27% of
emissions. This emission has increased the last few

University research groups have focused on investigating and raw material for the production of new materials. For example
developing new technologies for the generation of energy from the methane decomposition by catalyst like cobalt supported
renewable sources. These technologies include solar radiation, with aluminum, magnesium, silicon and titanium induce the
construction of hydroelectric power plants, assembly of formation of carbon nanofibers and nanotubes. These two last
windmills, hydrogen fuel cells and the replacement of common components have been of great relevance because they are
fuel sources as hydrocarbon derivatives. Methane is a nanoscale carbon materials which have a wide application field
hydrocarbon derivative, it is a side product of human activities such as hydrogen storage, chemical sensor, catalytic supports
that cannot be removed unless the chemistry of biodegradation, and field emission display features. This is possible because of
fermentation and combustion is completely changed. Because their magnetic, electronic, chemical and mechanical properties
methane is an unavoidable gas, we can take advantage of its provided by their nanoscale structures 24.
chemical properties that allow it to be used as fuel. Instead of
letting methane flows directly to the upper atmosphere, it One more application for methane usage is the creation of
should be trapped and reused. permanent porous materials with high methane volumetric
storage capacity known as metal-organic frameworks 25. This
One of many pioneers in making use of methane emission and kind of material can solve the problem for future hydrogen fuel
trapping was the Linköping University in Sweden. Their vehicles by substituting them. The main reason for this is
research was principally focused on the quantification of because hydrogen as a fuel is highly flammable and its storage
methane oxidation and its recovery applying a time Correlation is not easy as compared to normal fossil fuel derivatives.
Tracer System with Fourier Transform Infrared (absorption
spectroscopy) as a detection instrument in combination with CONCLUSIONS
nitrous oxide (N2O) as a tracer gas. Their studies were carried As it has been reviewed, technologies for trapping and reusing
out in open and closed landfills, confirming that closed landfills methane have been enhanced with the years and it is expected
had a higher percentage of oxidized methane than open fields, that in a close future these technological and scientific
reporting a gas recovery between the 14-65% according to it advances could be exploited as much as possible and enhance
lead to the U.S environmental Protection Agency to create a methane recycling. As the last examples presented, it is
sector called AgStar 20, the one that implements the use of expected that those technologies get even more developed for a
methane system recovery from livestock waste creating a cost- large scale application, and methane can be use as feedstock for
effective source of renewable energy. The beginning of this other products and applications rather than only energy as the
research began trying to reduce methane from landfills, but unique product. The applications presented in this paper
besides doing it, methane capture for its reuse was also review are not the only ones as there exist more cost-effective
achieved. The advantage of applying this technology in large opportunities for the reduction of methane emissions.
scale will be in certain way sustainable. The unique However, in order to efficiently use the applications developed
inconvenient for popularizing this, is the high cost of the in the laboratory on an industrial scale, more research still
absorption instrument employed for methane detection. needs to be done.
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On Selectivity and Stability: Can Metal Organic Framework be a

Green Industrial Catalyst?
John-Chu-Chia Hsu
KEYWORDS : MOFs, ZIFs, Industrial catalysis

ABSTRACT: There is much focus on improving zeolite’s selectivity and stability for greener catalysis in industry. Metal Organic
Frameworks (MOFs), as another class of porous material, can be readily tuned for their selectivity due to ease of functionalization.
However, their thermal and chemical stability may not high enough. A new type of MOF, called Zeolitic Imidazolate Framework
(ZIF), is meeting this challenge of stability, while still capable of easy modification for higher selectivity and even stability. Thus,
the ZIF may be a better candidate for the development of greener catalysts that drive down the environmental impact from the
chemical industries.
In discussions of porous materials used in industry, a

controversial issue is whether Metal Organic Frameworks
(MOFs) are better candidates than zeolites for the
development of green industrial catalyst. While some argue
that MOFs can be more selective for absorbing or even
converting waste and hazardous chemicals1, others contend
that MOFs lack the stability for recovery and reusability 2.
These two positions seem to be irreconcilable. However, a
closer examination of the field allows us to see that a class of
MOF, called Zeolitic Imidazolate Framework (ZIF), can not
only be modified easily for increased selectivity, but also
stability. These properties will allow chemical industries to
further lower their processes’ environmental impacts.
Despite the success of zeolites as industrial catalyst, there

remains a push towards greater selectivity and stability.
Zeolites are framework materials made of silica and aluminum
(See Fig. 1). Their porosity, structural robustness, and catalytic
activity make them suitable for industrial catalysis. 9 out of 10
industrial chemical processes utilize heterogeneous catalysts3.
While this global market is estimated to be between 15-20 Figure 2. From Hydrated Metal Salts and Organic Linkers to
billions USD per year, 35% of it constitutes zeolite based or Metal Organic Framework (Figure adapted from Sigma
supported metal catalyst4. Due to their structural stability as Aldrich9)
solid acidic catalysts, zeolites have been used by the refining Researchers in the field have demonstrated that pore size and
and petrochemical industry to reduce waste product, replace functionalities of MOFs could be engineered easily for
hazardous acid catalysts, and prevent plant corrosion5. On the selectivity. MOFs, like zeolites, are porous framework material,
other hand, due to their selectivity, they are being used to but they are constructed from metal and organic “linkers” (See
absorb more specific waste compounds6, or used as catalyst for Fig. 2). 1) Prior to the synthesis of MOF, one can choose from
synthesis of fine chemicals5. Compared to the homogeneous many different organic linkers, metals, and solvent conditions
catalysts that are more widely employed in the fine chemical to build a porous material of desired topology and property.
industries, heterogeneous catalysts like zeolite could yield Specifically, by changing the size and the chemical
significant lower amount of waste from washwater stream, functionalities of the organic linkers, researchers could vary
salts, and heavy metal6. Selectivity and stability of a catalyst structure and property of the resulting pore cavity1. 2) Such
seem to be the key that allows industries to lessen their modification is not always possible, Cohen argues, as it is
processes’ environmental impacts. restricted by the synthetic conditions for MOFs (e.g., long
Unfortunately, only a relatively small fraction of new zeolites hours of heating at 100°C or solvent incompatibility)10. A
has been discovered, compared to millions of zeolite structures second strategy addresses this challenge by allowing the
that have been postulated. This, Yaghi et. al. argue, is due to a addition of chemical functionalities after crystal formation,
lack of general synthetic method for zeolites.1 MOFs could be termed Post Synthetic Modification (PSM)10. PSM also makes
functionalized more easily. This has yielded porous materials purification easier because the crystal and the chemical
that have greater selectivity towards certain molecules7. solution are in a different phase10. 3) In response to the very
same challenge, the group of Yaghi developed a high
throughput synthesis method, allowing the thousands of
combination with different solvent, linkers, and metals to be
tested simultaneously and quickly11. MOFs with a wide range
of pore size and functionalities were subsequently generated,
some of which could be scaled up into gram quantities. With
these three strategies, researchers can easily give their MOFs
different topology, functionalities, and pore sizes, which are
relevant to engineering a material’s selectivity towards specific
Figure 1. From Silica and Aluminum to the Zeolite Framework. molecules.
(Figure from Professor T. Poon’s research website8.)

Published in Science12, Long and co-worker’s work showed Despite such control over selectivity, some researchers argue
that the topology of MOFs have a direct impact on their that MOFs are not suitable for industrial catalysts due to their
selectivity towards isomers of hexane. Their newly identified low thermal and chemical stability. Zeolites used in petroleum
framework, Fe2(BDP)3, is capable of separating linear hexane cracking, for example, often experience harsh conditions: a
from its branched isomers, a process that is implicated in the temperature of around 450 to 750°C, and a pressure at 70 atm14.
production of high-quality gasoline (BDP = 1,4- They are widely used not just because of their catalytic
benzenedipyrazolate). The sharply angled pore walls that are properties but also their structural robustness. For the most
also very flat are not encountered in zeolites. (See Fig. 3) The commonly studied MOF (MOF-5), the highest temperature it
researchers reasoned that the sharp crevices between the wall can tolerate in N2 is 300°C15. Efforts have been made to increase
of pores can retain linear hexane chain more readily, thus this limit, but it still falls way below zeolites’ over 1000°C of
allowing its branched isomers to flow through. Such a feature tolerance16. Furthermore, MOFs may not be able to withstand
is not encountered in zeolites probably because the metal node impurities from flue or synthesis gas present in an industrial
in a MOF has a higher coordination number, allowing greater process. For example, it may be hard to scrub off strong acids
structural diversity; whereas, those in zeolites do not (Fe of like SO4 if the MOF’s structural integrity tolerates it at all2.
MOF vs. Si of Zeolite). MOFs have a greater selection of metal Humidity poses yet another challenge to the structure for
nodes than zeolites, making MOFs’ topology more tunable for carbon dioxide capture or conversion2. MOFs can be easily
selectivity. functionalized, but if the structures are not robust enough to
endure harsh conditions, it will unlikely be practical for
industrial purposes.
Notwithstanding, a recent class of MOF, called Zeolitic

Imidazolate Framework (ZIF), was shown to have increased
thermal and chemical stability relative to its MOF
predecessors. As a mimic of zeolite, which composed mainly of
silica, a ZIF is composed of transition metal ions and
imidazolate links. (See Fig. 5). Using thermal gravimetric
analysis, Yaghi and co-worker found a type of ZIF (ZIF-8) that
could withstand thermal heat in N2 gas up to 550°C17—a 250°C
increase from 300°C of MOF-5. They also tested ZIF-8 in
boiling water and in organic solvents that are typical of an
industrial process—benzene or methanol—for 7 days; ZIF-8
Figure 3. The Sharply Angled and Flat Pore Walls of maintained its structural integrity as indicated by powder x-
Fe2(BDP)3 Framework (Figure adapted with permission from ray diffraction pattern. As a relatively new class of MOFs, ZIFs
AAAS12). have the potential to reach even higher thermal and chemical
stability for industrial catalytic purposes.
On the other hand, Yaghi et. al. showed that MOFs with the
same topology, but varied sizes and functionalities of pore
cavity, also exhibit different level of selectivity13. Their MOFs
take up CO2 in levels of selectivity that corresponds to the
dipole moment strength of their organic linker’s substituents:
–Cl, -CN, -Me, -Br, to –NO2 (See Fig 4.). -NO2 is the most
selective, then -CN, -Br, -Cl, then -C6H6, -Me, and finally -H.
The chemical functionalities of the linkers could be used to
rationally tune MOFs’ selectivity towards a molecule.
Figure 5. Zeolite-type Tetrahedral Topology Resulted from
145° between metals in ZIF (Left) or the Si in zeolites (Right).
(Figure adapted with permission from Ref. 15. Copyright
(2010) American Chemical Society.)
ZIFs can in fact be generated by high throughput method

developed in Yaghi’s lab11. Through this method, ZIFs’
functionality and stability can be optimized simultaneously. In
particular, Banerjee et. al. demonstrated that they could put
two different linkers together into a single crystal
(heterolinker) with one phase instead of multiple phases (i.e.,
each cavity has the same composition of two different linkers
and not a distribution of cavities with different compositions.)
The heterolinkers give rise to additional functional complexity,
Figure 4. Substituents on the Imidazolate Organic Linker for so that some of the structures exhibit higher selectivity
Selective Absorption of CO2 (Figure adapted with permission towards CO2 over CO. They are stable up to 390°C and in
from Ref. 11. Copyright (2009) American Chemical Society.) boiling benzene, methanol, and water for 7 days. High
throughput method provides a fast way to generate ZIFs that

have both higher stability and higher selectivity towards 3. Czaja, A. U.; Trukhan, N.; Muller, U., Industrial
specific molecules. applications of metal-organic frameworks. Chemical Society
Reviews 2009, 38 (5), 1284-1293.
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further suggests that functionality can be used to improve of zeolitic catalysts for the petroleum refining and
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Br, -Cl, -Me on imidazole), the researchers developed a ZIF that Elsevier: 2007; Vol. Volume 170, pp 54-65.
is capable of taking up the same moderate amount of CO2 in 5. Clerici, M., Zeolites for fine chemicals production.
humid or dry conditions. The ZIF can tolerate heat up to 450°C Topics in Catalysis 2000, 13 (4), 373-386.
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that hydrophobic cavities created by the substituent repels zeolites. Chem. Eng. Prog 1999, 95 (6), 47-53.
water molecules from entering and subsequently damaging the 7. Zhou, H.-C.; Long, J. R.; Yaghi, O. M., Introduction
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the functionalities be tuned to have selective capturing, but 8. Poon, T. Research Interests.
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To summarize, we saw that although the metals and the 10. Cohen, S. M., Postsynthetic methods for the
linkers give MOFs higher selectivity by taking on different functionalization of metal–organic frameworks. Chemical
topology and functionality, their practical industrial reviews 2011, 112 (2), 970-1000.
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throughput method can be used to quickly generate ZIF of
M.; Hudson, M. R.; Zajdel, P.; Brown, C. M.; Masciocchi, N.;
increased stability but also increased selectivity by introducing
Krishna, R.; Long, J. R., Separation of Hexane Isomers in a
more than one linker. Further, the functionality that the linkers
Metal-Organic Framework with Triangular Channels. Science
bear can be designed such that it further protects the structure
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ACKNOWLEDGMENT imidazolate frameworks. Proceedings of the National Academy of
The author is thankful of the peer reviewer for meticulous Sciences 2006, 103 (27), 10186-10191.
checking on grammatical errors, the class of Green Chemistry, 18. Nguyen, N. T.; Furukawa, H.; Gándara, F.; Nguyen,
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Carbon Dioxide under Humid Conditions by Hydrophobic
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framework; PSM, post synthetic modification. 19. Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.;
Nguyen, S. T.; Hupp, J. T., Metal-organic framework materials
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Synthesis of Polyurethane Using Castor Oil Based and Kraft Lignin
Based Polyols: A Review
HyunJune Jun
KEYWORDS : Polyols; Castor Oil; Kraft Lignin; Polyurethane;
ABSTRACT: There is an increasing demand for renewable, sustainable and environmentally friendly materials to make polyols
instead of petroleum based material. The aim of this review is focused on chemical and non-chemical methods to make bio-based
polyol, which are used in the synthesis of polyurethane products. Castor oil based and kraft lignin based methods are both shown
to have comparable or even better effects on the properties of the polyurethane compared to the conventional petroleum based
polyurethane. The kraft lignin based method is concluded to be a more suitable alternative to our conventional petroleum based
method.
1. INTRODUCTION derived from woods are the "green" alternative options.

Polyurethane (PU) is an important class of polymer that has Vegetable oil is an interesting option due to its ready
a variety of applications, such as in coatings, adhesives, availability, inherent sustainability, bio-degradability and low
elastomers, foams, and fibers [1]. Polyurethanes are made by cost [2,5]. Lignin is one of the most abundant aromatic
reacting polyols with polyisocyanates, and its structure and substances on Earth [6,7], and it is derived from wood during
properties can be varied by using appropriate polyols [2]. pulp and paper making processes [8]. Lignin is also attractive
Today, most of the polyols used in the manufacture of due to its low cost, sustainability and ready availability.
polyurethanes are derived from the petroleum industry [3,4]. The aim of this manuscript is to describe the use of castor oil
However, petroleum is non renewable, has an increasing trend and kraft lignin in the synthesis of polyols and the overall
in cost, and its industrial processes raise environmental properties of polyurethanes made from castor-oil based and
concerns due to greenhouse gas emission. Thus, materials that kraft lignin based polyols.
are renewable and environmentally friendly are required for
future sustainability. The use of vegetable oil and natural lignin
2. CASTOR OIL Scheme 1. Synthesis of polyol from castor oil using
Castor oil by nature contains at least 80% of ricinoleic acid alcoholysis
[9]. Ricinoleic acid is an unsaturated fatty acid formed with 18
carbons and it contains a hydroxyl functional group at 12th
carbon, which can react with polyisocyanate to form
polyurethane [9]. The average number of hydroxyl group per
castor oil triglyceride is about 2.7 (figure 1) [5].
2.1 Synthesis of castor oil-based polyols
The triglyceride of castor oil already contains hydroxyl
group which can act as reactive site for polycyanate, but the
hydroxyl number is relatively low (157 mg KOH g-1) compared
to the commercial polyols (392 mg KOH g-1) [3,5]. This results
in a soft polyurethane due to low cross-linking density [5].
Hydroxyl number is the weight of KOH (mg) that will
neutralize the acetic anhydride capable of reacting by
acetylation with 1 g of polyol [8]. It is calculated by multiplying
total hydroxyl value in the polyol by the molecular weight of
KOH [8]. In order to overcome the low hydroxyl number of
castor oil, different approaches have been made.
Teramoto et al. [10] used glycerol, which is a 10% byproduct

of biodiesel production from vegetable oil [11], as a mixture
with castor oil to overcome the disadvantage of low hydroxyl
number when using castor oil alone. No polyol was
synthesized in their study, but rather the castor oil was directly
used with glycerol at differing ratio of castor oil/glycerol. The
mixture of castor oil/glycerol was reacted with a dissocyanate
compound, PEA-TDI, to yield polyurethane elastomers, and its
bio-degradability increased with an increase of castor
oil/glycerol ratio. However, even with the use of glycerol, direct
use of castor oil is limited to the production of elastomer and
Figure 1. Structure of triglyceride in castor oil other products having very weak intermolecular forces due to
Mosiewicki et al. [3] used the alcoholysis reaction to increase the intrinsic property of castor oil having a poor hydroxyl
the number of hydroxyl group in castor oil. The alcoholysis was number within its structure.
performed by reacting castor oil with triethanolamine in the De et al. [12] synthesized hyperbranched polyester polyol
presence of lithium hydroxide as catalyst at 150 °C. The (HBPP) from castor oil by a two step method. The first step
chemical reaction is presented in the scheme 1. After the was the alcoholysis reaction between castor oil and glycerol
reaction, the hydroxyl number of the polyol was determined to using sodium hydroxide as catalyst at 220 °C to form
be 449 mg KOH g-1 with a viscosity of 670 cP, compared to the monoglyceride of castor oil. In the second step, the
commercial polyol, 392 mg KOH g-1 with a viscosity of 12500 monoglyceride of castor oil was undergoes esterification
cP. When polyurethane foam was made using each of these reaction with 2,2-bis(hydroxylmethyl)propionic acid using p-
polyols, the castor oil based foam had thermal conductivity, toluene sulfonic acid (p-TSA) as catalyst at 140 °C. The
thermal stability and mechanical properties comparable or chemical reaction is presented in the scheme 2.
even better than the commercial polyol based foam. With
addition of filler (wood flour in the experiment) in the foam,
castor oil based foam had increased thermal stability, but
decreased mechanical properties and increased thermal
conductivity, which are important components in
polyurethane foam. Thus slight improvements are required for
such drawback, but it is still a good alternative to replace
petroleum-based polyols.
Scheme 2. Synthesis of HBPP from castor oil
The hydroxyl number of the synthesized HBPP was

determined to be 420 ± 8 mg KOH g-1. Instead of synthesizing a
polyurethane, De et al. synthesized a hyperbranched epoxy from
HBPP. The synthesized epoxy had an outstanding toughness,
flexibility, elasticity, with acceptable biodegradability and
thermostability. Even though hyperbranched epoxy and

polyurethane are different polymers, HBPP could possibly
contribute to the mechanical properties and thermostability of
polyurethane, thus using HBPP for polyurethane synthesis
could be an interesting study.
Zhang et al. [13] synthesized castor oil based flame-retardant
polyol (COFPL) in a three step process. First step was the
glycerolysis reaction between castor oil and glycerol using
sodium methoxide and triethanolamine as catalysts at 180°C, Scheme 3. Kraft lignin oxypropylation reaction
producing castor oil monoglycerides and diglycerides. In the The reaction produced oxypropylated kraft lignin, which is
second step, castor oil monoglycerides and diglycerides were a chain extension of kraft lignin, and propylene oxide
epoxidized using formic acid, phosphoric acid and hydrogen oligomers, which is an important co-polyol that decreases
peroxide. In the third step, the epoxidized products were viscosity and glass transition temperature of lignin polyol. The
mixed with toluene, diethyl phosphate and synthesized kraft lignin polyol had a hydroxyl value of 387 mg
triphenylphosphine, producing COFPL with 3% in KOH g-1. When the following polyol was reacted to form a
phosphorus content. polyurethane foam, the foam exhibited good mechanical
The synthesized polyurethane foam from COFPL showed properties due to the high crosslinking of the polyol. This
extremely high degree of crosslinking density, highlighting the method did not require adding extra polyol such as glycerol,
good mechanical property. The Limiting oxygen index test and the oxypropylated lignin polyol could solely be used for
(LOI), which is a test to measure the fire resistance of a polyurethane foam with better mechanical properties than
material, indicated LOI value increase to 24.3% compared to commercial polyurethane foam.
normal polyurethane foam, thus COFPL based polyurethane Mahmood et al. [15] produced kraft lignin based polyol via
had excellent fire resistance. direct alkaline hydrolysis. The lignin was reacted with distilled
Zhang et al. [2] synthesized soy-castor oil based polyol from water using sodium hydroxide as a sole catalyst at a
epoxidized soybean oil and castor oil fatty acid. The castor oil temperature increasing up to 350°C, without any organic
was saponified into fatty acid by heating with sodium solvent and capping agent. The resulting kraft lignin based
hydroxide solution, and the resulting fatty acid was mixed polyol had aliphatic-hydroxyl number in the range of 236-352
with epoxidized soybean oil to form the polyols. At the ratio of mg KOH g-1, which is a suitable value for synthesis of
1: 2 for castor oil and epoxidized soybean oil, the polyurethane polyurethane foam.
film showed higher thermal and mechanical properties It is important to note that in general, the aromatic hydroxyl
compared to castor oil based polyol and methoxylated soybean group has higher reactivity than the aliphatic hydroxyl group,
oil based polyol. Only vegetable oils are used as raw materials and because of this property, kraft lignin is more readily used
in the absence of catalysts and solvents to synthesize the as a filler rather than a polyol precursor [16]. The kraft lignin
polyol, making this method a green process. has both aromatic and aliphatic hydroxyl group within its
structure, thus it is favourable to use it directly without
3. KRAFT LIGNIN making any chemical modification to form a polyol.
Lignin is an amorphous polymer derived from p-coumaryl Chahar et al.[17] used kraft lignin from black liquor that is
alcohol, coniferyl alcohol, and/or sinapyl alcohol [14]. the three similar to the one produced by paper industry and combined it
structures are shown in figure 2. with a polyol, poly(ethyleneglycol), of different molecular
weight ranging from 300 to 4000. The mixture was directly
used without chemical modification of kraft lignin, since it
could already act as a polyol. The mixture was reacted with 2,4-
diisocyanate using stannous octoate as a catalyst to synthesize
a polyurethane coating. Higher concentration of polyethylene
glycol contributed to the softness and stickiness, while the
increase in lignin concentration contributed to the brittleness
and poor adhesion property. However, controlling the amount
of lignin and polyol resulted in better adhesion and shear
strength properties, and the increased thermal stability of the
coating was observed with the increase of lignin use.
Figure 2. Three building blocks of lignin
Similarly, Hatakeyama et al. [18] studied the effect of the ratio
Lignin contains a large number of aliphatic and phenolic of kraft lignin and poly(ethyleneglycol) polyol on the
hydroxyl groups, which offers good reactive sites for mechanical and thermal properties of the synthesized
polyisocyanates [1]. The main source of lignin nowadays is from polyurethane foam. The results showed increased rigidity with
the kraft pulping process, and its byproduct, the black liquor, the increase of lignin due to high crosslinking between
contains 30~34% of lignin[7]. About 55 million metric tons of hydroxyl and polyisocyanate groups. In terms of thermal
lignin are produced each year in the form of black liquor [6]. stability, the use of kraft lignin increased the glass transition
3.1 The use of kraft lignin for polyols temperature of the polyurethane foam, and its value was
Li et al. [1], made a liquid polyol by oxypropylation reaction competitive to the petroleum based foam.
from kraft pine lignin. The purchased kraft lignin was dried, Pan et al.[19] studied the effect of replacing polyether polyol
and mixed with propylene oxide and potassium hydroxide by the kraft lignin. Polyether-modified polysiloxane was used
under heating. The reaction is described in scheme 3. as a surfactant, and Tin(II)-isooctoate was used as a catalyst.
The reagents were used with a blowing agent and reacted with
methyl diphenyl diisocyanate to form polyurethane foam. The
polyether triol was replaced with kraft lignin up to 28% (w/w),

and the foam had good structure and mechanical properties at life cycle environmental impacts of many types of lignin are still
19~23% (w/w) in kraft lignin content. undocumented.
4. SUMMARY AND DISCUSSION It is difficult to choose which method between castor-oil
It has been shown that the castor oil-based polyol and kraft based or kraft lignin based is better in terms of physical and
lignin-based polyol are good alternatives for replacement of thermal properties of the synthesized polyurethane, since both
petroleum-based polyol in the synthesis of polyurethane methods are determined to have a competitive performance to
products. In general, when the castor oil-based polyol and kraft the petroleum-based polyurethane. Also, both methods for the
lignin-based polyol are synthesized into polyurethane, both synthesis of polyol are designed to use least or no amount of
show a competitive or even better performance in terms of solvents and use a simple catalyst.
mechanical and thermal properties. In some cases, more studies However, looking at how both materials are derived and
and improvements are needed to overcome some drawbacks. their ready applicability into the synthesis of polyurethane
Using unreacted castor oil as a sole reagent for synthesis of foam, the kraft lignin seem to be more a attractive option than
polyurethane is not a preferred pathway, since it does not castor oil.
contain enough hydroxyl group that offers reactive site for Kraft lignin is extracted from the industrial waste (black
isocyanate. Thus the synthesis of castor oil into polyols is liquor) that is produced during the kraft pulping process. Black
highly favored to increase its hydroxyl number. Castor oil liquor contains about 30-34% of lignin [7], and it is used as
based polyol can be made from the alcoholysis and glycolysis burning fuel, but it is not cleaner than a natural gas [21] in
reactions, and the synthesis can be done under solvent free terms of atmospheric emission. Thus, using the black liquor as
conditions using a catalyst. For more complex polyol such as a lignin source is an efficient way to treat and use this industrial
COFPL by Zhang et al, the synthesis may require more uses of waste. On the other hand, castor oil is derived from the raw
solvents and additional catalysts. The renewability, biomaterial, castor plants. Considering factors such as tractor fuel,
degradability and sustainability of the starting material make pump power and fertilizer required for farming, the cost for
castor oil based polyol a viable alternative for polyol and making castor oil may be more expensive than kraft lignin.
polyurethane industry. The extracted kraft lignin can be modified into liquid polyol,
Kraft lignin can be chemically modified to yield a lignin but due to its rich hydroxyl property it can also be used directly
based polyol, or it can be directly used as a sole reagent and in the synthesis polyurethane products and replace a portion of
mixed with the existing commercially used petroleum based the commercial petroleum based polyols. Castor oil, as
polyol to synthesize polyurethane products. Oxypropylation mentioned previously, does not contain high value of hydroxyl
and alkaline hydrolysis are main synthetic pathways known group to react with isocyanate, and it is a weak reagent to be
from the literature to derive polyols from kraft lignin. Both used directly in the synthesis of polyurethane without
methods involve a simple catalyst, and uses no organic solvents undergoing chemical modification. In most cases, castor oil has
or capping agent. The kraft lignin contains both aromatic and to be converted into a liquid polyol to produce different variety
aliphatic hydroxyl groups which can act as reactive sites for of polyurethane products that are comparable to the petroleum
isocyanate, thus recent studies incorporated commercial based polyurethane.
polyols such as poly(ethylene glycol) and polyether triol with Being able to use a material without undergoing a chemical
kraft lignin to synthesize polyurethane products. With the reaction is a great advantage. In the methods seen for castor oil
kraft lignin method, a portion of petroleum based polyol can be in the previous section, the alcoholysis and glycolysis involve
directly replaced by kraft lignin without undergoing a chemical reaction at a temperature up to 220 °C. Also for kraft lignin, the
modification. oxypropylation and hydrolysis reaction requires controlled
One major drawback for both methods is that the chemical temperature and pressure for the reactions to occur. These
reactions do not occur at a mild condition and require reactions do not occur at a mild condition, thus they require an
controlled temperature and pressure. energy input, which is a drawback for both methods in terms
of energy cost. However, compared to the petroleum based
Helling et al. [20] conducted a life cycle assessment (LCA) for
polyol synthesis, which requires multiple steps such as
the production of polyol using castor oil, soybean oil and
dehydrogenation, steam cracking and fluid catalytic cracking
petrochemical. It was found that if each polyol is made using
for making the compounds necessary for the reaction[22],
the same polymerizing initiator, propylene oxide (PO), the
castor-oil and kraft lignin based polyol synthesis are much
castor oil and soybean oil would use 33% to 64% of the fossil
simpler, less expensive, and the reaction processes are
resources compared to the petrochemical based polyol. The oil
environmentally benign in terms of greenhouse gas emission.
based polyol also generates -13%( sequestration) to 46%
greenhouse gas emission compared to the petrochemical based
polyol. 5.CONCLUSION AND OUTLOOK
Bernier et al. [21] also conducted a life cycle assessment of With the increase in demands of renewable, sustainable and
kraft lignin for polymer applications. The environmental environmentally friendly materials, the vegetable oil and
impact of kraft lignin is directly related to the kraft pulping natural lignin attracts more and more interests of researchers
process, since 130 million tonnes of kraft pulp corresponds to in the synthesis of polyols for polyurethane manufacturing.
total release of 55 million tonnes of kraft lignin [6]. Optimizing Castor oil and kraft lignin are among the green options for
the use of CO2, H2SO4 and NaOH in the kraft pulping process making polyols used in polyurethane. Different strategies
could further minimized the environmental impacts of kraft involving a chemical or non chemical modification for
lignin. The lignin can originate from different pulping synthesizing polyols were reviewed in this manuscript.
processes such as kraft, sulfite, soda or organosolv and from Between the two proposed methods, kraft lignin is concluded
different feedstock such as hardwood, softwood and straw, to be a more favorable alternative than castor oil.
thus the property of the synthesized polyol and its The castor oil based method requires to use castor as raw
environmental impacts can vary from one type to another. The material, whereas the kraft lignin is extracted from the
industrial waste in the pulping process, allowing for efficient

waste treatment finding and use for byproducts. Also, the kraft Kraft lignin. Chemical Engineering Research and Design 2009, 87 (9),
lignin can readily be used without chemical modification and 1276-1292.
can replace a portion of petrochemical based polyol to [8] Lora, J.; Glasser, W., Recent Industrial Applications of
synthesize polyurethane products. Lignin: A Sustainable Alternative to Nonrenewable Materials.
Nevertheless, researchers are still working to discover Journal of Polymers and the Environment 2002, 10 (1-2), 39-48.
alternatives that can replace petrochemical-based polyols for [9] Gu, R.; Sain, M., CHAPTER 6 Green Polyurethanes and
polyurethane synthesis. Vegetable oils and wood lignin will Bio-fiber-based Products and Processes. In Green Materials from
continue to be the focus of research. Plant Oils, The Royal Society of Chemistry: 2015; pp 127-146.
[10] Teramoto, N.; Saitoh, Y.; Takahashi, A.; Shibata, M.,
AUTHOR INFORMATION Biodegradable polyurethane elastomers prepared from isocyanate-
terminated poly(ethylene adipate), castor oil, and glycerol. Journal
Corresponding Author of Applied Polymer Science 2010, 115 (6), 3199-3204.
Email: [email protected] [11] Haas, M. J.; McAloon, A. J.; Yee, W. C.; Foglia, T. A., A
process model to estimate biodiesel production costs. Bioresource
ACKNOWLEDGMENT Technology 2006, 97 (4), 671-678.
[12] De, B.; Gupta, K.; Mandal, M.; Karak, N., Biodegradable
I thank the Department of Chemistry of McGill University and the hyperbranched epoxy from castor oil-based hyperbranched
editors of the McGill Green Chemistry Journal for the guidance, and polyester polyol. ACS Sustainable Chemistry & Engineering 2013, 2 (3),
their help was much appreciated. 445-453.
[13] Zhang, L.; Zhang, M.; Hu, L.; Zhou, Y., Synthesis of rigid
ABBREVIATIONS polyurethane foams with castor oil-based flame retardant polyols.
HBPP, Hyperbranched polyester polyol; COFPL, Castor oil based Industrial Crops and Products 2014, 52, 380-388.
flame retardant polyol; LOI, Oxygen index test; [14] Chakar, F. S.; Ragauskas, A. J., Review of current and
future softwood kraft lignin process chemistry. Industrial Crops and
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Green Alternatives for the Synthesis of Metal Nanoparticles
Philippe Green
KEYWORDS: Metal nanoparticle, green nanoscience, alternative synthesis, solution-based synthesis, biological synthesis
ABSTRACT: Metal nanoparticles are major components of the nanorevolution. Synthesis of metal nanoparticles is traditionally
achieved through solution-based methods, however increased concern over green chemistry has led to the development of alternative
syntheses. An essential element of a greener nanoscience is to develop alternative syntheses and make them known. Such alternatives
include photochemical, electrochemical, mechanochemical and biological methodologies. This review introduces these alternative
methods and how they can viewed as environmentally friendly, hazardless and sustainable. A particular focus is given to solution-
based and biological nanoparticle syntheses. The solution-based method offers control over the size and shape of the nanoparticles,
but is not easily scalable. The biological method offers the great advantage of employing renewable feedstock, benign solvents and
the possibility of making a wide range of nanoparticles. However this route has been found to be rather long and to yield
polydispersed nanoparticles. Multiple successful syntheses are described and, depending on the availability of materials and
equipment to the scientist, these methods can lead to a more environmentally friendly synthesis of metal nanoparticles.
As the nanorevolution grows with ever increasing funding, hazardless. One such solution would be the application of a
concerns have been voiced over the employment of novel green nanoscience to ameliorate current processes by
nanomaterials with regards to human safety and the eliminating waste and hazardous materials all through a
environment1. With the wide range of promising applications nanomaterial’s life cycle1. Green nanoscience, like green
that could use nanomaterials, much research should also go chemistry, attempts to reduce or eliminate hazards to human
towards making nanotechnology environmentally friendly and health and the environment through product design and
process optimization of nanomaterials1. Green nanoscience interactions40. Methods such as lithography, etching, electro-
conforms to the 12 principles of green chemistry postulated by explosion, sputtering, mechanochemical milling and laser
Paul Anastas1,2,3. Making nanoscience greener through green ablation processes are currently employed41. However the top-
chemistry is a major concern for the future application of down method results in numerous defects such as imperfection
nanotechnology. Hutchison1 described three ways in which of the surface structure40. The intent of this review is to
research should be approached for a greener nanoscience: introduce the multiple alternatives by which metal
1. Develop safer alternative materials nanoparticles can be synthesized, satisfying Hutchison’s1 first
2. Identify the design rules for new nanomaterials criterion for a greener nanoscience. This should permit the
3. Reduce the hazards and increase the efficiency of nanoscientist to take a justified decision depending on the size
nanomaterials production and shape desired as well as the availability of certain materials
and equipment. A particular focus is given to biological
Metal nanoparticles are of considerable interest because of
synthesis and solution-based methods. Microwave, ionic
their numerous physical, optical, electrical and catalytic
liquids, super critical fluids and sonication will be
properties (Figure 1)4. The physical properties of these
encapsulated by solution-based methods. Photochemical,
nanoparticles leads to different applications, for example the
electrochemical and mechanochemical routes will briefly be
catalytic performance of gold nanoparticles (AuNPs) is highly
discussed.
influenced by their size and shape5,6. Thus a size and shape
controllable synthesis of nanoparticles is of great utility for
their specific application. Nanoparticles are usually SOLUTION-BASED METHODS:
synthesised with four ingredients: the metal salt, a solvent, a Solution-based methods are extremely simple. A solution of
reducing agent and a protecting agent. Many methods are metal salt is added to a reducing agent like sodium borohydride
commonly used, mainly the solution-based methods4,57-21 that and a protecting agent like thiols. In the case of AuNPs the
use water as a solvent, various reducing and protecting agents reducing agent reduces AuIII to Au0, leading to the formation of
and heat. The Turkevich method7,8, which uses sodium citrate the nanoparticles4 (Scheme 1). The Turkevich method7,8, later
as the reducing and protecting agent with heat, results in the improved by Frens9, has been widely considered to be one of
spherical synthesis of 2 to 150 nm AuNPs, has been found to be the most successful methods for AuNP synthesis (Figure 2).
one of the more popular options for nanoparticle synthesis. The However this method has severe limitations, such as the low
success of the method for its simplicity and size and shape colloid content and the exclusivity of water as a solvent10.
control is undeniable, however this method has faced Another well know method, developed by Brust et al.11,
challenges in large scale production10,26,27. In addition, the push employs a two phase (water-toluene) reduction of HAuCl4
for a greener chemistry for nanoparticle production has with sodium borohydride and alkanethiols. The two phased
sparked considerable interest in cleaner synthesis methods. system permits the formation of water and organic soluble
Photochemical4,28,29, electrochemical30-34, mechanochemical35- colloids10. The downsides of this reaction are the small sized
38, biological13,39-81 methods are already well-developed subjects colloids, 1 to 10 nm, high polydispersity and cost, as well as the
of research. In addition, the use of microwave 82-88, ionic usage of a harsh reducing agent10,11,12. Sodium borohydride,
liquids89-93, super critical fluids94,95 and sonication96-98 have hydrazine hydrate, etc. may lead to absorption of hazardous
resulted in successful nanoparticle synthesis. The ideal chemicals on the surface of nanoparticles which could then
synthesis should be able, by simply modifying the initial lead to undesired toxicity13.
conditions, yield a wide range of nanoparticle size while being
monodisperse, soluble in aqueous and organic solvents, utilize
benign reagents and be inexpensive. Another consideration
should be the use of a chemical which can both act as a reducing
and protecting agent yielding a better atom economy.
2
Absorbance
1.5 Scheme 1: Formation of thiol protected AuNPs by NaBH4

1 reduction
0.5
The use of oleyamine (OLA) as a reducing and stabilising
0
agent10,14 has attracted some attention since OLA offers the
400 600 800 advantage of being commercially available and inexpensive10.
Wavelength (nm) The nanoparticle size can be tuned by the amount of OLA
Figure 1. UV/vis of 10 nm glucose reduced AuNPs, added to the reaction mixture and it can be prepared in
demonstrating the surface plasmon resonance band aqueous or organic solvents10,14. Another interesting synthesis
involves the use of β-D glucose (dextrose) as a reducing
There are two main ways to synthesize metal nanoparticles: agent15,16. β-D glucose has the advantage of being
the bottom-up and top-down approaches40,41. The bottom up environmentally benign and renewable15. The extent of the
approach (self-assembly) employs small building blocks, such reduction can be controlled by monitoring the temperature and
as molecules, and, one by one, these blocks are assembled to the pH of the reaction15. The β-D glucose reduced nanoparticles
form larger structures. Chemical and biological methods are can be stabilised by starch15. These nanoparticles could be
commonly used for this approach, which when employed to compatible with a biological medium15. β-D glucose can also act
nanoparticle synthesis can led to nanoparticles with fewer as the protecting agent in the form of a negatively charged
defects, more homogeneous composition and a better control monolayer of gluconic acid16.
of size and shape40. In the top-down approach, a bulk material
is reduced in size by means of physical or chemical Seed mediated synthesis has often been employed for the
formation of nanospheres and nanorods16,17. In this process, a

nanoparticle is synthesized and subsequently used as a seed for stabilising and protecting agent31,86. CMC, being a biomaterial
further growth of the particle. To do so, small nanoparticles in applied in the food and medical industries, has also been
solution are used as the seeds. To obtain negatively charged employed simultaneously as both a protecting and a reducing
nanoparticles, the seed solution can be added to an ethanolic agent87. A quite nice synthesis was performed using β-D
solution with 4-mercaptobenzoic acid (4-MBA) at pH 8 and to glucose as the reducing agent and starch as the protecting
obtain positively charged particles, ascorbic acid can be used agent to obtain 1 to 8 nm AgNPs using MW irradiation15.
with cetylmethylammonium bromide (CTAB) as the
protecting agent16. This method permits the control of IONIC LIQUIDS:
nanoparticle size and nanoparticle interactions with the Ionic liquids (ILs) have been perceived as an alternative
surrounding medium. Roberts et al.18 have successfully solvent compared to organic solvents, due to their undetectable
developed a seed mediated synthesis of palladium vapor pressure89. The great advantage of using ILs for
nanoparticles. They used a 3.4 nm sized seed prepared by an nanoparticle synthesis is that they can be tuned to serve as both
ascorbic acid reduction and carboxymethyl cellulose (CMC) as the reducing and protecting agent12,83 . ILs are ionic
the protecting agent. These seeds were then placed in a compounds, therefore solvation and protection of metal ions is
solution of Pd2+ and ascorbic acid to reduce the free ions which superior in ILs compared to conventional organic solvents12. ILs
then accumulated on the seed. This method offers an easy form a protective layer which provides both steric and
control of the nanoparticle size by using non-toxic reducing electronic protection against agglomeration90. Alcohol ionic
and protecting agents in ascorbic acid and CMC18. liquids (AILs) have been used due to their great reducing
capabilities in the formation of AuNPs12. Using
Multiple other environmentally friendly reducing agents as (HEMMor)(BF4), Kim et al.12 have reported that nanoparticle
well as ascorbic acid, such as amine borane complex5, caffeine19, size is dependent on the size of the alkyl chain; particles were
tea extracts19, heparin20, chitosan20, starch21 and CMC22 have smaller for longer chains. Imidazole ILs such as 1-n-butyl-3-
been used in successful nanoparticle synthesis. methylimidazolium, have been shown to be efficient green
catalyst for several reactions in multiphase reactions90. Dupont
and Scholten90 offer an extensive review of the use of ILs for
nanoparticle synthesis and list a large number of syntheses in
ILs.
SUPERCRITICAL FLUIDS AND SONICATION:
Supercritical fluids (SCFs) have been proposed as an
attractive alternative for nanoparticle synthesis due to their
gas-like diffusivities, continuously tunable solvent power and
ease of complete elimination at the end of the process94.
Supercritical CO2 has been the most often used SCF due to its
relatively low price and environmental friendliness94.
Supercritical water (scH2O) has also been used for the
synthesis Ce, Fe, Al, Ti, Cu and Zn metal oxides, however the
formation of metal nanoparticles is hampered by the formation
of metal oxides95. Supercritical alcohols, such as methanol and
ethanol, have thus been employed to serve as the solvent and
reducing agent95. Cu, Ni and Ag nanoparticles have been
synthesized this way95.
Figure 2. TEM image of 20 nm citrate reduced AuNPs
Sonochemistry, employs ultrasound to create acoustic
cavitation (the growth and implosive collapse of bubbles in
MICROWAVE ASSISTED METHOD: liquid)96. The collapse creates intense heating which produce
The use of microwave irradiation (MW) has been actively high temperatures and pressures for a few microseconds96.
employed for organic transformations in non-solid and solid Multiple semiconductor nanocrystals, such as ZnS, Sb2S3,
state reactions82-84. Pericyclic, cyclisation, aromatic HgSe, SnS2, CdS, CdSe, PbS, PbSe, PbTe and CuS97, have been
substitution and alkylation reactions are just few reactions produced using ultrasound. Sonoelectrochemical methods
that can easily be performed under MW irradiation 82-84. MW have been used for the synthesis of AgNPs97. Zhu et al.98 were
offers numerous advantages such as shorter reaction able to synthesise 3 nm gold nanocrystals using ascorbic acid
completion times and homogenous heating83. These advantages as the reducing agent when sonicated for 1 to 3 hours.
may be extremely useful for large scale nanoparticle synthesis
as the mixing and distribution of heat are critical for
PHOTOCHEMICAL SYNTHESIS:
controlling the size distribution of the nanoparticles26. Large Photochemical synthesis of metal nanoparticles is a cost
scale synthesis of silver nanoparticles (AgNPs) has been effective and convenient technique that allows controlled
demonstrated by Yin et al.26 by using silver nitrate, trisodium reduction of metal ions to be carried out without using excess
citrate and formaldehyde. This resulted in a higher yield and reducing agents, elimination of adsorbing contamination on
improved selectivity when employing MW heating as opposed the product during the preparation process, absorption of
to heating with convection. However the use of formaldehyde, radiation regardless of the presence of light-absorbing solutes
a volatile organic compound (VOC), as a reducing agent and and uniform reduction in solution28. This method has also been
solvent should be avoided. A much cleaner synthesis involves
used to synthesise nanorods29. UV irradiation has been used to
ethanol as a reducing agent and polyvinylpyrrolidone (PVP) as
improve the quality of AuNPs and near-IR laser irradiation has
protecting agent 85. Ethanol, being a benign solvent, and PVP,
led to the enormous growth of thiol stabilized AuNPs4.
which is non-toxic and soluble in many solvents31, makes for a
greener alternative. PVP has also been used as both the

ELECTROCHEMICAL SYNTHESIS: and do not require sunlight to grow. Certain yeast species
The electrochemical process developed by Reetz30 generally exhibit strong detoxification processes which lead to the
involves five steps: 1) oxidative dissolution of a sacrificial metal formation of nanoparticles42. Yeast has mainly been employed
bulk anode, 2) migration of metal ions to the cathode, 3) in the synthesis of semiconductors43, such as reported by
reductive formation of zerovalent metal atom at the cathode, 4) Dameron et al.42, who demonstrated that when Candida glabrata
nucleation and growth of metal particles and 5) arresting the and Schizosaccharomyces pombe yeast were challenged with toxic
growth process and stabilizing the nanoparticles with metals they produced extracellular cadmium sulfide quantum
protecting agents31. Electrochemical synthesis avoids the use dots. There are few examples of the use of yeast for the
of toxic reducing agents and the products can easily be isolated synthesis of metal nanoparticles, however several groups have
from the precipitate31. The size of the nanoparticle can easily be demonstrated its feasibility13. Kowshik et al.44 have performed
tuned by controlling the current density, distance between the the synthesis of 2-5 nm silver AgNPs using the silver-tolerant
electrodes, reaction time, temperature and solvent polarity31. yeast strain MKY3. Agnihotri et al.45 employed the yeast
An elegant synthesis was performed by Yin et al.32 in which Yarrowia lipolytica, due to its biological features required for
they produced AgNPs protected by PVP. PVP was found to interactions with metals, to intracellular synthesis of 15 nm
accelerate silver particle formation and to lower silver AuNPs.
deposition on the cathode. Another attractive possibility for
using electrochemical procedures is the possibility to form VIRUS:
nanorods with specific aspect ratios33. Viruses are small infectious agents that can be employed as
Mechanochemical synthesis: templates for nanoparticle synthesis. Tobacco mosaic virus
Conventional nanoparticle syntheses often rely on large (TMV) has often been employed as a template in light-
amounts of solvents, ligands, reducing agents, auxiliaries, harvesting systems46, metamaterials (negative index of
phase transfer agents, and purifications steps35. A refraction)47 and nanowires48. TMV has been shown to
mechanochemical procedure offers a scalable, low energy and successfully direct the mineralization of PbS and CdS
rapid synthesis without the use of solvents and reducing crystalline nanowires and the formation of Pt, Au and Ag
agents35. Mechanochemical processes are characterized by the nanoparticles40,48,49. However very little has been reported on
repeated welding, deformation and fracture of the reactants36. the synthesis of nanoparticles from viruses.
This has the consequence that reactions that would normally
require a heat input can proceed without external heating36.
BACTERIA:
Ultra-small AuNPs, 1 to 4 nm in size, have been made under
Bacteria produce inorganic materials either intra or
mild mechanochemical milling through a galvanic reduction35.
extracellularly, in the nanoscale dimension, due to their
The nanoparticles can be stabilised using amine ligands, which
chemical detoxification of most toxic heavy metals43. The
provide control over nanoparticle size35.
detoxification results in a reduction or precipitation of the
Biological synthesis:
metal ion into insoluble non-toxic metal nanoclusters43.
Bio-inspired nanoparticle synthesis has developed as a novel
Intracellular production of nanoparticles poses the extra
route for sustainable synthesis39. Many alternative organisms
challenge of extracting the nanoparticles, for which ultrasound
have been employed, such as yeast, virus, bacteria, fungi, plants,
or detergent treatments are required43. Extracellular synthesis
plant extracts and algae 13,39,40. The use of these organisms has
occurs when cell wall reductive enzymes or soluble enzymes
led to the production of low-cost, energy-efficient, and non-
secreted by the microorganism are involved in metal
toxic metallic nanoparticles while using renewable feedstock,
reduction43. Extracellular production has been found to be
limiting waste production and using safe solvents39,40.
readily applicable in many different applications, such as
Biological methods can also be complemented by the
optoelectronics, electronics, bioimaging and in sensor
application of microwave, sonication and visible-light
technology43.
irradiation13. According to Iravani41, three main rules should be
followed for successful biological synthesis of nanoparticles.
Slawson et al.50 have demonstrated that Pseudomas stutzeri
1. Selection of the best organism: Focus should be put on the
AG259, a bacterial strain isolated from silver mines,
important intrinsic properties of the organism such as
synthesised 35 to 46 nm AgNPs in its periplasmic space. This
enzyme activity and biochemical pathways. For examples, was a rather surprising result as silver has often been
plants that have the potential to accumulate and detoxify considered to be an antimicrobial agent51, 52. However many
metals are good candidates. other groups53-56 have found that microorganisms can
2. Optimal conditions for cell growth and enzyme activity: effectively be used for metal nanoparticle synthesis. Bacteria
For optimal conditions, the nutrients, inoculum size, light, such as Morganella sp. RP-4253, Lactobacillus54, Brevibacterium
temperature, pH, mixing speed and buffer strength should casei55, Shewanella algae13 and even cyanobacteria such as
be adjusted for the best cell growth. Plectonema boryanum UTEX 48557 have been used to synthesise
Ag, Au, Pt and Au/Ag nanoparticles. Escherichia coli DH5α58 has
3. Optimal reaction conditions: To obtain the best also been found to mediate intracellular bioreduction of auric
nanoparticle yield, the bioreduction conditions must acid to Au0 nanoparticles. Rhodopseudomonas capsulata59, a
be optimized. The substrate concentration, the bio- photosynthetic bacterium produced extracellular AuNPs with
catalyst concentration and the electron-donor size and shape varying according to the pH. At pH 7 10 to 20
concentration, as well as the pH, temperature, nm spherical nanoparticles were produced while at pH 4 a
exposure time, buffer strength, mixing speed and mixture of 50 to 400 nm triangular nanoparticles and 10 to 50
light, must be adjusted. spherical nanoparticles.
YEAST:
Yeast are very common eukaryotic microorganisms. They are
chemoorganisms in that they use organic compounds as food

Table 1: Biological Synthesis of Metal Nanoparticles
Microorganism or plant Nanoparticle Size (nm) Intra or extracelluar Reference
Yeast
MKY3 Ag 2 to 5 Extra 44
Yarrowia lipolytica Au 15 Intra 45
Bacteria
Pseudomas stutzeri AG259 Ag 35 to 36 Intra 50
Morganella sp. RP-42 Ag 15 to 25 Extra 53
Lactobacillus Au 20 to 50 Intra 54
Ag 15 to 500 Intra 54
Brevibacterium casei Au 10 to 50 55
Ag 10 to 50 55
Shewanella algae Au 9.6 Intra 13
Pt 5 Intra 13
Plectonema boryanum UTEX 485 Ag Up to 200 Intra extra 57
Escherichia coli DH5α Au 17 to 33 Intra 58
Rhodopseudomonas capsulate Au 10 to 20 (pH 7) 59
Au 8 Extra 60
Thermonospora sp
Ag 28.2 to 122 56
Klebsiella pneumonia
Fungi
Verticillium Ag 13 to 37 Intra 61
Aspergillus fumigatus Ag 5 to 25 Extra 62
Trichoderna asperellum Ag 13 to 18 Extra 63
Verticillium luteoalbum Au <10 Intra 64
Au 8 to 40 Extra 65
Colletotrichum sp
Plants and plant extracts
Pelargonium graveolens Ag 16 to 40 66
Coffee extracts Ag, 20 to 60 19
Ag 20 to 30 67
Pd 20 to 60 19
Tea extracts Ag, 20 to 60 19
Ag 20 to 90 68
Pd 20 to 60 19
Au 200 to 500 69
Cymbopogon flexuosus Ag 10 to 35 70
Citrus sinensis Ag, Au - 71
Swietenia mahogany JACQ Au 14 72
Hibiscus rosa sinensis Ag 13 72
Au 6.5 to 17 73
Anacardium occidental Ag 15.5 73
Pd 2.5 to 4.5 74
Ag 4 to 30 75
Ocinum sanctum Au 12 to 38 76
Ag 50 to 80 77
Morinda citrifolia
Nyctanthes arbor-tristis
Algae
Spirulina platensis Ag 7 to 16 78
Au 5 to 10 79
Eolimna minima Au 5 to 80 80
One of the main issues with such syntheses is high particular applications where the shape and size have to be
polydispersity. Ahmad et al.60 have demonstrated that controlled with high precision.
Thermonospora sp, an extremophilic actinomycete, can yield
extracellular monodispersed 8 nm AuNPs. These syntheses FUNGI:
have been found to be rather slow, a strong barrier to industrial Fungi have many advantages for metal nanoparticle synthesis
applications. Shahverdi et al.56, in order to solve this problem, compared to other microorganisms due the presence of
employed Klebsiella pneumonia, Escherichia coli and Enterobacter enzymes, proteins and reducing components on the cell
cloacae. They reported that within 5 minutes of silver ion surface13. In addition, fungi are fastidious to grow, easy to
coming in contact with the cell filtrate, AgNPs were formed handle and easy for fabrication, and the nanoparticle
employing MW irradiation. In order for bacteria to be readily precipitated outside the cell is devoid of unnecessary cellular
implemented in large scale production, the speed and components43. They are taking center stage for biological
polydispersity both have to be accounted for. This lack of nanoparticle synthesis due to their tolerance and metal
control makes these types of synthesis much less attractive for bioaccumaulation capabilities40. Verticillium has been used by

Mukherjee et al.61 for the synthesis of 25±12 nm AgNPs. Fungi greening process in which benign solvents, reducing and
such as Aspergillus fumigatus62 and Trichoderna asperellum63 have protecting agents have been employed. Much progress has been
been used to synthesize AgNPs. Verticillium luteoalbum64 made in perfecting solution-based synthesis by using sugars or
produced <10nm AuNPs at pH 3 and a mix of spheres and rods plant extracts as reducing and protecting agents.
at higher pH in 24h while Colletotrichum sp65 produced 8 to 40 Electrochemical and mechanochemical processes offer a wide
nm AuNPs. range of advantages, such as the absence of a reducing agent
and scalability. Most of the research, however, has gone into
Plants and plant extracts: the very promising field of bioinspired synthesis of metal
Plants have shown great potential in heavy metal nanoparticles. This method employs the intrinsic properties of
accumulation and detoxification13. Numerous plants and fruits bacteria, yeast, virus, fungi, etc. to advantage to synthesise
have been shown to reduce and stabilize both single and multi- nanoparticles in a wide range of size and shapes. Much work
metal nanoparticles in one-pot photosynthesis13. This method has to be done to obtain monodispersion and better kinetics
has found great use due to the rapid formation of nanoparticles but this method should be regarded as a very good alternative
compared to other bioinspired methods. Geranium leaves for the near future.
(Pelargonium graveolens) has been shown to produce 16 to 40 nm
AgNPs in only 9h compared to the 24 to 124 hours required AUTHOR INFORMATION
when using fungi or bacteria40,66. Varma et al.19 have reported Philippe Green
the synthesis of Ag and Pd nanoparticles at room temperature
using coffee and tea extracts. For coffee extracts, Dhand et al.67 Department of Chemistry, McGill University, Montreal, Qc
also performed the synthesis of 20 to 30 nm AgNPs and for tea
leaf extract, Sun et al.68 also performed the synthesis of 20 to 90 ACKNOWLEDGMENT
nm AgNPs. This method required no usage of a capping agent,
Thanks to Professor Moores and Professor Rogers as well as the
is environmentally friendly and can be extended to Au and Pt
editors of the journal.
nanoparticles19. Lemongrass, Cymbopogon flexuosus69, was used in
a single step procedure at room temperature to synthesize ABBREVIATIONS
triangular gold nanoprisms. Citrus sinensis peel70 was employed
to prepare AgNPs at room temperature and 60°C. At room AuNPs: Gold nanoparticles; OLA: oleyamine; 4-MBA: 4-
temperature, the nanoparticles were approximately 35 nm mercaptobenzoic acid; CTAB; Cetylmethylammonium
while at 60°C they were approximately 10 nm. Therefore size bromide; CMC: Carboxymethyl cellulose; MW: Microwave;
control can be achieved by varying the temperature. Other AgNPs: Silver nanoparticles; VOC: volatile organic compound;
extracts such as mahogany leaves (Swietenia mahogany JACQ)71, PVP: Polyvinylpyrrolidone; ILs: Ionic liquids; AILs: Alcohol
Hibiscus rosa sinensis72, Anacardium occidental73,74 and Tulsi leaf ionic liquids; SCF: Super critical fluids; TMV: Tobacco mosaic
(Ocinum sanctum)75 have been used to synthesize Ag, Au, Pd and virus
Au/Ag nanoparticles. Roots extracts have also been used. A
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Current Developments in Green Chemical Extraction Techniques of
Lignocellulosic Materials: Implications to Next-Generation
Biorefineries
Bryan H. Lee
KEYWORDS: Green Chemistry, Biorefineries, Biomass, Extraction Techniques, Ionic Liquids, Supercritical CO 2
ABSTRACT: Biomass offers one of few sustainable alternatives to fossil fuels as a source of renewable carbon. In light of growing
concerns by society on the negative impacts of fossil fuels on the environment, and their inevitable depletion, research into the
development of chemical technologies to harness biomass (i.e. the biorefinery concept) has been extensive. It is important,
however, to realize that biorefineries are not inherently green – as outlined by the 12 Principles of Green Chemistry by Paul Anastas
and John Warner. The initial processing steps of many next-generation biorefineries will involve the extraction of natural
polymers and other valuable materials from lignocellulosic biomass. At the moment, conventional means of dissolving and
extracting cellulose from lignocellulosic materials involve very harsh solvents and reagents that are toxic and harmful to the
environment. This review focuses on current developments of two alternative green chemical extraction techniques that have
garnered significant attention in recent years: the use of ionic liquids and supercritical carbon dioxide. The applicability of these
methods to future next-generation biorefineries are discussed and current progress, challenges and future goals are highlighted.
INTRODUCTION growing unsustainability of a primarily fossil-dependent

In light of substantial data that has accumulated in the society. Currently, fossil-based energy resources constitute
literature in recent years concerning the contribution of fossil about three-quarters of the world’s primary energy
fuels to climate change1-3, and the rapid depletion of the world’s consumption.4 To add to this problem, crude oil has become
accessible fossil reserves2,4, we can no longer be ignorant of the important feedstocks in the manufacture of many consumer
products including: plastics, fertilizers, clothing, cosmetics and A significant challenge to the development of extraction
building materials.1,5 In the years to come, the transition from a techniques for next-generation biorefineries involve the vast
fossil-dependent society will be achieved in two steps: 1. radical array of different biomass feedstocks that will be utilized by
reform in the management of existing fossil fuel-based future supply chains. These feedstocks include: low-value
systems6; and 2. the development of technologies to utilize plants such as trees, grasses and heathers; byproducts from
renewable energy resources.5 To this end, the refinery of energy and food crops; and marine resource and food wastes.9
biomass (i.e. biorefinery concept) have been predicted by many This review will focus on the development of two solvent-
to be the eventual successor to fossil fuels and oil-based based green chemical extraction techniques that have garnered
refineries.5,7-9 Biomass is abundant, renewable (i.e. with cycle a lot of interest in the literature in recent years; namely, the use
times on the order of years) and is a sustainable source of of ionic liquids7,12 and supercritical CO2 (scCO2) 9,10 for the
carbon.7 Many proponents of biomass have also claimed that treatment of lignocellulosic (i.e. plant-based) feedstocks. These
the use of biofuels is carbon-neutral as the carbon dioxide methods will be assessed according to the twelve principles of
generated in the energy conversion will be sequestered back green chemistry – as defined by Paul Anastas and John Warner
into biomass in the biogeochemical cycling of carbon.4 – and their current progress and challenges will be outlined, as
It is important to realize however that biorefineries are not well as future goals for implementation in next-generation
biorefineries.
inherently green. The incorporation of green chemistry
principles to the development of next-generation biorefineries
will be pivotal in the realization of a truly sustainable CELLULOSE FROM LIGNOCELLULOSIC BIOMASS:
alternative to conventional fossil-based supply chains. These CURRENT DEVELOPMENTS
principles include: maximum utilization of the feedstock mass
in the final product (i.e. atom economy), minimized energy
demands, utilization of safer processes and materials and the Lignocellulose is the principal component of plant cell
generation of products that are non-toxic and totally walls.13 It is mainly composed of cellulose, hemicellulose and
biodegradable.7 Thus, it is imperative that we extend beyond lignin, as well as smaller amounts of pectin, proteins, ash, and
simply the use of renewable feedstocks in any discussion other valuable extractives (e.g. nonstructural sugars,
concerning the development of green and sustainable nitrogenous materials, chlorophyll and waxes).13 The exact
biorefineries. composition of plant biomass can vary significantly from one
species to another, with important implications to the
Figure 1 depicts an outline of some important extractives, and properties of the plant material.7,13 For instance, hardwood
their downstream chemicals, that can be obtained from contains greater amounts of cellulose, whereas wheat straw
biomass.7 contains more hemicellulose.13 The relative amounts of
The operation of the idealized biorefinery can be divided into cellulose, hemicellulose and lignin of some common plant
two parts: 1. production of high-value low-volume (HVLV) feedstocks are given in table 1 (adapted from Kumar et al.).13
extractives; and 2. The conversion of low-value high-volume Cellulose is an important precursor for the generation of
(LVHV) intermediates into energy and fuel products. 8 As many useful bio-platform molecules, such as lactic acid,
shown by figure 1, the extraction of natural polymers from levulinic acid and succinic acid.7 However, the large majority of
biomass will constitute the initial processing steps of many cellulose in lignocellulosic materials remain inactive, or
next-generation biorefineries.7-10 Thus, the development of unavailable for direct modification from unmodified
efficient and environmentally benign extraction techniques biomass.13,14 Thus, the pretreatment of plant biomass to
will be an area of research with important implications to the separate, or expose cellulose in lignocellulosic materials is an
development of green biorefineries in the years to come. important step that can greatly improve the efficiency and
costs associated with the manufacture of chemical products
derived from plant biomass.7,13 Traditional methods of cellulose
extraction involve the utilization of acid hydrolysis processes13
or the treatment of cellulose with carbon disulfide in alkali
conditions to prepare cellulose xanthate (viscose).7,14 However,
these techniques suffer from several drawbacks, including high
energy demands, harsh reaction conditions and significant
solvent wastes.7,13,15
Table 1. Relative Amounts of Cellulose, Hemicellulose and
Lignin in Some Common Plant-Derived Feedstocks13
Lignocellulosic Cellulose Hemicellulose Lignin
Material (%) (%) (%)
Hardwood 40-55 24-40 18-25
Softwood 45-50 25-35 25-35
Nut Shells 25-30 25-30 30-40
Corn Cobs 45 35 15
Grasses 25-40 35-50 10-30
Figure 1. Simplified biorefinery flowchart including some of the Wheat Straw 30 50 15
extractives and downstream chemicals to be discussed in this
report.

Waste Papers 60-70 10-20 5-10 solubility of cellulose in various IL solvents, the reader is
from Chemical directed to a review by Marsh et al. (2009).20
Pulps A major limitation to ILs is often related to compromises
between its rheological properties and solubilizing power
Solid Cattle 1.6-4.7 1.4-3.3 2.7-5.7
when designing ILs for industrial applications.16 Furthermore,
Manure
the solubility of cellulose in ILs was found to be highly sensitive
Reprinted (adapted) with permission from (Kumar, P.; to water impurities.16 In particular, significant impairment to
Barrett, D. M.; Delwiche, M. J.; Stroeve, P., Methods for the solvent properties of ILs was observed for concentrations
pretreatment of lignocellulosic biomass for efficient hydrolysis of water as low as 1 wt %.16 There have also been some
and biofuel production. Industrial & Engineering Chemistry disagreements in the literature21-23 as to whether ionic liquids
Research 2009, 48 (8), 3713-3729.). Copyright (2015) American are really “green”, owing to the toxicological properties and
Chemical Society. environmental impacts associated with some IL solvents.
Additionally, the large-scale use of microwave heating in
industrial applications have been the subject of some scrutiny
Ionic Liquids in the green chemistry community based on the sixth principle
Ionic liquids (ILs) refer to a class of organic salts that exist in of green chemistry, concerning the energy efficiency of
the liquid state at relatively low temperatures (< 100 °C). 15 In microwave-assisted methods.24
recent years, there has been significant interest in the use of
ionic liquids as environmentally-friendly alternatives to
conventional industrial solvents, such as volatile organic FRACTIONATION OF SECONDARY METABOLITES
compounds (VOCs).17 Some of the advantages to ionic liquids FROM WHEAT STRAW
in the context of green chemistry are as follows: 1. ionic liquids
are non-volatile, and therefore do not contribute to the Supercritical CO2
pollution of VOCs into the atmosphere17,18; 2. they possess very
Wheat straw is a LVHV agricultural byproduct with
good solubilities for a wide range of inorganic and organic
important uses to next-generation biorefineries as a source of
materials, thus requiring less volumes of solvent18; and 3. they
hemicellulose13, and other valuable secondary metabolites such
can be designed to be environmentally benign.17 Furthermore,
as waxes.9 Natural waxes exist as complex mixtures of long
the fine-tuning capabilities of ionic liquid solvents are
fatty acids and alcohols, sterols and alkanes.25 They have a wide
extensive, allowing for the optimization of reactions (i.e. yield
range of industrial applications, including: cosmetics, polishes
and selectivity) through the utilization and design of ionic
and coatings.25 Conventionally, the extraction of these waxes
liquid solvents.18
involve harsh volatile organic solvents including: hexane,
The development of ionic liquids to dissolve cellulose has chloroform, dichloromethane and benzene.25 In addition to the
been significantly advanced by the work of Rogers et al. in environmental and toxicological concerns associated with
recent years.16 In particular, solubilities of up to 25 wt % were these solvents, these methods are often highly unselective,
achieved by the Rogers group (2002) using ionic liquids, resulting in the co-extraction of many unwanted compounds
containing 1-butyl-3-methylimidazolium cations ([C4mim]+) (i.e. < 50% of wax present in total extract for most organic
and chloride anions, with pulsed microwave heating.16 This solvents).25 Thus, there is a need for alternative
was in comparison to typical solubilities around 10 wt % using environmentally-friendly, non-toxic and selective extraction
dimethylacetamide (DMAC)/LiCl binary solvent systems that methods for waxes from bulk lignocellulosic materials.25
have also been explored extensively in the literature for the
The use of supercritical fluids (SCF), and in particular,
environmentally-friendly, and non-derivitizing extraction of
supercritical CO2 (scCO2), for the extraction and fractionation
cellulose from biomass.16,19 The solubility of cellulose is
of waxes from wheat straw has been explored extensively in
primarily dependent on the ability of the solvent molecules to
the literature.9-10,25 Supercritical fluids refer to substances that
disrupt and penetrate the robust, intramolecular hydrogen-
are taken above its critical temperature and pressure.26 At this
bond network of supramolecular cellulose structures.16,19 It is
state, a single homogeneous fluid is formed with both gas- and
believed that the solubilizing power of these solvents is directly
liquid-like properties. Table 2 summarizes the general
related to the activity of the chloride ions in these solvent
differences in the densities, viscosities and diffusivities of gases,
systems – and in particular, the mobilization and interaction of
liquids and SCFs (data from report by Baiker).27
these chloride ions with the cellulose hydroxyl groups.16,20
Thus, ionic liquids present an intrinsic advantage over
conventional solvent systems, such as DMAC/LiCl, in that: 1. Table 2. Comparison of Some Physical Properties of Gases,
the effective concentration of Cl- ions is not limited by the Liquids and SCFs in the near critical region (data taken
solubility of the salt in the case of ILs; and 2. the fine-tuning from ref 27).
capabilities of the ion constituents in ILs provide significantly Dynamic Diffusion
more control over the activity and mobilization of the active Density
ions (i.e. Cl-).20 State Viscosity Coefficient
[kg·m-3]
There has been substantial progress in the development of [mPa s] [106 m2 s-1]
new IL systems for the dissolution of cellulose.20 In general, IL Gas 0.6-2 0.01-0.3 10-40
systems with cations based on methylimidazolium (MIM) and SCF 200-500 0.01-0.03 0.07
methylpyridinium (MPy) cores have been found to yield the
greatest success.20 Furthermore, small anions (i.e. hydrogen Liquid 600-1600 0.2-3 0.0002-0.002
bond acceptors), and chlorides in particular, have been shown
to be most effective for cellulose dissolution.16,20 For a full SCF systems for extraction often employ scCO2 due to its
comprehensive table of current results achieved for the relatively low critical parameters (i.e. 31.1 °C and 73.8 bar), low
cost and non-toxicity.26 The main advantages to scCO2

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Endangered Element: A review on palladium

Luca Poli
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, Canada, H3A 0B8
KEYWORDS: Catalysis, Palladium, Endangered, Depletion

ABSTRACT: Platinum group elements have found increasing uses as catalysts yet they are quickly becoming excessively expensive
and scarce. Palladium’s main uses are in automotive catalysis and as a catalyst in the chemical industry. This review investigates the
causes for resource depletion and provides alternatives to replace palladium with greener and more sustainable solutions. Fuel cells
for catalytic converters and biocatalysis for catalytic reactions are promising options in both fields, however both come with their
own downsides.
INTRODUCTION it to find many uses in modern technologies, especially by

replacing other PGE’s in catalysis because of comparatively
reduced toxicity [9], cost and improvements in efficiency.
We all recognize the value and benefits to mankind that
Nevertheless, palladium is still considered acutely toxic
chemistry has given us, however we often take for granted
[10], its price has tripled in the last five years and concerns
how these precious metals are extracted and produced. The
over scarcity are now emerging.
expectations of modern society for improved safety, lower
environmental impact, more sustainable practices and USES
lower energy use at a fair cost place tremendous demands
and responsibility on us as scientists. The complex task of Palladium has been used in jewelry, dental fillings [11],
the chemical industry is to balance current knowledge with computers, mobile phones, televisions, alloys for electrical
the robustness and durability of chemical processes used contacts and ceramic capacitors [12]. However, palladium’s
with these regulatory pressures and escalating costs. This principal use is in catalysis, especially automotive catalysis.
review will examine the difficulties faced when balancing As cars have become more common in society and our
technological advancements, environmental concerns and awareness of climate change has increased, demand for
scarce resources by assessing palladium’s use in modern catalytic converters has increased with it. Catalytic
society. converters are estimated to use 80% of all palladium used in
2015 [13].
Palladium’s discovery was made public in 1805 when

William H. Wollaston spoke in front of the Royal Society Chart 1: Breakdown of global palladium use in different
of London and declared he had obtained a novel metal sectors for 2014
through dissolving residues left from platinum in aqua
regia, which is a concentrated solution of hydrochloric and 9%
nitric acids [1]. Wollaston, who had discovered rhodium in Autocatalyst
the same year [2], had discovered palladium two years
before this however he explained he had remained 20% Jewellery
anonymous so that he would have time to understand and
explain all of the metal’s properties before putting his name 69% Industrial
to account [3]. Palladium is part of the platinum group 2%
Investment
elements (PGE) along with iridium, osmium, ruthenium,
rhodium and platinum. Palladium has a shiny, lustrous,
silvery-white appearance. At ordinary temperatures it is
strongly resistant to corrosion in air and to the action of
acids [4], it has the ability to diffuse large amounts of
hydrogen [5], it has good electrical and optical conductivity
[6], and it can form alloys to improve ductility [7] and
durability [8]. Palladium’s unique properties have allowed
Supply 2011 2012 2013 2014 2015
South Africa 2,560 2,320 2,464 2,125 2,480
Russia 3,480 2,890 2,610 2,628 2,600
Others 1,320 1,320 1,300 1,351 1,323
Total Supply 7,360 6,530 6,374 6,104 6,403
Gross Demand
Autocatalyst 6,155 6,705 6,958 7,351 7,457
Jewellery 505 445 355 279 245
Industrial 2,465 2,350 2,192 2,125 2,074
Investment -565 470 -8 932 -400
Total Gross Demand 8,560 9,970 9,497 10,687 9,376
Recycling -2,385 -2,290 -2,525 -2,750 -2,873
Total Net Demand 6,175 7,680 6,972 7,937 6,503

Difference 1,185 -1,150 -598 -1,833 -100
Table 1: A summary of global demand & supply for catalytic converter composed of rhodium, platinum and
palladium over the last 5 years palladium in differing ratios depending on the type of engine,
stabilized by cerium and zirconium. They are used to convert
Coupling reactions in the chemical sector have benefitted carbon monoxide (CO) and unburnt hydrocarbons (HC) to
hugely from palladium, from the Suzuki reaction of aryl
carbon dioxide (CO2) and water (H2O), while also reducing
halides and boronic acids [14] to the first discovered
oxides of nitrogen (NOx) to nitrogen (N2) and oxygen (O2)
palladium-catalyzed coupling reaction between a
Grignard reagent and an organic halide [15], they have [21]. Catalytic converters have been hailed as great tools for
become quintessential in organic synthesis. Coupling fighting climate change, however they have many limitations
reactions provide useful ways to form C-C, C-N and C-O in terms of functionality.
bonds between different hydrocarbon fragments, they
Due to scarce natural occurrence of PGE’s, several
have been used extensively in the pharmaceutical, fine
chemical and agrochemical industries [16]. Many environmental impacts are accrued in the process of mining
pharmaceutical companies have used coupling reactions and extraction, which must be taken into account when
as key steps in synthesis involving palladium as a catalyst examining the environmental impact of modern catalytic
[17]. converters. A life cycle assessment (LCA) of a catalytic
converter for passenger cars found that the electrical
consumption during mining and extraction needed to
Estimates of palladium abundance in the earth’s crust vary
produce one catalytic converter is 110 MJ. Electricity
from 0.015-0.0063 ppm [18], this places it as one of the
production in South Africa is mainly based on coal-fired
rarest metals on earth [19]. The ‘Chemistry Innovation
Knowledge Transfer Network’ has signaled a warning power stations; thus, it contributes significantly to a
because of the limited availability of palladium and the substantial amount of coal use corresponding to
increased demand in recent years. The price of palladium 11kg/catalytic converter [22]. Enforcing stricter emissions
saw a ten-fold spike in 5 years between 1996 and 2001 due control may also be counterintuitive, as car manufacturers are
to uncertain global supplies and increased demand, it has forced to advance catalyst technology. The solution may be
since decreased to 547 USD/ozt (correct as of 16/11/2015) concluded with a higher use of PGE’s. The benefits accrued
however the historic trend has been one of steady from reduced emissions may be outweighed by
increase. As is illustrated in Table 1, global demand has environmental impacts of the mining and extraction of PGE’s.
outstripped supply for four years running, despite For instance, a fuel cell vehicle under current development as
increases in recycling, and the trend is set to continue in an alternative for zero car exhaust emissions requires at least
the coming decade as emerging economies develop and 10 grams of PGEs, significantly more than that of a car
demand for cars increases. Recent reports by Johnson & installed with a catalytic converter [22]. Another LCA study
Matthey’s have pointed to Russia’s decreased supply as a concluded that the second greatest environmental burden of
sign that stockpiles may be close to exhaustion.
catalytic converters after CO2 emissions is due to the
Geopolitical instabilities in South Africa and Russia, the
chemical constituents of the catalyst, almost solely based on
largest extractors of palladium, may also cause decreases
in supply and price fluctuations. the addition of palladium [23].
Studies performed on airborne particulate matter and road

Palladium is becoming an endangered element; its current dust found increased levels of palladium in urban areas
use is unsustainable. This, however, does not mean that compared to rural areas due to automotive catalysts [24]. As
we will run out of palladium. Instead, mining will become a metal, palladium will bio-accumulate in the environment
prohibitively expensive and companies will no longer be and once a certain concentration is reached, 10 ppm according
able to profit. This will in turn force car manufacturers, to the European Medicines Agency (EMA) [25], negative
technology companies and industrial chemists to find health effects from palladium exposure will start to be seen;
alternatives. By applying the ’12 Principles of Green dermatitis, stomatitis, skin irritation and cancer. “Chemical
Chemistry’ [20] (PGC) to current chemical processes in products should be designed so that so that at the end of their
the two largest sectors where palladium is used. This
function they do not persist in the environment and break
review will aim to provide an insight into the current
down into innocuous degradation products” [20] (PGC-10).
advancements being made to tackle the problem of
depleting palladium. “A raw material of feedstock should Current advancements in catalytic converters are diverse;
be renewable rather than depleting whenever technically increasing efficiency of key catalytic reactions [26], synthesis
and economically practicable” [20] (PGC – 7).
of ‘bio-palladium’ based catalysts [27], improved recyclability
of catalytic converters in diesel cars through acid washing
[28] and novel catalytic systems such as PremAir® which
CATALYTIC CONVERTERS directly reduce ground level ozone to oxygen [29]. This is
great chemistry in itself, but it has misunderstood the true
meaning of green chemistry. Instead of trying to improve the
A multitude of different catalytic converters have been efficiency of catalytic converters we should be looking to
developed, most modern automobiles use a three-way eliminate the need for them at all. In turn reducing the need

for palladium and its consequential environmental also been used in Suzuki coupling reactions [41][42].
implications. However both syntheses still use palladium as a catalyst.
Fuel cells, especially polymer electrolyte fuel cells (PEFC’s), Biocatalysis, which is the act of performing catalytic
appear to be a good alternative however the need for larger reactions in living organisms, is uniquely suited to the
amounts of PGE in the catalyst, due to low temperatures development of green chemistry routes for complex
(80°), high acidity and a difference in kinetics between molecules. High selectivity, mild conditions [43], low cost, no
reactions at the anode and cathode side [30], has held fuel risk of bioaccumulation and use of renewable feedstock
cells back. Fe- and Co-based electrocatalysts for this reaction makes enzymatic catalysis a good candidate to replace
have been studied for over 50 years, but they were palladium-based catalysts. Biocatalysis has been applied to
insufficiently active for the high efficiency and power density pharmaceutical syntheses [44] at the industrial scale and is
needed for transportation fuel cells. PEFC catalysts have also gaining momentum as a viable alternative to metal-based
suffered from fast degradation rates [30]. Recent catalysts. On the other hand, enzymes will require solvents to
developments in PFEC technology has allowed non-precious function.
metal catalysts (NPMC’s) to be used for oxygen reduction;
cyanamide- [31] and polyaniline- derived [32] NPMC’s have CONCLUSION
been established. Studies into degradation rates have found
there to be a trade-off between lifetime of catalyst and
activity [33], but further work needs be performed on In this review data has been presented to show the various
optimizing the relationship. However we must not forget uses of palladium contributing to its current increase in
that the sustainability of PEFC’s will invariably depend on demand, which will soon make it prohibitively expensive to
the production, storage and transportation of hydrogen. No mine forcing different industries to look for alternatives. The
matter how many improvements we make to the catalytic focus was on the largest contributors to palladium demand:
activity of fuel cells, the majority of environmental pollution automotive catalysis and the chemical industry. Modern
will occur prior to the usage of the fuel. palladium based catalytic converters posed many
environmental issues including toxicity of palladium, waste
produced during extraction of palladium and low
recyclability. Advancements in efficiency are not enough;
CHEMICAL INDUSTRY
eliminating the need for catalytic converters by using PEFC’s
may be a good solution, however even they do not come
without difficulties. Palladium-based catalysts have been
Palladium’s principal use in industry is to catalyse coupling
excellent for coupling reactions used everywhere from
reactions; from bulk chemicals to pharmaceutical syntheses
pharmaceutical synthesis to bulk chemical reactions,
it is almost indispensable. “Catalytic reagents are superior to
although with recent price hikes alternative shave been
stoichiometric reagents” [20] (PGC – 9), while catalysts
considered such as using less expensive metals and
provide improvements in atom economy and energy
biocatalsysts. All alternatives will have downsides and
efficiency they still hold some of the limitations of
upsides however the difficulty is in deciding which green
stoichiometric reactions such as solvent use, by-product
chemistry principles to value more on. No future solution will
formation, toxicity, high costs and non-renewable precious
be green; it will be merely greener than its predecessor.
metals.
There are many ways to optimise palladium-catalysed AUTHOR INFORMATION

coupling reactions by increasing efficiency in all areas; room Corresponding Author
temperature Suzuki coupling [34], using ionic liquids to Luca Poli
improve recyclability of the catalyst [35], using microwaves
to reduce energy use [36] and performing reactions in water
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Visibly green chemistry: in favour of polyhydroxyalkanoates (PHAs)
to replace conventional petroleum-based polymers
Allen Li
KEYWORDS. PHA, biopolymers, green polymers, petroleum replacements.
ABSTRACT: Given the difficult problems facing traditional petroleum-based polymers, a replacement that is sustainable,
biodegradable, comparable, and economical is desired. There is mounting evidence and considerable research in favour of adopting
polyhydroxyalkanoates, PHAs, as the biopolymer of choice. Recent advances in this technology support the argument in favour of a
transition away from conventional plastics. Taken together, the sustainable production, biodegradability, compatibility, and
nontoxicity of PHAs makes for a compelling case toward their adoption. In the near future, improvements in economic
competitiveness will further enhance the long-term relevance of PHAs.
INTRODUCTION because they can be structurally modified to have diverse

Plastics and polymers are ubiquitous in the world today. These physical properties [1]. Unfortunately, the vast majority of
materials are used in applications as diverse as water bottles these materials are synthesized from polluting petroleum
and biologic stents. As synthetic compounds, they are preferred sources, and stalwarts such as polyethylene and polypropylene
exhibit minimal biodegradation when they reach their end of elucidated, among which are paths to sustainable sourcing and
life. Plastics production exceeds 75 billion pounds every year, production, evident biodegradability and nontoxicity,
of which at least 40% ends up in landfills, causing an important competitive physical properties, and economic feasibility.
accumulation of waste worldwide [2]. Even if much effort is Given these stellar properties, there is great incentive to
invested in recycling those materials, the challenges of sorting migrate to these biopolymers in the near future. Consumers
the used material and structural weakening limit its viability and industry alike should therefore closely examine such a
[3]. While there is significant research in the field of transition.
remediation, considerable effort is necessary to limit the
negative consequences of these petroleum-based polymers. The
principles of green chemistry can be applied to this endeavour, SUSTAINABLE SOURCING AND PRODUCTION
and one of the most privileged solutions is the development of The design of better, greener polymers, such as PHAs, starts at
new classes of polymers. These should be made from renewable the cradle. As with any other product technology, it is of great
resources and biodegrade in ambient conditions while importance to avoid the pitfall of shifting environmental
retaining the most desired qualities of traditional polymers [4]. burdens elsewhere in the life cycle [9]. To solve the plastics
problem, this idea must be a priority; thus, the best solution
produces no material waste that nature cannot handle [2].
Polyhydroxyalkanoates, or PHAs, are one such group of Fortunately, PHAs fulfill this criterion. They are produced from
materials. These biopolymers possess diverse and easily an array of renewable sources, such as sucrose, starch, and even
variable physical properties that allow them to directly carbon dioxide [2]. In fact, it is possible to produce PHA by
compete with synthetic plastics [5]. Perhaps the most popular taking advantage of precursors found in existing waste
is poly(3-hydroxybutyrate), or PHB, and it is this variety that streams. This reduces the impact of the waste. Some of these
was first discovered by Maurice Lemoigne nearly a century ago sources include dairy byproducts [10], raw sewage [9],
[4]. PHB is itself a member of a class of PHAs called short chain fermented paper mill wastewater [11], and even discarded fruit
length PHAs, or scl-PHAs, which contain up to five carbon [12]. By leveraging these novel sources, it is possible to
atoms per unit monomer [4]. Larger examples are called sustainably source the materials needed to synthesize PHAs.
medium chain length PHAs, or mcl-PHAs, and contain up to
fourteen carbon atoms [4].
Sustainability considerations do not end at the sourcing of
feedstocks. The production process itself must also strive to
abide by the principles of green chemistry. Unfortunately, some
current commercial PHA production procedures exhibit higher
fossil fuel demands and carbon emissions than conventional
plastics manufacturing. This results from poor choices for
feedstock [9]. The use of non-renewable feedstocks accounts
for up to a third of the total energy requirements of PHA
production, and the use of inefficient bioreactors can add 30%
or more on top of that proportion [9]! Fortunately, by using
creative and inexpensive precursor sources, such as the ones
previously mentioned, the feedstock expense can be drastically
reduced [13].
As research progresses, the goal of an entirely sustainable

manufacturing process becomes possible. This is expected
because PHAs are synthesized as a store of energy and
nutrients [4]. In fact common strains of bacteria such as A.
Figure 1. Chemical structure of polyhydroxyalkanoates. Top: eutrophus, A. latus, or recombinant E. coli synthesize most
General structure of PHAs. Bottom: Structure of PHB varieties of PHAs [14]. These bacteria naturally produce PHAs
when exposed to an environment abundant in carbon, but
Regardless of their size, PHAs are synthesized by self-sufficient limited in another nutrient, such as nitrogen or phosphorous
organisms, among which are over 300 species of bacteria [4]. [4].
They are made via biosynthetic pathways involving a chain of
enzymatic reactions, but unsurprisingly, the pathway differs
The capability to biologically synthesize PHAs is not limited to
for each producer and polymer [6]. For example, PHB is
bacteria. Many other organisms can be genetically modified to
synthesized in three steps: a condensation of acetyl co-enzyme
produce polymers. As long as a PHA synthase gene is
A (acetyl-CoA) molecules, followed by their reduction, and
transferred, a synthase protein is activated, and substrates can
finishing with polymerization [6]. In an alternative route,
be reliably provided, many organisms can produce PHAs [15].
PHAs can be synthesized by metabolism of fatty acids [7]. All
Since the genes required for PHA production are easily isolated,
of these naturally occurring syntheses involve aqueous
plants may be adapted to produce large quantities of these
processing environments and generate only nontoxic wastes
polymers [16]. With oil-producing plants, this process is
[5]. When this process is translated to commercial production,
particularly efficient [2].
PHA manufacture requires just two simple stages [8].
The final step of PHA manufacturing is isolation and extraction

In recent years, PHAs have become the subject of considerable
of the polymer. Traditionally, this task employs organic
research and development. Clear advantages have been
solvents such as toluene and chloroform. While this achieves environments, PHAs manage to degrade completely within
PHAs of high purity, these chemicals are toxic and harmful to nine months, with ambient water temperatures not exceeding
the environment. Fortunately, recent developments have six degrees [3]. In freshwater lakes, the degree of degradation
ascertained the viability of replacing these solvents with milder reaches 100% within eight weeks [21]. Overall, complete
ammonium hydroxide and sodium hydroxide solutions at biodegradability has been observed under various conditions, a
concentrations as low as 0.2 M [17]. This substitution yields remarkable feat for such useful materials [17].
only a slightly impure product, not below 94 percent purity
[17]. Streamlining of the entire process means that PHA
The speed of biodegradation is as remarkable as the products
production will soon be a sustainable and environmentally
the process yields. Under aerobic conditions, the only products
friendly process.
are water and carbon dioxide [5]. Under anaerobic conditions,
BIODEGRADABILITY AND NONTOXICITY the products are carbon dioxide and methane gas [2]. None of
Given their origin, it is not surprising that PHAs are highly these products are particularly dangerous, and all can be reused
biodegradable under ambient conditions. The degradation in various industrial and practical applications. When PHB is
process simply reflects the natural purpose of PHA as a source degraded, the chief product is 3-hydroxybutyric acid, which is
of nutrients for microorganisms. As such, these organisms a naturally occurring and innocuous component of blood
break down the polymer to derive energy [18]. Studies illustrate plasma [5]. Thus, PHB is particularly well suited to medical
these polymers completely degrade in aerobic conditions after use. The implications of these properties are significant. With
short periods of time; observed half-lives are as short as PHAs, it is possible to realistically imagine a world where
seventeen days [19]. This timescale is remarkable even carelessly littered bottles and bags can safely disappear into the
compared to those of other biopolymers such as poly(lactic ground, and where plastic rings no longer pose a significant
acid), which has significant difficulty degrading outside threat to marine wildlife.
controlled conditions [20]. Even when disposed in aquatic
Table 1. Comparison of key physical properties of selected polymers [5]. Reproduced with permission.
Polymer Melting Point (ºC) Young’s Modulus (GPa) Tensile Strength (MPa)
P(3HB) or PHB 180 3.5 40
P(4HB) 53 149 104
Polypropylene 176 1.7 34.5
Polystyrene 240 3.1 50
Table 2. General comparison of polymer properties [5]. Reproduced with permission.
Property scl-PHAs mcl-PHAs Polypropylene

Crystallinity (%) 40-80 20-40 70
Density (g cm-3) 1.25 1.05 0.91
Tensile strength (MPa) 4 – 43 20 34
Glass transition (ºC) -148 – 4 -40 – 150 -10
Extension to break (%) 6-1000 300-450 400
UV resistance Good Good Poor
Solvent resistance Poor Poor Good
Biodegradability Good Good None
COMPATIBILITY AND COMPETITIVENESS crystalline, brittle, and stiff with high melting points and low
In spite of their low environmental impact, PHAs are glass transition temperatures [5]. PHB melts at 180 ºC and
functionally comparable to conventional petroleum-based breaks with less than ten percent elongation. Both properties
polymers. Bacterial PHAs have sufficient molecular mass to make them excellent choices for packaging applications [22].
have polymer characteristics similar to polypropylene and On the other hand, mcl-PHAs are thermoplastic with low
others [1]. Since dozens of bacterial strains produce polymers melting points [5]. They are capable of stretching long
of varying structures, PHAs can largely match the diversity of distances without breaking, which make them well suited for
synthetic polymers. In addition, PHA exhibits diverse physical making films and adhesives [5]. In addition, almost all PHAs
properties with modifications to the length of the chain and the have a high degree of polymerization, are insoluble in water,
presence of functional groups [5]. and are UV-resistant [2]. Table 1 compares some of the most
important properties of common PHAs and petroleum-based
polymers.
As a result, for almost every physical property that
distinguishes synthetic polymers, there is a comparable
analogue in the PHA family. For example, scl-PHAs are It is a valid question to ask why competing biopolymers, such
as PLAs, are not preferable compared to PHAs. To answer this
argument, it must be noted that the competing polymers lack engineering, wherein the design of pathways becomes
structure variability and material properties PHAs possess, important. Providing PHA synthase enzymes at consistent
thus limiting their practical use [4]. For instance, most PLAs concentrations to suitable substrates can result in significant
have softening points of around 60 ºC, a temperature low economic improvements [15]. Additionally, as productivity
enough to cause their deformation under sunlight or while increases, the fixed costs of equipment and overhead
holding a hot beverage [20]. With great diversity, different significantly decrease [17]. At those prices, PHAs become
PHAs can replace many conventional polymers for all sorts of directly competitive with conventional polymers, and will
uses without the limits of narrow, specific applications [5]. likely have a large impact on their adoption.
CONCLUSION
ECONOMICS AND YIELD Green chemistry is concerned with improving the environment
No matter the benefits, the paramount concern of adopting any and fostering sustainable development. It seeks to provide
new technology or product is price, and biopolymers are no solutions to the problems traditional chemistry face. One of the
exception. Fortunately, the competitiveness of PHAs with most challenging problems facing the world today is that of
petroleum-based polymers extends to price. While previous polymer use and buildup. As PHAs have shown, research and
methods produced PHAs at costs exceeding those of development in chemistry can have far-reaching effects toward
traditional plastics by factors of 20, recent improvements and solving this quandary. Chemistry has made adopting these
sensible design considerations reduce the cost to much more biopolymers one of the most solidly sustainable choices
competitive levels [5]. To attain this goal, two primary routes ordinary consumers can make. It is up to firms to
are necessary. First, improvements to the production process wholeheartedly begin the transition away from polluting
increase the quality, quantity, and value of PHAs. Secondly, the petrochemical polymers and embrace a new generation of
valorization of existing waste streams spawns opportunities to sustainable, biodegradable, competitive, and economical ones.
produce PHAs at minimal cost, thereby lowering the price for PHAs are helping make the world we live in more sustainable
everyone. and less hazardous. The economic barrier to their adoption is
being surmounted, and consumers and firms alike are taking
note. With such clear progress being made, everyone can
As an example, improvements in the efficiency of PHA
benefit from this true example of green chemistry at work.
synthetic processes reduce the cost by increasing the yield per
unit of input. For some time, bacterial PHA production was
quite inefficient, posting yields below 25%. Recently however,
procedures using cheap recombinant E. coli specimens have AUTHOR INFORMATION
resulted in yields exceeding 75%, and this percentage is
expected to rise [17]. In the recombination exercise, a gene that Corresponding Author
encodes for a degradation enzyme can be inactivated, resulting Allen Li
in an increased yield [23]. Additionally, immediate cost [email protected]
reductions can be realized by reducing the cost of feedstock,
since that component alone constitutes half of the total ACKNOWLEDGMENT
expense [24]. Costs can also be minimized at the recovery The author thanks Profs. Audrey Moores and Robin Rogers for
process, where a considerable proportion of total cost their valuable guidance with this project. Correspondence with
originates [25]. Clearly, these innovative approaches to PHA fellow Editors is also greatly appreciated.
production significantly reduce its price.
ABBREVIATIONS
On the same token, turning waste streams into PHA
PHA, polyhydroxyalkanoate; PHB, polyhydroxybutyrate; PLA,
production pathways can result in a cost reduction of 40% to poly(lactic acid).
50% while remaining practical and free from significant capital
expense [24]. The procedure involving the use of fermented REFERENCES
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6. Huisman, G. W. et al. Synthesis of poly-3-
earlier, PHAs have superior physical properties, making them hydroxyalkanoates is a common feature of fluorescent
the best choice for companies seeking a sustainable polymer.
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Nonetheless, the price is still falling. As plant production is 1954.
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biotechnological production of relevant
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8. Tsuge, T. Metabolic improvements and use of fermentation. Appl. Microbiol. Biotechnol. 1999, 51, 13-21.
inexpensive carbon sources in microbial production of 18. Jendrossek, D. and Handrick, R. Microbial degradation
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development. Biopharm Journal. 2015, 1, 48-63. 20. Nampoothiri, K. M. et al. An overview of the recent
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for the production of polyhydroxyalkanoates using polyhydroxyalkanoates and oil palm-based composites.
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67-74. 22. El-Hadi, A. et al. Correlation between degree of
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PNAS. 1994, 91, 12760-12764. 2313-2320.
The Ugliness of the Personal Care Industry: The harmful

environmental effects of ingredients used in personal care products
and the use of green chemistry for sustainable development
Sokina Joseph
KEYWORDS: Sustainable development; Personal Care products; Green chemistry; Environmental Impacts; UV filters;
Aquatic biota; Pollutant
ABSTRACT: Everyday, millions of people use personal care products (PCPs) and often times are unknowing that these products
are inflicting harm to the environment. With the growth expecting to reach $265 billion, it is of dire importance to address the
ramifications these products have to the environment. Owing to the fact that consumers drive the market, scientific knowledge
regarding the implications of commonly used ingredients commonly, could help mitigate the associated negative impacts. This
review underscores the harmful effects of current ingredients in PCPS, more specifically; ingredients used in oral, hair and skin care
products. With sustainable development in mind, the alternative ingredients suggested by researchers and industry are evaluated
with the green chemistry principles in mind. Moreover, the question put forth is whether the alternatives are green. Through
awareness, public sentiments could help steer research efforts to safer, and greener solutions.
1. INTRODUCTION 2. Atom Economy : Attempt to utilize all materials used in

the process
The personal care product industry currently stands at $200
billion1 and is predominately driven by diversity and 3. Less Hazardous Chemical Synthesis: chemical products are
innovation because we demand it. In detail, the industry designed to achieve their desired function but with
develops and manufactures cosmetics products which is minimal toxicity
defined by the Food and Drugs Act as “Any substance, or mixture
of substances, manufactured, sold or represented for use in 4. Designing Safer Chemicals: minimize toxicity of the
cleansing, improving or altering the complexion, skin or teeth molecule
and includes deodorants and perfumes” 14. Everyday many of us
use one of the personal care products (PCPs) and unknowingly 5. Safer solvents and Auxiliaries: The use of solvents or
expose the environment and ourselves needlessly to harm. separation agents should be used as little as possible or
Elimination of these products entirely is ideal but grossly not at all
unrealistic. In particular, the current forecast for the personal
care industry shows an upward trend which is a result of an 6. Design for Energy Efficiency : Energy requirements should be
improvement in the economy and no proof of slowing down. 16 assessed and minimized and if possible reactions should
with the rise of disposal income expected in the approaching be conducted under ambient temperature and pressure
years, consumers are more likely to try and look for products
that promise multiple benefits. With this knowledge, it is 7. Use of renewable Feed-stocks : The raw material or feedstock
imperative to know when it comes to your PCPs, what the should be renewable
ingredients and the company’s values are. Moreover, are the
ingredients harmful and is the company concerned with green 8. Reduce Derivatives: Unnecessary derivatives should be
practices. avoided or minimized
With the ubiquitous use of these products, the risks posed 9. Catalysis: Catalysts are to be used to increase selectivity
by these to our environment need to better understood. Many reduce waste and reaction time
personal care products contain several chemicals used to
achieve various functions or provide a specific benefit. Studies 10. Design for Degradation: Chemical products should be
have provided proof that the chemicals currently used in
designed in a way that they can break down and not
personal care products have a negative effect and pose a risk to
persist in the environment
the environment. Identifying the problems can help steer a
more focused research in the direction of tackling these issues.
11. Real Time Analysis of Pollution Prevention : Analytical
Currently, a globally overarching goal, is to achieve methods need to be developed in a way to allow for real-
sustainable development, defined as “development that meets time, in-process monitoring and control in order to
the needs of the present without compromising the ability of ensure hazardous substances are not made
future generations to meet their needs” 2 Along with the market
forecast for this industry, the most viable option for obtaining 12. Inherently Safer Chemistry for Accident Prevention: choose and
sustainable development, is by means of green chemistry, a develop procedures that inherently minimize the risks
pivotal element to accomplishing this goal. Before delving into for accidents
some of the impacts of personal care products it is essential to
have a firm handle of what is green chemistry Along with these green chemistry principles, Jessop et al1
suggested cost-effectiveness and the carcinogenicity of
Essentially, it is the practice of implementing 12 principles, first ingredients needs to also be considered.
introduced in 1998 by Paul Anastas and John Warner 30
The objective of this paper is to review some of the current
1. Prevention : prioritize preventing waste as much as ingredients used in personal care products and the problems
possible rather than clean or treat created waste that arise, hindering a sustainable development. The focus will
mainly be on commonly used ingredients in oral, skin and hair

products and their environmental impacts. Through the
implementation of some of the green chemistry principles,
progress has been made in offering alternatives to toxic
chemicals. Of the 12 Green Chemistry Principles the main focus
will be geared towards prevention, design for safer chemicals,
use of renewable feedstocks, and design for degradation.
2. ORAL
The quest for healthier teeth and gums has been endless with
chemistry playing a crucial role in the improvement of overall
oral health. Some of the ingredients used in these oral products
have proven to be an environmental problem. Moreover,
triclosan [ 5-chloro-2(2, 4-dichlorophenocy)phenol; TSC; see
structure Figure 1] a halogenated phenol3, has been used in oral
products more specifically, as an antibacterial in mouthwash
and toothpaste. 4 Additionally, research has shown their
effectiveness in killing several types of bacteria, some fungi and
are a primary player in the prevention of bacterial growth. 3,4
Recently, studies have exhibited the health implications of
TSC5 including being a liver tumor promoter. Along with the
health concerns there is strong evidence to suggest that TSCs
pose a threat the environment. No known natural sources of
TSC exist with this it can be concluded that its presence in the
environment is due to human activity.6 Figure 2. Possible pathways for releases of TSC to the
environment. Modified from Health Canada6.
2.1.1 Aquatic environment
A range of problems arise due to the use and presence of TCS

in the environment. Moreover, the impact of triclosan to the
aquatic environment has been explored extensively. The
analysis of the eco-toxicological studies have demonstrated
Figure 1. Triclosan (TSC) is commonly used as antimicrobial that triclosans are toxic to bacteria and can bio-accumulate. 4
disinfectant in PCPs. TCS is ubiquitous and found in various environmental
settings(Figure 2).7
2.1 ENVIRONMENTAL IMPACTS
With the release of TCS in WWTPs, often times free
Toothpaste, which employs triclosan, is released down the chlorine is also available as it is commonly used during
drain, discharged into sewers and carried to Waste Water wastewater treatments. Moreover, when a free chlorine, which
Treatment Plants (WWTPs). Figure 2 depicts the possible is employed during wastewater treatment, reacts with phenol,
pathways for release of TSC to the environment. 2-chlorophenol and 4-chlorophenol are the initial products.
These are further chlorinated to form 2,3-dichlorophenol and
2,6-dichlorophenol to produce 2,4,6 TCP, full depiction is
present in Scheme 18. Additionally TCSs can react with free
chlorines to produce chloroform.
Additionally, it has been suggested that the complex matrix of

wastewater could react with triclosan and the extent of the
environmental implications, which are not fully understood.

Scheme 1. Reaction scheme showing reaction mechanisms and chemical structures for triclosan and its
decay products
2.2 ALTERNATIVES Chalcone synthesis can be accomplished solvent-free, meeting

number five of green chemistry principle, Safer solvents and
Ideally, it is best to prevent the formation of waste rather Auxiliaries. More specifically, Saini et al11 showed that chalcones
than clean it up. While TCS has been shown to be removed were obtained in high yield and high purity by grinding
from water using reverse osmosis, this process has its piperanal and the acteophenone in the presence of solid sodium
drawbacks such as fouling 9, finding a way to eliminate the hydroxide, a general depiction is shown in scheme 2 .
need for water remediation is more beneficial. This could be Additionally, its potential to replace TSC is exhibited, as it
done by replacing TCS with an ingredient that does not persist proved to have good activity against gram-positive and gram-
in the environment and is inherently safer. Chalcones (see negative bacteria viz staphylococcus aureux, Escherichia coli,
structure Figure 3) a flavonoid and a renewable resource, has Steptococcus viridiaus and K.Salmonilla. 11 Additionally,
shown promise to replace these TCS and provide antimicrobial Chalcones12 were shown to improve the efficacy of anti-
resistance10. In particular, it was shown to inhibit some strains microbrial agents to treat oral conditions such as gingivitis, and
of bacteria that TCS inhibits as well, in particular, Streptococus plague just to name a few.
mutans, bacteria known to contribute to human dental decay.
Scheme 2. 13 14 Method reported for the synthesis of chalcones
Making the connection to the green chemistry principles,

Scheme 2 depicts this a reaction that is void of solvents and
Figure 3. Basic 1,3-diphenyl-2-propen-1-one framework of proceeds at ambient temperature and pressure and is derived
flavonoid natural product, chalcone, suggested as a from a natural feedstock. The persistence of chalcone in the
replacement for triclosan in toothpaste products environment is not a problem however this aspect hasn’t been
fully researched.
The chalcone and TSC are similar in that they contain
aromatic rings, however, chalcone is found in nature.

Another green surfactant is alkyl polyglycoside (APG). It is
manufactured from renewable resources, are readily
3. HAIR biodegradable and are low in toxicity .They contain a large
sugar-based hydrophilic head (i.e glucose, galactose, maltose,
Many of us use shampoo which serve to cleanse the hair and etc.) and hydrophobic hydrocarbon tail (cite analysis of the
scalp in addition to enhancing the hair compatibility and influence of alkl). The problem with pure APG is it is too
appearance. The main ingredients used in shampoo are expensive to be used in an industrial application. Surfactant
surfactants which are mainly responsible for cleaning.15 They blends have offered a solution to reducing the cost of pure green
are effective cleaning agents because of the nature of its surfactants, some are found in table 2.
structure; its hydrophobicity and hydrophilicity. The
hydrophobic side interacts with the dirt of the hair while the
hydrophilic suspends the surfactant and bounds dirt to water.
In many shampoos, sodium laureth sulfate (SLES, see structure Table 2. Naturally derived surfactant examples.18
Figure 3), is used as the main active surfactant.16 It has several
desirable characteristics such as its solubility in water, and its Name Natural source Benefit
insensitive to water hardness.
Disodium cocoyl Coconut fatty High foaming
glutamate acids
Sodium coco- Coconut and Non-drying with

Figure 4. Sodium Laureth Sulfate (SLES), a chemical glucoside tartrate amino acid from skin and hair
surfactant responsible for the foaming action of shampoo and fermented sugar conditioning
toothpaste. 18 properties
3.1 ENVIRONMENTAL IMPACTS
The surfactants pose a problem to the environment. For Saponins19 have been explored for their potential as
instance, while SLES is derived from a natural source - coconut surfactants. It occurs in different tissues of a large number of
and/or palm oil, it is manufactured via a chemical process. plant species and are predominately glycosides possessing one,
Moreover, the nature of this process, ethoxylation, is known to or more sugar chains attached to the aglycone, the nonpolar
result in contamination with 1,4 dioxane, a carcinogen.17 While parts of the molecule. Saponins are obtained from oleochemical
a product may be marketed as natural this does not mean it is feedstocks and an important source of these saponins is the
green nor does it mean that it is clear of any pollutants. Yucca Schidigera plant. However, the supply from plant sources
has been limited making the products less available and
3.2 ALTERNATIVES resulting in a high cost. Additionally, the saponins make a good
lather but have low cleansing properties making its use in
3.2.1 Naturally- derived surfactants industrial application unlikely.
A novel soybean oil-based polymeric surfactant (SBPS) 3.2.2 Surfactants from Waste Biomass20
demonstrated its ability to meet major requirement of shampoo
while being non-toxic, environmentally friendly and derived Recently, microbes were studied for their potential to
from renewable sources, meeting many of the green chemistry degrade waste biomass to produce useful bio-surfactants.
principles aforementioned. 15 The hydrophobic ends of the Based on the fact that humic acids are capable of reducing the
macromolecules were derived from soybean oil and the surface tension of water, and solubilizing hydrophobic
hydrophilic portions were based on ethylene glycol units. compounds.20 An alkaline treatment was used to convert
Additionally, the physicochemical properties were studied comport to surfactant-like material, figure 7. The potential to
along with their cleaning ability, foaming characteristics, and commercialize the product was not assessed.
viscosity in order to study the utility of this novel surfactant in
shampoo. Popadyuk et al evaluated the novel SBPS along with
commercial shampoo and was able to conclude that soybean is
a viable replacement. Scheme 3 depicts the facile synthesis of
this copolymer.
Scheme 3. Synthesis of the SBPS copolymer, where R is

soybean fatty acid component. Adapted from Popadyuk et
al15
Figure 7. Structure for surfactant-like humic material and are safe for use as additives to personal care products
extracted from compost. which would lead to a reduction of commercial UV filters.
4. SKIN Lignin 28, one of the most abundant biopolymers on earth29

Recently, Qian et al28, studied the effectiveness of lignin
With the growing recognition of the harmful effects of addition to pure suncreams via magnetic stirring. They
ultraviolet (UV) radiation this has lead to the development of demonstrated that the commercial sun protection factor (SPF)
chemicals, more specifically, UV filters to mitigate the effects. 15 sun lotions saw an enhancement, in fact with the addition of
These filters have become popular because of their protective lignin the SPF could reach up to 30. This nature-inspired lignin
role in reducing skin damage which has shown to eventually system provides an alternative to replace some synthetic
lead to premature skin aging 21 They work to absorb UV chemicals.
radiation and mitigate the negative effects of sunlight exposure
and protect skin. Some common UV filters include, The use of microbial ‘sunscreen’ compounds has been
oxybenzone, avobenzone, methoxycinnamate and growing as they have shown to provide a photoprotective
Benzophenone-2 (BP-2).6 mechanism. Scytonemin, a cyanobacterial, is a lipid-soluble
and stable pigment. Under UV light it was seen to be effective
4.1 ENVIRONMENTAL IMPACTS in acting as a shield for the cells. Melanin, known from fungi
and bacteria. These have shown resistance to UV light and
These UV filters are meant to be applied externally to the could potentially be employed in personal care products.
outermost layer of the skin, however, concerns have risen with
regard to their ramifications to the environment. UV filters 5. ISSUES WITH GREEN INGREDIENTS
approved for use have been detected in surface water, and
drinking water.22 Nowadays, UV filters are considered Achieving high performing products with more green
emerging contaminants due to their widespread presence in alternatives is the biggest challenge faced and the performance
the environment and because of the unknown risks associated does not yet match that of conventional ingredients. A
with their presence.22 UV filters can enter the environment in suggested alternative blending ingredients could reduce
various ways, for instance, directly from recreational activities harmful ingredients as was the case with some of the proposed
when they are washed off from the skin as a result of green alternatives for surfactants and UV filters. Additionally,
swimming. The UV filters are lipophilic and end up problems can occur when trying to scale up from laboratory to
accumulating in sediments and biota16 proving to be a problem. manufacturing which could mean a less controlled
environment. Moreover, natural ingredients tend to be more
4.2 ALTERNATIVES susceptible to bacteria as it finds it more nutritious. 18
In addition to meeting as many of the 12 principles of Green 6.CONCLUSION

Chemistry as possible, desirable alternatives to these UV filters
would need to be characterized as readily biodegradable, low Eliminating current toxic chemicals in personal care
toxicity to aquatic organisms, non-sensitizing, non-irritating products (PCPs) needs to be addressed. With the current
and pose little to none toxicological problems to humans. forecast of the PCP, the need to replace toxic chemicals is
needed. With some of the green chemistry principles viable
Gelatin, produced by the partial hydrolysis of collagen, is a alternatives can be found and success can be made. Efforts need
natural biopolymer widely used due to its biocompatibility, to be focused on understanding the full implications of the PCP
biodegradability, and low cost and have been employed in ingredients as there is a lack of information regarding this.
various cosmetic products.23 Additionally, it does not produce Looking at improving the biodegradability of ingredients, the
harmful byproducts upon enzymatic degradation. Recently, reduction of harmful chemicals either by completely replacing
rutin-entrapped gelatin nanoparticles (GNPs) were designed the toxic chemicals or by finding ways to reduce the need of the
and associated with ethylhexyl dimethyl PABA (EHDP), harmful chemicals through blending them with natural
ethylhexyl methoxycinnamate (CHMC) an alternative to products. Lastly, biodiversity needs to be considered when
synthetic-based sunscreen. Encapsulation of natural trying to find ‘green’ alternatives, it is important not to
ingredients such as rutin, can offer improvements in sun jeopardize the system.
protection effectiveness by reducing the amount of UV filters
in sunscreens24. This leads to the prevention and inherently AUTHOR INFORMATION
safer chemistry.
Corresponding Author
Some plant oils have been shown to possess some natural * Sokina Joseph ,[email protected]
sunscreen abilities. For example, sesame oil resists 30% of UV
rays. Additionally, the active ingredient, epigallocatechin-3- ACKNOWLEDGMENT
gallate (EGCG), a phytochemical found in green tea has shown
to work as sunscreen. 25 However, they cannot be used as a sole I would like to thank Prof. Robin D. Rodgers and Prof. Audrey
Moores for their assistance and mentorship as well as the McGill
sunscreen ingredient and must be used along with current UV
Green Chemistry Journal Editorial Board for the editing and
filters. The benefit with using the plant extracts or biopolymers
publishing of this article.
is this minimizes the need for UV filters despite not completely
replacing them. ABBREVIATIONS
Additionally, green coffee oil26,and extracts of carica TCS, Triclosan; SLS, Sodium Lauryl Sulfate ; PCPs, personal
papaya27 , natural products, have undergone cytotoxicity assay care products; , EGCG; epigallocatechin-3-gallate; GNP,
gelatin nanoparticles; EHDP, ethylhexyl dimethyl PABA;
CHMC, ethylhexyl methoxycinnamate; 2,4 DCP, (14) P. J. Naik, D. V. P. and P. S. D. Der Chem. Sin. 2013, 4
(dichlorophenol); 2,4,6 TCP(trichlorophenol); UV ultra violet.
(4), 68–72.
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Sustainable Water-Splitting Methods to Produce Hydrogen
Nora Abbassi-Mohadjel
KEYWORDS: Water-splitting, Electrolysis, Photoelectrolysis, Photoelectrochemical, Thermochemistry, Hydrogen fuel
ABSTRACT: Hydrogen is primarily used in the chemical industry, but with the depletion of fossil fuels, hydrogen fuels are becoming
an attractive alternative especially because the only by-product is water. This article reviews the technologies related to hydrogen
production by water-splitting methods. These methods include electrolysis, photoelectrolysis or photoelectrochemical processes
and thermochemistry with solar powered energy. The efficiencies of each method were compared as well their realistic use for the
future. It was found that the amount of water it takes to produce hydrogen is not a critical problem in comparison to the production
of gasoline. Although great aspects come from these methods, more research will be needed to have better and consistent efficiencies.
1. INTRODUCTION production of hydrogen fuels. Currently, however, 95% of

The urgency in finding an alternative to the world’s commercialized hydrogen is produced from fossil fuels by
diminishing fossil fuels have never been greater than today. steam reforming and coal gasification [1]. In the long run, it is
Today, the increase in greenhouse gas emissions due to carbon not sustainable to produce hydrogen from non-renewable
dioxide has been the main culprit of global warming and hydrocarbon sources. For cleaner processes of hydrogen
climate change. The global economy and energy supply production, one possible solution to help mitigate global
depends largely on fossil fuels. This has led to the hyper- warming is to explore renewable energy sources that replace
consumption of these non-renewable resources, which in turn fossil fuels, such as hydrogen [2]. Hydrogen could be the ideal
has resulted in the escalating atmospheric carbon dioxide fuel, as it possesses very high energy density and the only
concentration and the rapid depletion of fossil fuel resources byproduct is water; there is no climate-altering carbon dioxide
[1]. Scientists have become more and more interested in the released from hydrogen during combustion [3]. As Leonardo Di

Vinci once said, “Water is the driving force in nature;” pun
intended in this case.
However, there most definitely are problems or disadvantages

of renewable primary energy since energy sources such as solar
energy, wind energy and ocean energy are regionalism,
intermittence and unstorability, which will result in instability
of power source [4].
Apart from its use as a clean energy resource, hydrogen can be
used for various other purposes in chemical process industries.
It can be used to crack hydrocarbons, saturate compounds or
remove sulphur and nitrogen compounds [5], as well as it is
used as a reactant hydrogenation process to produce lower
molecular weight compounds [6]. Hydrogen is well known in
manufacturing ammonia, methanol and synthesis gas [7] as
well as a good oxygen scavenger and can therefore be used to Figure 1. A schematic illustration of a basic water electrolysis
remove traces of oxygen to prevent oxidative corrosion [8]. The system [15]
future widespread use of hydrogen is likely to be in the 2.1 New electrolyte composition and system for water
transportation sector, where it will help reduce pollution. electrolysis
Aside from the uses of hydrogen, the main concern today is the
2.1.1 Ionic liquid/Water electrolyte exhibits good
production of hydrogen itself. Currently, however, are these
conductivity and is chemically inert to metal electrodes [4]. In
new methods really reliable? How much water will be used if
conventional water electrolysis, corrosive reagents such as
these processes were to be commercialized? This review will go
NaOH, KOH and H2SO4, are usually used as conductive salts,
through a variety of renewable hydrogen production
however these cause serious destruction in the corrosive
technologies with the emphasis on their applications in the
electrolyte and lose catalytic activity for the catalyst in the
world by looking at water-splitting methods and their energy
metal electrodes. Therefore, low stability of metal electrodes is
efficiencies. There has been a great deal of research in splitting
another major problem of water electrolysis.
water to make hydrogen and oxygen. Water splitting can be
divided into three categories: (2) electrolysis, (3) In 2006, Souza et al. [11] used BMIFB4 as conductive electrolyte
photoelectrolysis or photoelectrochemical processes, (4) for hydrogen production by water electrolysis that resulted in
thermochemistry. no effect on the catalytic process of electrodes. This mechanism
was consistent with a variety of metals such as gold,
2. ELECTROLYSIS molybdenum, nickel, titanium and platinum electrodes [4].
Furthermore, this lead to maximum optimization for the
Water electrolysis for hydrogen production has many
following: electrode materials, type of ionic liquid and
advantages such as high purity and simple process by passing
concentration in water. “The best efficiency of about 99% was
electricity through two electrodes in water. The water
obtained in the solution of 10 vol% BMIMF4 and 90 vol%” [11].
molecule is split and produces oxygen at the anode and
In more recent studies, such as in 2012, Pool et al. [16] designed
hydrogen at the cathode [9]. Hydrogen produced by water
a molecular electrocatalyst {[Ni(P2N2)2](BF4)2} as medium in
electrolysis is considered as the best energy carrier to adjust the
highly acidic ionic liquid/water electrolyte to promote the
balance between the generations of power source by renewable
reduction of protons to H2. This was inspired by the fact that
primary energy and energy demand for end-use [4]. Although
the Molybdenum electrode was a great substitute to Platinum
the prospect of the sustainable energy route is inspiring, the
electrode as it had better efficiency, cost and stability of
problems are low gas evolution rate and high energy
hydrogen production. “However, the viscosity of ionic liquid is
consumption of water electrolysis. Generally, energy
large, which affects negatively the transportation rate of ions.
requirement is up to 4.5 -5.0 kWh m-3 H2 in conventional
Current density, i.e. hydrogen production rate, is also low in
industrial electrolyzers [4].
ionic liquid/water system.” [16]
Today, some industrial electrolyzers involve an aqueous

solution of potassium hydroxide (KOH) (due to its high 2.1.2 Alkaline electrolyzers are typically composed of
conductivity) and are referred to as alkaline electrolyzers [10]. electrodes, a microporous separator and an aqueous alkaline
Recent studies have also tried ionic liquids for conventional electrolyte of approximately 30 wt.% KOH or NaOH [17]. In
water electrolysis as well as more developing types like proton alkaline electrolyzers nickel with a catalytic coating such as
exchange membrane (PEM) electrolysis and Solid oxide platinum, is the most common cathode material [18]. For the
electrolysis cells (SOEC) [11-14,45]. anode, nickel or copper metals coated with metal oxides, such
as manganese, tungsten or ruthenium, are used [18]. Platinum,
in most cases however is known to be very expensive. Recent
studies show that the aim of presented work is lowering the
cost and the energy consumption of the conventional alkaline
water electrolyzer by raising its efficiency using combinations
of d-metals from different parts of transition series as activating
compounds [19]. “Such combination metals like cobalt and
tungsten based ionic activators are added directly into the
electrolyte during the electrolysis process and concluded to be
extremely active and reduces the energy per mass unit of
hydrogen produced” [19].
Firstly, in the alkaline cell, the decomposition of hydrogen and

OH- occurs when water is introduced in the cathode [20, 45].
Then, O2 is formed when the OH- travels through the
electrolytic material to the anode and the hydrogen gets left
behind in the alkaline solution [20]. Outside the electrolyzer,
the hydrogen is then separated from the water in a gas liquid
separation and typically achieves efficiencies of 59-70% based
on the lower heating value of hydrogen [20, 45]. The overall
reactions at the anode and cathode are [20, 45]:
Anode:
4𝑂𝐻 − → 𝑂2 + 2𝐻2 𝑂 (1)
Cathode:
2𝐻2 𝑂 + 2𝑒 − → 𝐻2 + 2𝑂𝐻 − (2)

Figure 2. Schematic representation of PEM electrolysis [22]
Overall:
The following table (Table 1) presents a comparison of the two
1 types of commercialized electrolyzers looked at thus far.
𝐻2 𝑂 → 𝐻2 + ( ) 𝑂2 , ∆𝐻 = −288𝑘𝐽𝑚𝑜𝑙 −1 (3)
2
Table 1. A comparison of the two types of commercialized

2.1.3 Proton exchange membrane (PEM) electrolysis electrolyzer. [15]
PEM electrolyzers build upon the recent advanced PEM fuel Parameter Monopolar PEM
cell technology [21]. This perfluorosulfonic acid polymer (also alkaline electrolyzer/cell
known as Nafion) has ben used in chlor-alkaline electrolysis electrolyzer
and also in fuel cells. PEM electrolysis is a process just reverse
of a PEM fuel cell (Figure 2). Water is split into oxygen, Cell voltage 1.85 2V
protons and electrons on one electrode (anode) by applying a
DC voltage higher than a thermoneurtal voltage. Protons pass Number of cells N/A 7-51
through the polymer electrolyte membrane and on the cathode
combine with electrons to form hydrogen. [22] The O2 gas Current density 0.25 Acm-2 1.075 A cm-2
remains behind with the unreacted water. There is no need for
a separations unit. Depending on the purity requirements a Temperature 70 ℃ 65 ℃ (outlet)
drier may be used to remove residual water after a gas/liquid
separations unit. PEM electrolyzers have low ionic resistances Current 10 kA 1 kA (maximum)
and therefore high currents of >1600 mA cm-2 can be achieved
while maintaining high efficiencies of 65-82% [23,45]. The Scale 200 kW N/A
reactions at the anode and cathode are [23,45]:
Hydrogen 42 m3 h-1 0.42 m3 h-1
Anode: production rate
2𝐻2 𝑂 → 𝑂2 + 4𝐻 + + 4𝑒 − (4)
Oxygen 21 m3 h-1 0.21 m3 h-1
Cathode: production rate
4𝐻 + + 4𝑒 − → 2𝐻2 (5) Hydrogen gas H2 > 99.5% H2 > 99.995%

purity
Overall is the same as for alkaline electrolyzers:
Oxygen gas O2 > 99% O2 > 99%
1
𝐻2 𝑂 → 𝐻2 + ( ) 𝑂2 , ∆𝐻 = −288𝑘𝐽𝑚𝑜𝑙 −1 (6) purity
2
Demineralized N/A k < 0.25 S cm-1

water
conductivity
2.1.4 Solid oxide electrolysis cells (SOEC)

The key components of an SOEC are a dense ionic conducting the lowest efficiency so they have the highest electrical energy
electrolyte and two porous electrodes. The fundamental costs [15]. Adding ionic activators to alkaline electrolytes or
mechanisms involved in SOEC operation are shown in Figure using ionic liquid/water electrolyte improve the
3. [24] Water at the cathode combines with electrons from the electrocatalytic activity and stability of electrodes [11].
external circuit to form hydrogen gas and negatively charged Electrolyzers are not only capable of producing high purity
oxygen ions [25]. The oxygen ions pass through the solid hydrogen, but recently, high-pressure units are being
ceramic membrane and react at the anode to form oxygen gas developed [28]. Currently, electrolysis is more expensive than
and generate electrons for the external circuit. Advantages for using large-scale fuel processing techniques to produce
high temperature electrolysis with a solid oxide based hydrogen. And, if non-renewable power generation is used to
electrolyzer include: the use of a solid electrolyte, which, unlike make the electricity for electrolysis, it actually results in higher
KOH for alkaline systems, is non-corrosive and it does not emissions compared to natural gas reforming [29]. Several
experience any liquid and flow distribution problems [25,45]. different approaches have been proposed to address these
shortcomings. These include renewable sources of energy such
Operating at high temperature, the SOEC components must as solar, wind, and hydro, to produce the electricity [29,45], or
meet certain requirements for efficient and cost-effective excess power from existing generators to produce hydrogen
hydrogen production such as: (1) “the dense electrolyte should during off-peak times [30,45], and high temperature
be chemically stable and have good ionic conductivity with low electrolysis. There have been several studies on the cost of using
electronic conduction to achieve high energy conversion renewable energy for electrolysis, all reaching the conclusion
efficiency because the presence of electronic conduction will that as the cost of natural gas increases renewable energy will
lower the ionic conduction of the electrolyte and current become economically competitive at central production
efficiencies of the cell.” [24] (2) “The dense electrolyte must be facilities as well as at distributed generation points especially
gastight to eliminate any possibility of recombination of H2 and if carbon dioxide and other pollutants are included in the
O2, but it should be as thin as possible to minimize the ohmic analysis [31, 32,45].
overpotential” [24]. (3) “The thermal expansion coefficients of
both electrodes should be close to that of the electrolyte to
prevent material failure of the electrolyte due to exceedingly
high mechanical stress induced by thermal expansion
mismatch.” [24] (4) “Interconnect materials are needed in
large-scale hydrogen production plant.” (5) “The cost of the
raw materials and the manufacturing cost should be as low as
possible.” [24] Table 2. Comparison of different electrolyzer technologies [15]
High temperature electrolysis efficiency is dependent on the Technology Efficiency Maturity

temperature and the thermal source. The efficiency as a
function of electrical input alone can be very high with Alkaline 59-70% Commercial
efficiencies 85-90% being report [21]. However, when the electrolyzer
thermal source is included the efficiencies can drop
significantly (down to about 40-60% efficiency) [25,45]. PEM 65-82% Near term
electrolyzer
Solid oxide 85-90% Mediate term

electrolysis cells
3. PHOTOELECTROLYSIS AND
PHOTOELECTROCHEMICAL (PEC)
In the PEC process, solar energy is converted into chemical

energy in the form of hydrogen through photoelectrolysis by
using sunlight to directly decompose water into hydrogen and
oxygen, and uses semiconductor materials. [33] This is similar
to photovoltaics, where two doped semiconductor materials
are brought together forming a p-n junction [34] Different
Figure 3. Schematics of SOEC hydrogen production [24] semiconductors work at particular wavelengths of light and
energies. “PEC is considered to be one of the most promising
2.2 Comparing electrolysis methods technologies for hydrogen production as it is based on
perpetual solar energy, is environmentally safe and can be
SOEC electrolyzers are the most electrically efficient, but are used on both large as well as small scales and the technology
the least developed of the technologies. SOEC technology has is uncomplicated” [33]. To capture sufficient solar radiation to
challenges with corrosion, seals, thermal cycling, and chrome generate electric potential, the sunlight absorbing electrode
migration [26,45]. PEM electrolyzers are more efficient than must be arranged to face the sunlight window and wired
alkaline, do not have the corrosion and seal issues that SOEC, externally or internally with the counter electrode to form a
but cost more than alkaline systems [27,45]. Alkaline systems closed circuit. [35] At the junction, a permanent electric field
are the most developed and lowest in capital cost. They have is formed when the charges in the p- and n-type of material
rearrange [24, 36,45]. The reaction mechanism below shows semiconductor surface or corrosion of the electrode via
how the usage of electricity splits the water molecule by an dissolution [24,36,45]. Current photoelectrodes used in PEC
imposed electric potential [35]: that are stable in aqueous solutions have a low efficiency for
using photons to split water to produce hydrogen. The target
efficiency is >16% solar energy to hydrogen.
2𝐻2 𝑂(𝑙) = 𝑂2 (𝑔) + 4𝐻 + (𝑎𝑞) + 4𝑒 − , 𝜙𝐴 (7) To achieve the highest efficiency possible in a tandem
configuration, “current matching” of the photoelectrodes must
= 1.23 𝑉 𝑜𝑛 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑜𝑓 𝑎𝑛𝑜𝑑𝑒 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛) be done. Electron transfer catalysts and other surface
enhancements may be used to increase the efficiency of the
2𝐻 + (𝑎𝑞) + 2𝑒 − = 𝐻2 (𝑔), 𝜙𝐶 (8) system. These enhancements can minimize the surface over-
potentials in relationship to the water and facilitate the
= 0.00 𝑉 𝑜𝑛 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑜𝑓 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛) reaction kinetics, decreasing the electric losses in the system.
Fundamental research is ongoing to understand the
where 1.23 V is the standard potential of the anode that mechanisms involved and to discover and/develop appropriate
indicates the theoretical minimum requirement. The sunlight candidate surface catalysts for these systems [38,45]. In
absorbing material has a prominent role in determining the addition to semiconductor devices for photoelectrolysis, it is
hydrogen production efficiency. The potential created by the possible to use suspended metal complexes in solution as the
electrode material must exceed the bottom theoretical limit of photochemical catalysts [36,39,45]. Typically, nanoparticles of
1.23 eV to split water molecules, plus overcoming the electric ZnO, Nb2O5, and TiO2 (the material of choice) have been used
resistance of the closed circuit. [35] [20,31,45]. Two of the most promising dyes are the N3 dye and
the Black dye [39,45]. The advantages of these systems include
“The process can be summarized for a photoanode-based the use of low cost materials and the potential for high
system as follows: (1) a photon with greater energy than the efficiencies [39,45].
bandgap strikes the anode creating an electron-hole pair. (2)
The holes decompose water at the anode’s front surface to form In comparison with water electrolysis, the production of
hydrogen ions and gaseous oxygen, while the electrons flow hydrogen and oxygen is more challenging for the
through the back of the anode which is electrically connected photoelectrolysis or photochemical processes. It is more
to the cathode. (3) The hydrogen ions pass through the difficult for the photochemical unit to efficiently track the sun
electrolyte and react with the electrons at the cathode to form because of the structure and operating complexity of the
hydrogen gas. (4) The oxygen and hydrogen gasses are equipment. [35] Say if the equipment is tilted, this may affect
separated, for example by the use of a semi-permeable the efficient sunlight tracking as the contact between an
membrane, for processing and storage.” [24,36,45] electrode and water may be changed. “The lack of a
combination of a stable, efficient light absorption system
consisting of suitable photoelectrodes and light windows
partly accounts for the low efficiency. [35] Current research
involves overcoming the low light absorption and
unsatisfactory stability in time for these systems [37,45].
5. THERMOCHEMICAL REACTIONS
The thermochemical water splitting processes promise to

produce hydrogen and oxygen from water and heat without
using electricity. This process is also called high temperature
water splitting process where the chemical reactions are driven
by high temperature heat in the range of 500-2000 ℃. [33,40]
Carrying the reaction out using a series of chemical

Figure 4: Components of a photoelectrolysis or photochemical transformations can reduce the temperature. The reaction
unit [35] systems are assembled to use water as the only input and have
hydrogen as the only output. Ideally, all other chemicals are
The hydrogen production efficiency is generally limited by recycled with minimal loss within the process. The following
imperfections in the crystalline structure, bulk and surface examples illustrate the principle [41,45]:
properties of the photoelectrodes, the material’s resistance to
corrosion from the aqueous electrolytes, and the ability to drive Thermolysis:
the water decomposition reactions [37,45].
1
𝐻2 𝑂(𝑔) = 𝐻2 (𝑔) + ( ) 𝑂2 (𝑔), 𝑇 > 2500 𝐾 (7)
In order to maximize the efficiency of this process, the 2
energetics of the electrochemical reaction must be harmonized

with the solar radiation spectrum, which is a non-trivial Zinc-zinc oxide:
problem. A mismatch of the solar radiation and materials can 1
produce photo-generated holes that can cause surface 𝑍𝑛𝑂 = 𝑍𝑛 + ( ) 𝑂2 (𝑔), 𝑇 = 2473 𝐾 (8)
2
oxidations leading to either a blocking layer on the

𝑍𝑛 + 𝐻2 𝑂(𝑔) = 𝑍𝑛𝑂 + 𝐻2 (𝑔), 𝑇 = 900 𝐾 (9)
Nickel-manganese ferrite:
𝑁𝑖𝑀𝑛𝐹𝑒4 𝑂6 + 2H2 𝑂(𝑔) = 𝑁𝑖𝑀𝑛𝐹𝑒4 𝑂8 + 2𝐻2 (𝑔), (10)

𝑇 = 1073 𝐾
𝑁𝑖𝑀𝑛𝐹𝑒4 𝑂8 + 𝑁𝑖𝑀𝑛𝐹𝑒4 𝑂6 + 𝑂2 (𝑔), 𝑇 = 1273 𝐾 (11)
Sulfur-iodine:
1
𝐻2 𝑆𝑂4 (𝑔) = 𝑆𝑂2 (𝑔) + 𝐻2 𝑂(𝑔) + ( ) 𝑂2 (𝑔), 𝑇 = 1123 (12)
2
2𝐻𝐼(𝑔) = 𝐻2 (𝑔) + 𝐼2 (𝑔), 𝑇 = 573 𝐾 (13)
𝐼2 (𝑎𝑞) + 𝑆𝑂2 (𝑔) + 2𝐻2 𝑂 = 2𝐻𝐼(𝑎𝑞) + 𝐻2 𝑆𝑂4 (𝑎𝑞), (14)

𝑇 = 373 𝐾
The basis for using multistep closed-cycle chemical processes

to reduce the temperature required for thermal water-splitting
has been the subject of numerous articles [32,45].
“In choosing the process there are five criteria, which should be
met [20]. (1) Within the temperatures considered, the 𝚫𝑮 of
the individual reactions must approach zero. This is the most
important criterion. (2) The number of steps should be
minimal. (3) Each individual step must have both fast reaction
rates and rates which are similar to the other steps in the
process. (4) The reaction products cannot result in chemical-
by-products, and any separation of the reaction products must

Table 3. Summary of the characteristics of various solar-to-hydrogen technologies [24]
Methods Water electrolysis Photoelectrolysis Photochemical Thermochemical
Reaction Potential Potential Photon-activated Thermal splitting

mechanism electrons
Form of energy Electricity Electricity Photon Thermal

input
Whether or not No Yes Yes No

the H2 production
unit mist be
constructed
together with the
solar energy
capturing device
External or External Internal Internal External

internal energy
supply
Basic components 2 electrodes and 2 electrodes and At least 1 More than 3 thermal
for engineering electrolyte electrolyte, and sensitizer at least reactors
apparatus sunlight window 1 catalyst, and
sunlight window
H2 and O2 Separately Mix Mix Separately

produced
separately or in
mixture
Overall 30% 16% 10% 45%

production
efficiency
Suitable for large Medium scale Fueling station Fueling station Large scale
scale production and fueling
or fueling stations station depends
on production
scale
Additional Depends on Not necessarily Not necessarily Needed

hydrogen production scale
distribution
network
be minimal in terms of cost and energy consumption. (5) However, this might not be economically feasible. In addition,
Intermediate products must be easily handled [36].” [45] a better understanding of the relationship between capital
costs, thermodynamic losses, and process thermal efficiency
There may be processes that meet the five criteria [36,45], may lead to decreased hydrogen production costs [43,45]. The
however, they are still not competitive with other hydrogen current processes all use four or more reactions, and it is
generation technologies in terms of cost and efficiency, which believed that an efficient two-reaction process may make this
is the major focus of research in those processes [36]. In technology viable [43]. Improvements are currently needed for
addition, these processes require large inventories of highly materials, lowering cost and increasing efficiency [43,45]. The
hazardous corrosive materials. The combination of high current overall efficiencies are believed to be close to 45-50%
temperatures, high pressures, and corrosion results in the need achievable by using these processes [43,45].
for new material.
Below in table 3 shows a summary of the characteristics of
It is believed that scaling up the processes may lead to various solar-to-hydrogen technologies.
improved thermal efficiency overcoming one of the principle
challenges faced by this technology [43,45].
ChemSusChem 1.5 (2008): 417-424.
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The projected annual demand for hydrogen generation is
estimated at 150 Mtonnes/year, which is equivalent to 100
[12]J.M. Norbeck, J.W. Heffel, T.D. Durbin, B. Tabbara, J.M.
billion gallons of water/year. As domestic water usage in the US
Bowden, M.C. Montani, Hydrogen Fuel for Surface
is around 4800 billion gallons/year and conventional power
generation is 70 trillion, the amount needed for hydrogen Transportation, Society of Automotive Engineers Inc.,
generation would not be a significant perturbation [44]. Warrendale, PA, 1996, p. 548.
Corresponding Author [13]J. Pettersson, B. Ramsey, D. Harrison, Journal of Power

Sources 157 (2006) 28–34.
Nora Abbassi-Mohadjel
ACKNOWLEDGMENT [14]S.A. Grigoriev, V.I. Porembsky, V.N. Fateev, International
Journal of Hydrogen Energy 31 (2006) 171–175.
Financial support from McGill University is gratefully
acknowledged. The guidance of Dr. Moores and Dr. Rogers was [15] K. Zeng, D. Zhang / Progress in Energy and Combustion
very appreciated. Science 36 (2010)
ABBREVIATIONS [16] Pool DH, Stewart MP, O'Hagan M, Shaw WJ, Roberts
Proton exchange membrane (PEM) electrolysis, Solid oxide JAS, Bullock RM, et al. Acidic ionic liquid/water solution as
electrolysis cells (SOEC) both medium and proton source for electrocatalytic H2
evolution by [Ni(P2N2)2] 2þ complexes. Proceedings of the
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How current hydrogen producing fuel cells show promise of a green,
zero-emission energy generation
Richard von Celsing
KEYWORDS: Solar-to-fuel cells, artificial photosynthesis, water splitting, photoelectrochemical cell, hydrogen evolution catalyst, oxygen-
evolving complex
ABSTRACT: Society has never been more concerned about our limited fossil fuel reserves. One possible solution is artificial
photosynthesis, which has the potential to meet our substantial energy consumption without excessive and unrealistic investment
in infrastructure. Most research is devoted to splitting water into hydrogen and oxygen because the only byproduct of hydrogen fuel
is water. Artificial photosynthesis is a very active field of research though it is mostly focused on improving particular processes
rather than developing fully functioning solar-to-fuel cells. The fuel cells that have been built recently have shown significant
promise as they do split water into hydrogen and oxygen effectively, however their efficiency is far too low. Furthermore, once
efficient solar-to-fuel cells have been developed, they need to be scaled up and robust enough to be commercially viable which is
potentially just as challenging. There is definitely no set time frame for industrial scale fuel cells but it is quite improbable that they
will be a reality in the next couple of decades.
1. INTRODUCTION considered the cause global warming.3 As a result, there is

extensive research dedicated to finding sustainable energy
One of the great challenges for our society in the near future is sources.4 Current renewable sources are hydroelectric,
our growing global consumption of energy which has led to geothermal, wind and solar power which have public opinion
global warming and the rapid depletion of unsustainable fuel divided over their ability to meet our current and future energy
reserves, namely fossil fuels.[1,2] There are a numerous demands.5 The majority of the public do believe that our energy
environmental concerns associated with fossil fuels, chiefly needs can be met by renewable energy sources.6 The biggest
carbon dioxide emissions into the atmosphere, which is widely challenge for renewable energy is economic viability with the

media highlighting the substantial cost of government are photosystems II and I (PSII & I), shown in figure 1.
subsidies.7 Another issue is the conflicting estimates and Photosystems are large pigment proteins that are responsible
calculation of cost for renewable energy, which kindles for the photochemical reactions that drive photosynthesis. 18a
existing public doubt.8 Photosynthesis begins at photosystem II, which absorbs 4
photons of red light with a variety of pigments (mostly
It is estimated that the annual energy consumption of the
chlorophylls) and excites pigments’ electrons. The electron
global population is equivalent to the energy captured in one energy is passed through to the reaction centre where the
hour by biological processes from sunlight.9 Solar power is the
charge separation occurs. This leads to the reduction
broad term used to describe harnessing this energy.
plastoquinone to plastoquinol and the oxidization of water to
Predominant methods include the use of photovoltaic cells to
produce 4 protons and oxygen (scheme 1).22
directly convert sunlight to electricity or solar thermal
methods involving focusing large quantities of light on a highly
absorptive heat engine. Unfortunately, these methods suffer
from low efficiency (<30% for industrial methods),10 meaning
large losses of potentially useful energy. Additionally, there are 4hu
no suitable methods to store large quantities of electricity, thus 2H2O O2 + 4H+ + 4e-
far. Ideally, we would produce a fuel so we could easily
transport, store and use large quantities of energy.11 Another Scheme 1 – the oxidation water half-reaction
proposal is to replace fossil fuels with biofuels, indirectly The electrons get transferred through cytochrome b6f from the
harnessing the power of the sun through plants. Biofuels were plastoquinol to photosystem I where they are excited by
initially viewed as sustainable and environmentally friendly.12 another 4 red photons to a higher energy state. The electrons
However, subsequent studies on the environmental combine with the potential gradient of protons to reduce
consequences of biofuels have altered how they are viewed. 13 NADP to NADPH and drive the thylalkoid-bound ATP
Biofuels have been shown to have significant detrimental synthase to chemiosmotically produce ATP.23 The electron
effects on the environment, such as carbon dioxide emissions transport chain that the electrons are transferred through is the
and the current limitations of biorefinery.14 Presently, they are initiator of the chemiosmotic potential across the thylakoid
generally considered a good option in the short term to membrane; it is often called the Z-scheme. NADPH and ATP
decrease our dependence on fossil fuels but they are not a long- can then reduce carbon dioxide into carbohydrates in the ‘dark’
term solution without significant technological advances. (light independent) reactions of oxygenic photosynthesis
Photosynthesis is the process that nature has been refining over (scheme 2).
billions of years to harness the power of the sun. 15 The Italian 4hu
scientist, Giacomo Ciamician, was the first to propose the idea CO2 + 4H+ + 4e- (H2CO) + H2O
artificial photosynthesis in 1912,16 foreseeing the energy
problems we now face. Without sufficiently advanced Scheme 2 – the reduction of CO2 to carbohydrates half-
chemistry there were no breakthroughs until the discovery of reaction
the Honda-Fujishima effect in 1972, providing the first example While photosynthesis is a highly intricate and effective process
of water photolysis.17 But, it is only in the last 5 years that for providing plants with the energy they require, the
artificial photosynthesis has been researched in ardor.18 conversion rates of light to storable energy in the form of sugars
Natural photosynthesis is the ultimate ‘green’ energy is only around 4.5% by most calculations.24 In fact, it is believed
production method consuming carbon dioxide and producing that plants only achieve around 1-2% conversion.24 The current
easily applied energy in the form of sugars. While global energy consumption means that we must build artificial
photosynthesis is the process of converting sunlight, water and leaves with far better yields in order to support our needs.
carbon dioxide into carbohydrates and oxygen specifically, However, many of the individual reactions in photosynthesis
artificial photosynthesis encompasses any process that uses are exceedingly efficient and serve as good models for future
sunlight to store energy in the chemical bonds of a fuel. [18b,19] photosynthetic devices, especially photosystems I & II.
There are two different but complementary goals of artificial Both photosystems have a similar structure; they are light-
photosynthesis.20 The first involves the photolysis of water, the harvesting complexes made up of numerous pigments coupled
use of light to dissociate water into hydrogen (H2) and oxygen to a reaction centre where charge separation occurs.[18c,25,26] The
(O2) in a photoelectrochemical cell. Hydrogen is the fuel charge can then be applied to perform the pertinent oxidations
produced with this method. The other is the photochemical and reductions. It is this arrangement that researchers use as a
reduction of carbon to produce higher energy carbon-based blueprint in their design of artificial systems. Although
fuels, generally methanol, ethanol or formic acid. Most research considerable research has been done on solar fuel cells, few
is focused on water splitting since hydrogen is a cleaner fuel have ever been constructed. This paper shall give an overview
than the hydrocarbons, only producing water as a byproduct of existing solar fuel cells and the advances made in solar fuel
opposed to carbon dioxide. Additionally, hydrogen fuel is more cell technology over the last 30 years.
energy dense than traditional fuels.21 This means it requires less
storage space and is easier to transport.
2. NATURAL PHOTOSYNTHESIS
Oxygenic photosynthesis is the most effective known process
to convert sunlight into applicable, productive energy. The two
most interesting components for the design of ‘artificial leaves’

3. COMPLETE SOLAR FUEL CELLS under 100 mW cm-2 illumination giving an efficiency of 6.2%.
There have been only a small number of attempts to build Overall solar-to-fuel efficiencies (SFE) of 4.7% were obtained
complete solar-to-fuel cells. The majority of research is still using Si solar cells with 7.7% efficiency. These results compare
devoted to improving the individual processes that would be favourably to Si photovoltaic (PV) cells, which have a 6% SFE.
applied in future cells, since they are still considerably short of Even, the most efficient (and expensive) PV cells only have
the standards required to build a commercially viable fuel cell. solar-to-fuel efficiencies up to 18%33 and these water-splitting
However, those cells that have been created provide a useful cells have yet to test using more efficient solar cells.
insight into the most pressing processes that need to be
These cells are entirely artificial and inorganic negating the
improved and illustrate how close we are to constructing fully
photodegradation concerns of using PSII, however the Co-
operational and scalable solar fuel cells.
OEC is not nearly as efficient as PSII. These cells would be a
3.1 Inorganic Solar Fuel Cells very green way to produce fuel if their efficiencies were
Oxidation of water
Figure 1 – “Light-dependent reactions of photosynthesis in the thylakoid membrane of plant

cells.” by somepics is licensed under CC BY 4.0
Oxygen evolving complexes (OECs) are a key feature required competitive with other energy production methods. The most
for water splitting in photosynthesis that all artificial systems prevalent environmental concern with this set-up is the
include. Nocera et al. made a meaningful step towards scarcity of molybdenum, as it is a relatively rare metal.34
developing a commercially viable artificial leaf when they Similarly, zinc could be problematic in the future as well.
discovered that certain artificial oxygen-evolving complexes However, nickel and cobalt are two of the most abundant
(OECs) can be self-repairing if they are formed in situ.27 This metals.34 In comparison to other fuel production methods the
imitates the self-repair mechanisms that occurs in natural environmental cost of these metals is small. Other methods
photosynthetic systems with proteases, which repair and either produce carbon dioxide or require batteries that use far
remove the oxidatively damaged constituents of PSII.28 The larger quantities of limited and toxic chemicals including
first artificial OEC that demonstrated self-repairing behaviour metals. Thus, the phosphate and silicon cells can be regarded
is a Co2+ and phosphate aqueous solution. The explanation is as ecologically friendly, in relative terms.
that the Co2+ and phosphate are in equilibrium so cobaltate 3.2 Biovoltaic Cells
ions will reform after it has been oxidized. Cobalt and
phosphate are not the only pairing that exhibit this behaviour, One of the closest attempts to replicating natural
another example is nickel-borate.29 This discovery is important photosynthesis is the biovoltaic cell constructed by Kothe et
in addressing the photodegradation present in systems using al.35 The group had previously published papers on the
PSII and most other catalysts.30 Furthermore since the Co-OEC individual half-cells they developed using PSI in the
catalyst operates in neutral water, simple hydrogen evolution photoanode36 and PSII in the photocathode.37 The authors
reaction (HER) catalysts can be used in place of platinum, for noted that the half-cells had severe deficiencies. The electrons
example NiMoZn, which can achieve current densities as high provided by PSII could not be directly applied in H2 evolution
as 1000 mA cm-2.31 as they were insufficiently energized. The photoanode, on the
other hand, either needed an external potential to be applied or
Nocera et al. were also involved in the development of the first sacrificial electron donors to be able to reduce the desired
standalone water splitting cell in 2011 with 3 amorphous electron acceptors. Subsequently, the group managed to couple
silicon solar cells.32 The solar cells were packed in with a triple the half-cells, in doing so, closely replicating the Z-scheme.
junction and interfaced with the Co-OEC and NiMoZn The semi-artificial photoelectrochemical cell (PEC) operated
catalyst. The system managed to produce 8mA cm-2 with 1.8V as a closed system with no sacrificial electron donors or
acceptors. This is a very significant step towards sustainable The basic set-up was PSII absorbed the light and oxidized
PECs that have a net energetic output. When the cell was water. The resulting electrons were shuttled through
exposed to red photons, the PSII oxidized the water to oxygen Fe(CN)63-/ Fe(CN)64- to the artificial photocatalyst in an
and simultaneously the PSI reduced the oxygen. PSI cannot aqueous solution. Two typical semi-conductors (CdS and
reduce oxygen directly so methyl vi0logen (MV) gets reduced SrTiO3:Rh) were used as a basis to prepare the photocatalysts
by PSI and then regenerates by reducing oxygen. The (Ru2S3/CdS and Ru/SrTiO3:Rh) tested in this study. These
photocathode has the same half-reaction as scheme 1. The were chosen because they possess continuous absorption
photoanode however, follows reaction scheme 3. spectra that are partly complementary to PSII absorption. A
self-assembly approach was used in order to link the
hu photosystem and photocatalyst. The Ru2S3/CdS photocatalyst
MV2+ + e- MV+ achieved a OWS activity of 411 mol H2 (mol PSII)-1h-1, however
the maximum OWS activity of Ru/SrTiO3:Rh was 2,489 mol
MV+ + O2 O2- H2 (mol PSII)-1h-1. Since the O2 evolution activity was much
lower for the Ru2S3/CdS system, it suggests that the difference
in OWS activity is due to Ru2S3/CdS causing conformational
O2- + 4H+ 2H2O changes in PSII. Both reactions had a stoichiometric ratio for
H2:O2 of 2:1 indicating that electron transfer through the Fe
Scheme 3 – the half-reaction occurring at the photoanode of the
complex was effective. The high OWS activity of Ru/SrTiO3:Rh
biovoltaic cell developed by Kothe et al.35
is comparable to the estimated turnover of just PSII, around
Interestingly, the hydrogels connecting PSI and PSII to their 3,751 mol H2 h-1, which suggests that PSII can be stable in a
electrodes need different redox potentials in order to follow the hybrid system. It is worth noting that all the reactions were
Z-scheme. conducted in mild conditions but the OWS activity for both
photocatalysts declined much more quickly over 2 hours when
The electrical power output of the photobiovoltaic cell is very the pH was raised from 6 to 7.
low. The limiting factors are the photocurrent density in the
half-cells and the potential between the redox hydrogels. The principal problem with this hybrid system is that it suffers
While this PEC is far from the performance required for significant deterioration after a few hours of exposure to light.
commercial applications, it is notable for mimicking of the Z- The inorganic photocatalysts are known to be stable over
scheme using both photosystems. Additionally, since the half- several hours40 so it must be the PSII that degrades.
cells are separate, oxygen-sensitive biocatalysts such as Investigations are needed to find a method to stabilize PSII, so
nitrogenase and hydrogenase can feasibly be coupled to PSI, that it can endure the photo-oxidative stress it faces under
potentially increasing the H2 production immensely. Other irradiation, and suppress singlet oxygen radical side reactions.
plans to improve upon this design are to implement hydrogels
Overall, this system is relatively productive and clearly
with more appropriate potentials in order to increase the
demonstrates the possibility of PSII-inorganic photocatalyst
power output by raising the cell voltage and current density.
hybrid cells. Problematically it does involve the rare metals:
The photobiovoltaic cell is a largely green system since most of ruthenium, rhodium and cadmium. It could be justifiable since
thee components are directly extracted from plants large amounts of H2 would be produced from nanoscopic
themselves; however, there would be the cost of farming the amounts of metal. Iron is not environmentally benign but the
plants from which the photosystems are obtained. But it would iron can be recycled preventing significant environmental
be trivial in comparison to the energy gained from a cell that is consequence. Cyanide, however, is toxic to humans and, more
moderately efficient and robust. Methyl viologen is a toxic acutely, to aquatic life.41 Cyanide is essentially environmentally
chemical, but there should be no human exposure during benign if it disposed of through thermal hydrolysis with the
operation and relatively little methyl viologen is needed since byproduct being formate and ammonia. Of course any spills
it is a regenerating catalyst.38 Harmful chemicals including will still be very harmful to the environmental. PSII again will
pyridine and chloroform are used in its synthesis and disposal be extracted from plants but the cost should be worth it
through incineration does lead to gases such as carbon dioxide, provided the PSII does not degrade quickly.
nitrogen oxides and hydrogen chloride. This system is far from
ideal but in comparison to current and alternative methods it
is relatively ecologically friendly. Furthermore, future research 4. CONCLUSION
could find a much more sustainable catalyst, which could make
this method a very ‘green’ way to generate fuel. Three fundamentally different types solar-to-fuel cells were
examined in this paper, completely artificial, hybrid and
3.3 Inorganic Hybrid Cells biovoltaic. Completely artificial cells are appealing because the
issue of photolytic degradation of PS I and II can be avoided.
Another approach is to use hybrid systems to perform solar
However, there is no known oxygen-evolving complex that can
overall water splitting (OWS). It is the oxidation of water by
achieve the thermodynamic efficiency of PSII. Nocera et al. did
PSII that is the truly remarkable activity of natural
create inorganic cells that produced hydrogen,32 but its SFE
photosynthesis, reaching a maximum thermodynamic
needs to be improved as well as scalability of it. The most
efficiency of 70%.18a In consequence, researchers have created
biological approach is using the components used in natural
solar cells using PSII and artificial photocatalysts to reduce the
photosynthesis using both PS I and II. The principal issue is
protons to hydrogen. Wang et al. had significant success in
preventing photodegradation of PS I and II. Kothe et al. did
2014, developing a photosystem that reached activity of about
manage to stabilize the photosystems for a couple of hours and
2,489 mol H2 (mol PSII)-1h-1 under visible light irradiation.39
use them in a functional cell,35 of course the lifetime of the
The cell also achieved OWS under solar irradiation outdoors,
photosystems needs to be vastly improved before biovoltaic
indicating its potential for future industrial implementation.
cells can be considered for industrial use. Finally, hybrid
systems try to integrate the most advantageous qualities of M. E.; Perkins, L. J.; Schlesinger, M. E.; Volk, T.; Wigley, T.
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A Methanol Economy based on Renewable Resources
Thomas Garrow
KEYWORDS: Methanol Economy, Methanol, Carbon Dioxide, Electrolysis
ABSTRACT: The current world reliance on fossil fuels is unsustainable and poses serious environmental consequences. Renewable
energy technologies in the form of wind, solar, hydroelectric, and geothermal have proven to be effective alternatives, yet lack a
method of convenient energy storage. Storing this energy in the form of methanol by conversion of CO2 has proven to be commercially
viable. Current methods of production of methanol and CO 2 capture are outlined and the argument for a methanol economy
propounded.
1. INTRODUCTION is widely considered as playing a major part in climate change

While great strides in the advancement of human societies have and global warming.2 The exploitation of fossil fuels since the
been made possible from the abundance of energy in fossil fuels, Industrial Revolution has allowed the unprecedented
the world’s dependence on this non-renewable resource is development of human society, but it is imperative that we now
becoming increasingly detrimental. More than 80% of the turn our gaze to more sustainable methods of energy
world’s energy consumption comes from fossil fuels, and while production and lead the way for a Green Revolution.
recent discovery and exploitation of unconventional resources Many methods currently exist for the production of renewable
such as shale gas have lowered the price and extended their energy – solar, wind, hydroelectric, geothermal. Primarily these
foreseeable lifetime, their depletion is inevitable.1 Besides the methods are used to generate electricity. A major drawback in
finite availability of fossil fuels, there are many other associated this type of energy production is that electric power needs to
issues that arise from their use such as the emission of SO 2, be scaled to follow the demand on the electrical grid.3
NOx, volatile organic compounds (VOCs), carbon monoxide, Furthermore, solar and wind power are highly variable.
and particulate matter, each having deleterious environmental Regional solar flux, cloudy conditions, and daylight hours are
effects.2 The rate at which fossil fuels are being consumed has large limitations for solar energy. Variable wind conditions and
surpassed the natural carbon cycle, causing an accumulation of consistency also pose a problem. Therefore a more convenient
CO2 in the atmosphere.2 This accumulation of a greenhouse gas

way of storing this energy must be realized in order for rate of climate change and global warming demands an
renewable energy to be viable. immediate solution. Thus it is far more sensible to implement a
One method of storing this energy would be to convert it to Methanol Economy, wherein the inherent challenges are not
methanol, as proposed by proponents of a Methanol Economy only far less formidable, but has proven to be commercially
in which this molecule is used for fuel and raw material.4 In viable.
this paper, the argument for such a Methanol Economy is put
forth and outlines the methods of converting CO2 to methanol. 3. METHANOL ECONOMY
In light of the challenges faced with a Hydrogen Economy,
2. HYDROGEN ECONOMY proponents such as Nobel Prize recipient George Olah have
One of the proposed methods of storing renewable energy is in advocated a Methanol Economy in its stead.3-4 Being a stable
the form of hydrogen gas, H2. This would be primarily liquid, methanol would be much more preferable than dealing
accomplished through the electrolysis of water to yield oxygen with the complications of a pressurized gas or super-cooled
and hydrogen gas. The resulting combustion of H2 would yield liquid.3-4 The existing infrastructure for gasoline would only
water (eqn. (1)). need to be modified in order to accommodate methanol, as
opposed to being built from the ground up.3-4 While methanol’s
volumetric energy density is only 50% that of gasoline, it is
2H2O  2H2 + O2 (1) nearly triple that of H2.3-5 Additionally, methanol burns cleaner
than gasoline, and has lower CO2 emissions.3-4 The argument
This method is attractive in the sense that it is clean, with no for a Methanol Economy is based on its practicality, and its
production of CO2 or other hazardous compounds5. ability to be incorporated on a relatively short timescale. While
Proponents of this method point to a potential Hydrogen using H2 as a fuel may be attractive, given the rate of climate
Economy, whereby this process provides energy for change and global warming, it is much more sensible to
transportation and industry.3-4 However, serious limitations consider employing a Methanol Economy, at least until the
exist with this method. While H2 has one of the highest energy technology and economic feasibility of using H2 improve.
densities per unit mass, its energy per unit volume is very low.3- Of particular incentive toward a Methanol Economy is the
5 This poses a problem especially for mobile applications, such productions of methanol from renewable feedstocks such as
as the transportation sector, where the volume must not be biomass and CO2 capture. These processes have the potential
exceedingly large. In order for H2 to be feasible as an energy not only to be carbon neutral, but also carbon negative if
source in vehicles, it must be contained in a small enough renewable energy is employed.3-4, 9-10 The ability of recycling
volume so as to be practical to be transported. Two methods of CO2 is potentially limitless, either by direct capture from
accomplishing this, compression and liquefaction, are highly industrial power plants or by that from atmospheric CO2.3-4, 11
energy intensive, and would cost around 20-40% of the Many methods in this area are being researched, including
intrinsic energy value of the initial gas, respectively.3-5 As a gas, absorption into liquids, adsorption onto solids, or by
high pressures are needed, while very low temperatures are membrane separation.3,11 The capture of CO2 from sources such
required for liquefaction.3-5 Furthermore, H2 is inflammable as fossil-fuel burning power plants, where high concentrations
and explosive, further complicating its ability to be safely3-5. In of CO2 emissions exist, and subsequent recycling into
addition to these barriers, H2 has the ability to escape through methanol is an attractive option. As technologies for direct air
solid metal pipes and embrittle metals.3-5 capture of CO2 become more viable, transitioning from its
In light of these drawbacks, much effort has been placed into capture from these plants would be an attractive solution to the
finding alternatives to H2 storage. Among these are material issue of greenhouse gases.3-4, 11
based storage methods such as absorbents and metal hydrides.6
Among the physical adsorption methods are Metal Organic 4. CARBON CAPTURE
Frameworks (MOFs), Covalent Organic Frameworks (COFs), Many options exist and are being developed for the capture of
Polymers with Intrinsic Microporosity (PIMs), and zeolites.7 CO2. These are based on processes such as absoption of CO2
These mediums rely primarily on Van-der-Waals forces for into liquids, adsorption onto solids, and separation by
adsorption.7 While there is potential for these mediums, they membrane.3-4, 11-16 All of these processes are influenced by the
are currently limited by low temperatures or high pressures
concentration of CO2, temperature and pressure, and
needed for significant adsorption.6-8 Metal hydrides have been
impurities present in the gaseous mix.11-16
an active area of research for H2 storage. The current challenges
facing this medium are due to their weight and low H2 density
per unit mass.6-7 Additional complications exist such as their 4.1 CO2 from Industrial Plants
exothermic absorption process, which would necessitate One method of capturing CO2 is by its direct capture from
removal of heat upon refueling, expansion upon refueling fossil-fuel burning power plants, petrochemical plants, cement
creating stress upon the container, long refueling times, and production, and refineries.3-4, 11-16 This method exploits the high
with certain metal hydrides such as AlH3 complicated concentration of CO2 generated by these plants.3-4 While it
syntheses.6-7 Coupled with these challenges is the fact that no might seem that the obvious solution would be to capture CO2
infrastructure currently exists for H2, and the cost to develop from a source with the highest emissions, the partial pressure
one would be enormous.3-4 of CO2 plays a large role in its ease of separation, with higher
Considering the challenges associated with the use of H2 as a partial pressures requiring less energy.16 Additional energy
fuel - the inherent hazards, physical properties, storage would be required for CO2 separation, as well as compression
methods, the time and cost of creating an infrastructure and or liquefaction.16 Additionally, the presence of impurities in the
distribution, it would be more practical to use methanol as a flue gas would increase the energy needed as well as the cost. 16
storage medium. The potential for H2 as a fuel holds potential, In post-combustion capture, CO2 is absorbed into amines, NH3,
and may be a viable source of energy in the future. However the or alkaline solvents.3, 16 The CO2 is then released from the

solvent by heating or decreasing pressure.16 This method is
relatively easily incorporated into existing plants, however the CO2 + 3H2 ⇌ CH3 OH + H2 O (2)
process can be costly.16 An alternative is to use O2 in the
combustion process instead of air, which could increase the
purity of the flue gas, and potentially reduce the amount of This method typically employs the use of a metal catalyst, such
energy needed.3, 16 However, this poses additional problems as Cu or Zn based complexes.3, 11-17 This process is primarily the
such as adapting equipment to enable this process, and is costly method of methanol production from syngas in industry. 3-4, 11-17
due to the need for O2 production.3, 16 However, there currently exist plants that make use of CO 2
from industrial carbon capture and H2 from electrolysis, such
as in Carbon Recycling International’s plant in Iceland.3, 14 This
4.2 Direct Air Capture plant has an annual production of 4500 m3 of methanol,
The direct capture of CO2 from the atmosphere is a particularly capturing CO2 from a neighboring geothermal plant and
attractive method. In contrast to capture from point sources, producing H2 from electrolysis from geothermally produced
direct air capture (DAC) can be employed without the need for electricity.3, 14 The success of this plant has led to plans for
proximity to the emission source.3-4, 11-16 This is especially useful construction of another with a ten-fold production capacity.3
when considering that direct capture from the transportation Other companies around the world have similar plants. In
sector would be economically prohibitive and impractical.3 Japan, Mitsui Chemicals produces methanol from industrially
In contrast to capture from industrial sources, which rely on captured CO2 and H2 produced by photo-electrolysis of water.3
the combustion of fossil fuels, this process has the potential to A similar plant in Canada is being designed by Blue Fuel Energy
solely remove CO2 from the atmosphere if renewable energy is using hydroelectric and wind power to produce H2.3
used. However, currently the various methods involved are
more energy intensive and costly than capture from industrial 5.2 CO2 to Methanol via electrochemical conversion
sources, ranging approximately 2-4 times the energy needed
from this process.3, 16 Furthermore, the process of capturing An area of development is in the conversion of CO2 to methanol
CO2 is more complicated due to its lower concentration in the by electrochemical reduction. This process is outlined in the
atmosphere, and the difficulty in the separation process following reaction.
between water and CO2.3, 11-16
Currently there exists many methods for DAC capture, and the CO2 + 6H+ + 6e-  CH3OH + H2O (3)
design of novel materials is an active area of research. The types
of materials used are very diverse, from solid porous materials,
The process involves various types of metal electrodes
polymers, alkali metals on carbonates, ionic liquids, to name a
immersed in a solvent, typically water, with CO2 pumped into
few.11-16 The use of solid adsorbents such as zeolites, metal
solution.14, 18 A voltage is applied, CO2 is reduced and reacts
organic frameworks (MOFs), activated carbon for example
with protons to form methanol.14, 18 While this process has been
work primarily by their large surface areas, but tend to have
performed on a laboratory scale, there exist many barriers
poor selectivity, especially in the presence of water.3, 11-16
before its viability on an industrial scale can be realized.18
Research into improving these mediums, such as surface
Typically this process is energy intensive, with low
modifications, are being developed.11-16 Ionic liquids have
efficiencies.18 Competition for reduction at the cathode
shown to have large capacities for CO2 absorption, although
between CO2 and H2O further complicate this, with excess H2
their high viscosity poses a problem for absorption and
being produced.18
desorption rates.16 Consequently, the use of ionic liquids
supported by porous membranes such as MOFs are being
developed and have shown high potential.16 The use of strong 5.3 CO2 to Methanol via Photocatalysis
bases such as KOH and NaOH are effective in CO2 capture, The photocatalytic reduction of CO2 to methanol is similar to
although their corrosiveness and high temperatures (>700 °C) the electrocatalytic reduction process but uses light energy to
needed for regeneration pose a problem.3, 16 Materials using drive the reaction. While this process has potential, the issues
amines on solid supports have shown promise, and can be associated with electrochemical conversion, namely low
regenerated with much lower temperatures (<110 °C).3, 16 selectivity, high energy cost and low efficiencies, also apply.18-21
Finally, given the concern that the aforementioned Additional problems arise with the scattering of light and the
technologies will carry a considerable cost for large scale use, photo-efficiencies of the catalysts.18 Until great advancements
efforts to develop DAC systems from waste materials, such as in this field are achieved, this technique will not be viable on an
nut shells, coffee grounds, industrial silica waste, are being industrial scale.
researched.14
While DAC faces many technical challenges and is at present
far from being realized on a large scale, it should not be 6. CONCLUSION
dismissed as being unrealistic. Whereas other renewable An alternative to the current world reliance on fossil fuels is
resources such as fuel crops and biomass are fundamentally necessary due to their limited resources and associated
limited, this process has the distinct advantage of having a negative environmental effects. The development of renewable
limitless feedstock of atmospheric CO2 while simultaneously energy technologies such as wind, solar, geothermal, and
solving the problem of elevated levels of this greenhouse gas.14 hydroelectric have proven to be viable alternatives. However
these technologies produce primarily electricity, which is
difficult to store. Therefore a method of storing this energy for
5. HYDROGENATION OF CO2 TO METHANOL later use is needed. Among the possible methods for storage,
There are a number of pathways to produce methanol from methanol is a particularly suitable medium given its physical
CO2. One method is by direct hydrogenation of CO2 by H2.3-4, 11- properties and synthesis pathways. The ability to produce
17 In order for this process to be carbon neutral, the use of H by
2 methanol from CO2 is not only commercially viable, but has the
electrolysis from renewable energy would be required.3-4 potential to reduce the atmospheric concentration of this

greenhouse gas. As the technologies for CO2 capture and frameworks for H2 storage." Phys Chem Chem Phys 16(35): 19001-19010.
conversion continue to be improved, so too will its cost and 9 Martín, A. J., et al. (2015). "Towards sustainable fuels and chemicals through
productivity. If climate change and global warming are to be the electrochemical reduction of CO2: lessons from water electrolysis." Green
combatted in the immediate future, a Methanol Economy is Chem. 17(12): 5114-5130.
10 Alberico, E. and M. Nielsen (2015). "Towards a methanol economy based on
worth serious consideration. homogeneous catalysis: methanol to H2 and CO2 to methanol." Chem
Commun (Camb) 51(31): 6714-6725.
ABBREVIATIONS 11 Markewitz, P., et al. (2012). "Worldwide innovations in the develop
VOCs, Volatile Organic Compounds; Covalent Organic pment of carbon capture technologies and the utilization of CO2." Energy &
Frameworks, COFs; Polymers with Intrinsic Microporosity, PIMs; Environmental Science 5(6): 7281.
Direct Air Capture, DAC
12 Lackner, K. S. (2014). "CHAPTER 4. The Use of Artificial Trees." 80-104.
REFERENCES 13 Goeppert, A., et al. (2012). "Air as the renewable carbon source of the future:
an overview of CO2 capture from the atmosphere." Energy & Environmental
1 Key World Energy Statistics 2015, International Energy Agency Science 5(7): 7833.
(IEA), Paris, 2015. 14 Wang, J., et al. (2014). "Recent advances in solid sorbents for CO2capture and
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Working Groups I, II and III to the Fifth Assessment Report of the 15 Queen, W. L., et al. (2014). "Comprehensive study of carbon dioxide adsorption
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3 Goeppert, A., et al. (2014). "Recycling of carbon dioxide to methanol into fuels and chemicals by catalytic, photocatalytic and
and derived products - closing the loop." Chem Soc Rev 43(23): 7995- electrocatalytic processes." Energy & Environmental Science 6(11):
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4 Olah, G. A. (2005). "Beyond oil and gas: the methanol economy." Angew Chem 17 Wang, W., et al. (2011). "Recent advances in catalytic hydrogenation of carbon
Int Ed Engl 44(18): 2636-2639. dioxide." Chem Soc Rev 40(7): 3703-3727.
5 Zehner, O.(2012). Green Illusions: The Dirty Secrets of Clean Energy 18 Das, S. and W. M. A. Wan Daud (2014). "A review on advances in
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6 Xia, Y., et al. (2013). "Porous carbon-based materials for hydro 19 Fresno, F., et al. (2014). "Photocatalytic materials: recent achievements and
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1(33): 9365. 20 Protti, S., et al. (2014). "Photocatalytic generation of solar fuels from the
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On the Effectiveness and Sustainability of Large-Scale CdTe
Photovoltaic Cell Use
Sebastian G. F. Drake
KEYWORDS: Photovoltaic Cell, Solar Cell, CdTe, thin-film
ABSTRACT: The environmental damage caused by the use of fossil fuels has created a need to develop alternative energy sources
with significantly less harmful environmental impacts. Solar energy is one of the fastest growing energy sources, with many different
types of photovoltaic cells being developed. One such technology is thin-film CdTe photovoltaic cells. This review investigated the
economic, practical, and environmental consequences of these CdTe devices. Life cycle analyses were used to determine
environmental impact. Energy payback time and manufacturing costs were used to examine relative economic and energy efficiency.
It was concluded that pursuing this technology and its benefits due to efficiency, cost, and versatility in greater applications would
indeed be suitable for large-scale use despite to risk to the environment and human health caused by cadmium toxicity and tellurium
scarcity.
INTRODUCTION
The environmental consequences of energy production and

consumption have only recently come to the attention of the
public. The vast majority of the world’s energy currently comes
from fossil fuels, meanwhile, "Most of the observed increase in
global average temperatures since the mid-20th century is very
likely due to the observed increase in anthropogenic GHG
(Green House Gas) concentrations" (IPCC, 2007).

Figure 1: efficiency development of different types of photovoltaic
Our new-found awareness has led to a significant push by cells over the past 40 years1.
governments and citizens alike to discover renewable sources
of energy to replace greenhouse-gas emitting fossil fuels. The
need for alternative energy from an economic and security Solar energy has emerged as one of the largest alternative
perspective was made painfully clear during the oil crisis in the energy sources, accounting for 1% of total global energy
1970 which displayed the vulnerability of the world’s economy production. In 2015, solar PV demand is expected to grow by
to foreign-supplied energy. up to 25%, with double digit growth expected for the rest of
the decade. As research and development in this industry
progresses, it is important to understand the impacts,
Thin-film Cadmium Telluride photovoltaic cells (CdTe PV)
advantageous or disadvantageous, of any new technology that
are a specific type of PV cell whose characteristics make it a
is conceived. Every photovoltaic cell has production costs and
very tempting avenue for further development and large-scale
environmental impacts depending on the type of cell involved.
production. In 2013, CdTe PVs accounted for 5.4% of all solar
In 2014, investment in solar energy sources reached $150
cells. This paper will evaluate the advantages and
billion. For governments to develop well informed regulation
disadvantages of CdTe photovoltaic production and use, along
and policy, the full consequences of whatever technology they
with its more long-term environmental impacts and
incentivize must be known.
sustainability.
Semiconductors are used for photovoltaic cells due to the

DISCUSSION
phenomenon of exciton generation. When a semiconductor
absorbs a photon, an electron is promoted from the valence
Figure 1 shows the efficiency development of photovoltaic band to the conduction band, above a forbidden region of
cells over the past 40 years. It is clear that CdTe solar cells are energies known as the band gap. That electron is now free to
not the most efficient cells available. The record efficiency of flow (hence conduction band) and so is drawn into a metal
thin-film CdTe photovoltaic cells is 21.7% as of 2015 while contact with a galvani potential, creating an electromotive
highly complex multijunction cells have reached 46%. force.
Although not the best, they are competitive in terms of The key, then, is to absorb as much of this light as possible to
efficiency with silicon based PV cells, currently the most encourage as much electron excitation as possible. The
common type, and have several other advantages to be maximum theoretical efficiency of a solar cell is dependent on
discussed later. Many mass-producible solar cells with the band gap by the Shockley-Queisser limit2. The band gap of
efficiencies at around 20% are competitive with conventional CdTe is ~1.5eV, very near to the ideal of 1.34eV predicted by the
sources of energy. It is predicted “that solar systems will be at model. This coincidence makes CdTe a near-ideal material for
grid parity (production cost of solar=production cost on grid) solar light absorption, hence the enthusiasm for its use in solar
in up to 80 per cent of the global market within 2 years”. panels.

tellurium production should market share continue to increase
at its current rate. With market share of solar energy set to
increase to 10% by 2030, tellurium production would have to
increase by a factor of 40 to meet such levels of demand11.
However, it has been shown that modules using 1/30th of the Te
can achieve around two thirds normal efficiency 12. Historical
increases in copper production, a major source of tellurium,
improved refining techniques as well as discoveries of more
tellurium-rich deposits in the ocean provide significant
avenues for future Te productionxvi.
CdTe thin films perform remarkably well against other solar

cell types in many categories. In terms of energy, a review of
photovoltaic LCAs by Bhandari13 et al showed the energy
payback time (EPBT, amount of time to harness as much energy
as it took to produce) of CdTe (~0.7 years) is the best of major
competing technologies including amorphous Si (~1 year),
Figure 2: Basic schematic of CdTe Thin Film photovoltaic cell. CIGS (~1.3 years), poly-crystalline Si (~1.6 years), and mono-
Design interpreted from Romeo et al. (2004)3. (TCO=Transparent crystalline Si (~1.7 years).
Conducting Oxide)
Another life cycle analysis confirmed CdTe films supremacy in
Figure 2 is a simple schematic of the thin-film CdTe EPBT, and also found CdTe to have the lowest material input
photovoltaic devices in question. The very simple construction per service (kg material/kWh), the lowest global warming
of these devices along with the low number of materials used potential based on carbon emissions, the lowest ocean
heavily contributes towards their low manufacturing costs of acidification potential, and the lowest ecotoxicity potential14
thin-film PV cells. Manufacturing costs of CdTe films have compared to poly-Si and CIGS. The superiority of CdTe is
reached $0.57/W4. The films can be applied to a wide variety of largely due to the smaller amount of materials needed to
substrates, giving additional freedom to manufacturers to produce them, as even though cadmium is highly toxic, other
reduce costs5. technologies produce much higher volumes of such hazardous
waste. Compared to conventional energy sources, CdTe PV
cells are greatly superior in terms of emissions of cadmium
The simplicity of manufacturing is also determined by the itself, giving off 0.02-0.3 g Cd/GWh compared to 2-3.1 g
material properties of the film itself. Thin films are very flexible; Cd/GWh from coal burning power plants. CdTe PVs also gives
they can be bent and twisted unlike rigid crystalline solar off less cadmium than mono- and poly-Si, who both had
panels. This flexibility allows for installment in more awkward emissions around 0.9g Cd/GWh, triple that of CdTe films
and uneven places such as a curved surface. CdTe films also (Fthenakis et al., 2008)15. The use of CdTe films also led to
have a large temperature tolerance, with the ability to sustain reduced emissions of arsenic, chromium, lead, mercury, and
significant performance at high temperatures. The nickel.
combination of these properties has seen CdTe films be the
ideal material for use in space6, as their versatility lends itself to
such hostile environments. CONCLUSION
The advantages and disadvantages of thin-film CdTe
photovoltaic cells have now been examined. It still remains,
Cadmium, the main component of the films, is a widely however, to see whether this technology can actually be
available and cheap material. It is a significant component of considered a “green” technology.
many zinc ores, and so is largely produced as a byproduct of
zinc smelting7. Cadmium, however, is a highly toxic heavy
metal with a very low lethal dose of 135mg8. Exposure can lead Thin-film CdTe solar cells are some of the most resource
to kidney failure, liver failure, prostate cancer, and lung cancer. efficient, energy efficient, and waste reducing PV technology on
Having cadmium present in high quantities is very dangerous the market. This technology prevents waste cadmium that
to human life, and it is known to accumulate in plant, animal, would be produced should alternative technologies be used. Of
and marine life9. competing technologies, CdTe films incorporate far more of its
starting materials into the final product. The energy
requirements to produce these films are also completely
Tellurium, the other main component of the thin film, is an recovered after less than a year.
extremely rare element. It is almost as rare as platinum, with an
abundance of only 1 ug/kg10. The abundance of tellurium is low
enough that production of CdTe thin films would be limited by
3 10
4 11
5 12
6 13
7 14
8 15
9

CdTe films necessarily produce toxic waste because the 1 Top Solar Power Industry Trends for 2015 | IHS. (2015).
central component is a toxic heavy metal. The only way to fix https://www.ihs.com/info/0115/top-solar-power-industry-trends-for-
this would be to find an alternative metal to serve in cadmium’s 2015.html
1 Global Trends in Renewable Energy Investment 2015. (2015,
place. There are metals that can do this, however, all of them
March 1). Retrieved from http://fs-unep-
are either rare, toxic or both. Although generated levels are centre.org/publications/global-trends-renewable-energy-investment-
minimized, the persistence of cadmium is a hazard, especially 2015
when used over an extended period of timexiii, xiv. Because 1 Shockley, W., & Queisser, H. (n.d.). Detailed Balance Limit of
cadmium is a by-product of the smelting of other metals, it is a Efficiency of p-n Junction Solar Cells. J. Appl. Phys. Journal of Applied
waste product that must be processed in some regard. Physics, 510-510.
Fthenakis et al argue that CdTe PVs are actually one of the 1 Romeo, A., Terheggen, M., Abou-Ras, D., Bätzner, D., Haug, F.,
most environmentally safe ways to trap and keep cadmium Kälin, M., . . . Tiwari, A. (n.d.). Development of thin-film Cu(In,Ga)Se2
localized compared to other more dispersive methods like its and CdTe solar cells. Prog. Photovolt: Res. Appl. Progress in Photovoltaics:
inclusion in fertilizers16. Research and Applications, 93-111.
1 First Solar Reports Largest Quarterly Decline In CdTe Module
Cost Per-Watt Since 2007. (2013, November 7). Retrieved from

The depletion of Tellurium is the major limitation of the http://cleantechnica.com/2013/11/07/first-solar-reports-largest-
application of CdTe films. Tellurium is a very limited and non- quarterly-decline-cdte-module-cost-per-watt-since-2007/
renewable feedstock. This can be remediated by either
1 News. (n.d.). Retrieved from
concerted recycling to maximize use of all Te that has been http://www.renewableenergyfocus.com/view/34056/flexible-thin-
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produced. Luckily, recycling programs have been put in place, 1 Romeo, A. (n.d.). Potential of CdTe thin film solar cells for space
one in particular by First Solar, the largest producer of thin film
applications. Lecture presented at 17th European Photovoltaic
CdTe PVs, which is able to recover up to 95% of Cd and Te 17, in Conference and Exhibition in Thin Films Physics Group, Laboratory
addition to developing mobile recycling facilities. They also for Solid State Physics, Swiss Federal Institute of Technology, Zurich.
claim that the CdTe-PV industry can be fully reliant on 1 Scoullos, M., Vonkeman, G., Thornton, I., & Makuch, Z. (n.d.).
recycled PV modules by 2038. Cadmium. Environment & Policy Mercury — Cadmium — Lead Handbook for
Sustainable Heavy Metals Policy and Regulation, 71-272.
1 Cadmium dust (as Cd). (2015, February 13). Retrieved from
In conclusion, thin-film CdTe photovoltaic cells may create http://www.cdc.gov/niosh/npg/npgd0087.html
toxic waste, but they do so at lower levels than almost all other 1 Frazier, J. (1979). Bioaccumulation of Cadmium in Marine
major forms of photovoltaic energy production, and are one of Organisms. Environmental Health Perspectives, 75-75.
the best ways to sequester the inevitable wastes of other 1 Ayres, R. (2002). A handbook of industrial ecology. Cheltenham, U.K.:
industries. Improvements in tellurium production and Edward Elgar Pub.
recycling will mitigate supply restrictions on CdTe PV 1 Zweibel, K. (2010). The Impact of Tellurium Supply on Cadmium
production. This technology is a relatively low-impact, cheap, Telluride Photovoltaics. Science, 699-701.
1 Matin, M., & Dey, M. (n.d.). High performance ultra-thin CdTe
effective, and so viable long-term energy source.
solar cell with Lead Telluride BSF. 2014 International Conference on
AUTHOR INFORMATION Informatics, Electronics & Vision (ICIEV).
1 Bhandari, K., Collier, J., Ellingson, R., & Apul, D. (2015). Energy
Sebastian G. F. Drake payback time (EPBT) and energy return on energy invested (EROI) of
solar photovoltaic systems: A systematic review and meta-analysis.
Phone: 514-867-5309 Renewable and Sustainable Energy Reviews, 133-141.
1 Raugei, M., Bargigli, S., & Ulgiati, S. (n.d.). Life cycle assessment
E-mail: [email protected]
and energy pay-back time of advanced photovoltaic modules: CdTe
REFERENCES and CIS compared to poly-Si. Energy, 1310-1318.
Fthenakis, V., Kim, H., & Alsema, E. (n.d.). Emissions from 1 Fthenakis, V.M., Kim H.C., and Alsema, E., Emissions from
Photovoltaic Life Cycles. Environmental Science & Technology Environ. Sci. photovoltaic life cycles, Environmental Science and Technology, 2008,
Technol., 2168-2174. 42, 6.
1 Photovoltaics Report. (2015, November 17). Retrieved from 1 Fthenakis, V. (n.d.). Life cycle impact analysis of cadmium in CdTe
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http://www.nrel.gov/ncpv/ s_WADE.pdf
17

Chemical Valorization of Coffee Bean Waste
Ross Koby*
KEYWORDS: Coffee, Waste, Biodiesel, Biorefinery, heavy metal remediation, bio-based plastics,
ABSTRACT: Coffee is a popular beverage consumed by a large proportion of the adult population worldwide. Its production is a
key component to the economy of many countries. Because of the large amount of the coffee plant grown, there is a massive amount
of agricultural and industrial waste associated with it. This article serves to highlight several proposed uses of various types of
coffee waste, and show how they can be beneficial.
INTRODUCTION there is a potential profit of more than $8 million/year from

Coffee is one of the most popular beverages in the world and only Starbucks’ waste in the United States3 being used to make
also the 2nd most traded commodity after petroleum1. Because biodiesel and fuel pellets.
of this, there is an astounding amount of solid coffee waste, the As shown in Table 1, spent coffee grounds have a variety of
covering of the beans known as the husk, or the extracted interesting components that are themselves valuable without
ground bean, known as spent coffee grounds (SCG). In bulk any processing.
availability, this waste is mostly from the industrial production The uses for coffee waste most frequently investigated are
of instant (soluble) coffee, though the solid waste from coffee production of biodiesel via transesterification of extracted oils,
shops and restaurants is still quite significant. There are over 6 use of solid waste as a sorbent or for metal extraction,
million tons of spent coffee waste created every year just from extraction of small organic molecules such as phenolic
instant coffee production, with most discharged to the compounds, or use as a feedstock in biorefineries. The rest of
environment. This creates issues due to the toxic nature of this paper will focus on modern coffee waste valorization
caffeine and tannins2, in addition to other bioactive techniques, including those mentioned before.
polyphenols, notwithstanding the fact that this waste can
ferment and spontaneously combust.
With this much waste created, there is an environmental
imperative to utilize it to reduce harm from simply dumping it.
At the same time, there is serious economic potential in 6
million tons of organic material full of interesting compounds
available at very low costs or for free. One article estimates that

Table 1: Spent Coffee Grounds (SCG) Composition4 used as a sugar source for yeast to produce alcohol and a variety
of other compounds. Some of the more interesting compounds
Parameter Content (wt%) produced by yeast on coffee husk are flavoring and aroma
Cellulose 8.6-13.3 compounds, including isoamyl acetate and ethyl-3-hexanoate,
responsible for the scents commonly associated with bananas,
Hemicellulose 30-40 pears, and pineapples.
Proteins 6.7-13.6
Oil 10-20
Lignin 25-33
Polyphenols 2.5
Caffeine 0.02
Coffee Detoxification
Coffee must be detoxified before it is used in situations
where its bioactive components might have detrimental
effects5. These deleterious effects are primarily due to caffeine
and tannins. Caffeine, part of the methylxanthine class, is not
particularly harmful to humans6. To reach the FDA reported
toxic dose of 10 g, more than 50 cups of very strong coffee must
be consumed. In other words, one must purposefully try to
poison themselves with caffeine. However, plants and many
animals are much more susceptible to caffeine toxicity. It is Figure 1: Biosynthetic Pathway of Gibberellic Acids in Fungi13
toxic and a teratogen for rats, and also known to be quite toxic Coffee waste can also be used as a feedstock for biogas
to dogs, rabbits, and cows7. It is theorized that caffeine is production, which is mostly methane. This is usually done via
present in plants as a form of “chemical weaponry” to defend anaerobic fermentation. A flowchart of this process is shown
young tissue from herbivores and pathogens. Spraying plants below in figure 2. It is a particularly good feedstock, producing
with caffeine solutions or engineering them to produce caffeine 730 m3 of biogas per ton, as compared to between 250 and 500
themselves8 has been shown to reduce predation9. In other m3 per ton of sugar, agave, or corn waste14. It is also shown to
words, agricultural coffee waste that will be in contact with be a good plant growth medium, again, making it a good
plants or animals should have at least some caffeine and other fertilizer.
xanthines removed. This is important for its use as a fertilizer,
which has been shown to be very beneficial to sandy soils in
tropical environments which do not hold water very well10.
Using a waste product as fertilizer is important, as it disposes
of waste, adds value to it, and provides fertilizer for people who
cannot afford to buy commercially produced mineral
fertilizers. Coffee is often produced and processed in countries
with lower buying power, so utilizing a common waste Figure 2: Stages of Anaerobic Digestion15
product could be very beneficial to the quality of life for people
in these countries.
Polyhydroxyalkanoates and Carotenoids
Coffee waste can be detoxified by a variety of means. One Polyhydroxyalkanoates (PHAs) are biodegradeable and
method that has been investigated and shown to be successful biocompatible polymers similar in properties to polypropylene
is degradation of the pulp or husk by fungi. The husk is the part and polyethylene. They are not currently popular or common
of the harvest bean removed to yield a usable bean. Using a because of their high production cost. Polypropylene has a cost
variety of Aspergillus and Rhizopus strain fungi, up to 90% of of under 1 USD per pound16, sometimes as low as 65 cents per
pound. PHA is priced by Metabolix, the main producer, at
caffeine and 60% of tannins were degraded11. This is extremely
between 2.25 and 2.75$ per pound17 Using a waste material
important for coffee husk use as a feed source for animals, as
such as SCG would significantly lower this cost, making it
they can only be used for less than 10% of animal feed without
competitive with conventional petrol-based plastics. PHAs are
treatment. Coffee husks are rich in nitrogen and a variety of
themselves promising materials, as there are many types of
minerals, making them valuable resources.
PHAs that are easily mixable to customize the physical
properties of the plastic. The method for producing PHAs is
Biological Processing the fermentation of oils with different bacteria4. Bacteria
As previously mentioned, fungi can be grown on coffee husk, produce these polymers as a storage for carbon, and future
and it can be used as a growth medium for a variety of different energy source. As will be mentioned later on, SCG can have a
mushrooms. In addition to using fungi for detoxifying SCG, relatively high amount of free fatty acids that can, for example,
they can be used to produce valuable materials, such as citric make it difficult to use as a biodiesel source. However, this free
acid or gibberellic acid12, a plant growth hormone. A reaction fatty acid content makes it better for PHA production. Some of
scheme showing the biosynthesis of gibberellic acids is shown the compounds found in SCG can have antimicrobial action,
below in figure 1. As coffee husk has a fair amount of like polyphenols. This can be solved by detoxifying the SCG or
fermentable sugars (50% carbohydrates by weight), it can be extracting these compounds.

shown to remove large amounts of heavy metal ions from
Carotenoids are another valuable type of compound that can aqueous solutions. Due to the carboxylic, lactonic, and
be produced via biotechnological conversion. They are phenolic functional groups on the surface of the husks, they are
currently used in the food industry, and due to their anti- able to bind to or chelate metal ions. Compared to many other
carcinogenic properties, are expected to be used in or as popular biosorbents, coffee husks perform very well (~7 mg
pharmaceuticals. This makes investigating novel production metal adsorbed / g sorbent). In addition, they are able to adsorb
methods important. Like with PHAs, biotechnological some of the more common heavy metal contaminants such as
production of carotenoids is expensive due to the cost of the Cu(II), Zn(II), Cd(II), and Cr(VI). Currently, coffee husks do
source materials. If waste materials such as SCG can be used, not have an alternative use besides possibly a biofeedstock as
the cost goes down significantly. Carotenogenic yeast can use mentioned before, meaning they are a great candidate for
the SCG solids remaining after oil extraction, allowing for use biosorbent use in countries that have a large amount due to
of the entire waste stream without relying on combustion. coffee production. Again, access to a cheap, effective material
could be very useful for countries that cannot afford to
purchase expensive remediation chemicals or equipment.
Biodiesel from Coffee Oils
As shown in table 1, spent coffee grounds have a significant
oil content. In an article by the Misra group3, 15 g of oils could Table 2: Biodiesel Data from Misra Paper 3
be recovered by refluxing dried coffee grounds for an hour in
about 300 ml of a low boiling point organic solvent. After Test Name Test Method Limit Results
recovery of the oils by rotary evaporation, the solvent can be Free Glycerin (Mass ASTM D 6584 max 0.020 0.006
reused. The free fatty acids were removed by saponification %)
using a basic solution, then rotary evaporation. Less polar
solvents extracted a smaller amount of free fatty acids, yielding MG(Mass %) ASTM D 6584 N/A 0.076
a better oil mixture for transesterification. With optimized DG(Mass %) ASTM D 6584 N/A 0.027
transesterification conditions, 100% yield biodiesel was TG(Mass %) ASTM D 6584 N/A 0.000
possible. This biodiesel was of higher quality19 than that from
cooking waste oil in multiple ways, including stability due to total glycerin (mass %) ASTM D 93 Max 0.240 0.109
antioxidant content, and a pleasant coffee-like odor. With phosphorus (ppm) ASTM D 4951 Max 10 2.0
respect to the biodiesel produced, it can be high quality. Data
Ca+ Mg (ppm) EN 14538 Max 5 2.0
regarding this quality is shown below in table 2. In addition,
after extraction of oil, the solid leftover can be used for fuel Na+ K (ppm) EN 15438 Max 5 2.0
pellets due to the high concentration of lignocellulosic Viscosity at 40°C ASTM D 445 1.9-6.0 5.84
material. It should be noted that this method of biodiesel
production must be altered for a scale up, meaning it might not TAN (mg KOH/g) ASTM D 664 Max 0.50 0.35
be industrially feasible. oxidation stability by EN 14112 min 3.00 3.05
rancimat (h)
Considering the world supply of SCG, there is the possibility cloud point (°C) ASTM D 2500 N/A 11.0
of producing 340 million gallons of biodiesel per year from
coffee waste. This is equivalent to about 8.1 million barrels. pour point (°C) ASTM D 97 N/A 2.0
Currently, only about 10,000 barrels of biodiesel are produced
per day in the United States, compared to almost 5 million sulfur, by UV (ppm) ASTM D 5453 15 8.0
barrels of distillates per day, which consists of mostly diesel
though includes jet fuel and fuel oil. This means that using SCG
as a biodiesel source would make a significant increase in the
amount of biodiesel available, adding a production of 22,000
barrels per day. In a paper by Boonamnuayvitaya21, coffee residues (SCG)
were pyrolyzed and mixed with clay in a 80:20 ratio to be used
as a sorbent. This ratio was chosen due to increasing
As is shown in table 2 below, coffee oil based biodiesel can effectiveness with increased coffee residue content, and the
meet industrial requirements and is a potential drop in physical property limitations above 80:20. An 80:20 ratio
replacement for diesel in many applications, including allowed 4 mm granule sizes, typical for a packed-bed
vehicular use. However, in a paper by Mata et al, the quality of adsorbent. For this material, amine, carboxylic, and hydroxyl
biodiesel produced was insufficient. This seemed to be due to groups were the main surface functional groups. This led to
high free fatty acid and moisture content, which are known to slightly different adsorption properties and selectivity than
lead to poor biodiesel. In this paper, the free fatty acids were with the husks. The sorbent was most effective at capturing
esterified as opposed to being saponified, then removed. This Cd(II), Cu(II), Ni(II), Pb(II), and Zn(II). Compared to the
may be a simpler process but could be responsible for the lower coffee residue itself (pyrolyzed or unaltered) or the clay, the
quality biodiesel that does not meet ASTM standards. sorbent mixture was much more effective. It was shown that
these sorbents can be regenerated, with 90% of the metal ions
adsorbed being removable by washing with distilled water.
Adsorbent Qualities and Applications After washing, the sorbent was active for more than 5 uses.
Solid coffee waste has been shown to have impressive
adsorbent characteristics, even without any modifications. An Extraction of Phenolic Compounds
example of this is a paper by Oliveira20, where completely
Coffee is a source of a large variety of polyphenol compounds
untreated coffee husks, a residue of coffee production, was
including chlorogenic acids, caffeoylquinic acids,

dicaffeoylquinic acids and feruloylquinic acids. These and their 1. Zuorro, A.; Lavecchia, R., Spent coffee grounds as a
metabolites have been shown to be beneficial to the human valuable source of phenolic compounds and bioenergy. Journal of
body22, and have potential uses as nutritional supplements or Cleaner Production 2012, 34, 49-56.
pharmaceuticals. One mechanism for their beneficial effect is 2. Haile, M., Integrated volarization of spent coffee
the chelation of metal ions that can mediate hydroxyl radical grounds to biofuels. Biofuel Research Journal 2014, 1 (2), 65-69.
formation23.
3. Kondamudi, N.; Mohapatra, S. K.; Misra, M., Spent
Even in SCG, there are phenolic compounds remaining. In Coffee Grounds as a Versatile Source of Green Energy.
work by Lavecchia1, these were extracted using aqueous Journal of Agricultural and Food Chemistry 2008, 56 (24), 11757-11760.
ethanol using mild conditions to preserve the activity of the 4. Obruca, S.; Benesova, P.; Kucera, D.; Petrik, S.; Marova,
phenolic compounds. The extractable phenolic compound I., Biotechnological conversion of spent coffee grounds into
content was high for SCG compared to other commonly polyhydroxyalkanoates and carotenoids. New Biotechnology 2015, 32
investigated materials, such as grape pomace, carrot peel (6), 569-574.
waste, apple peel waste, and kiwi peel waste. In addition, SCG 5. Pandey, A.; Soccol, C. R.; Nigam, P.; Brand, D.; Mohan,
R.; Roussos, S., Biotechnological potential of coffee pulp and coffee
can be used as a fuel source after extraction of phenolic
compounds, or have oil extracted, or be used as a feedstock in husk for bioprocesses. Biochemical Engineering Journal 2000, 6 (2),
153-162.
biorefineries. It should be noted that coffee bean waste from
6. Stavric, B., Methylxanthines: Toxicity to humans. 2.
different types of coffee plants have different phenolic
Caffeine. Food and Chemical Toxicology 1988, 26 (7), 645-662.
compound content, with as much as 20 or 30% difference
7. Eteng, M. U.; Eyong, E. U.; Akpanyung, E. O.; Agiang, M.
between Arabica and Robusta. A.; Aremu, C. Y., Recent advances in caffeine and theobromine
toxicities: a review. Plant Foods Hum Nutr 1997, 51 (3), 231-243.
CONCLUSION 8. Kim, Y.-S.; Sano, H., Pathogen resistance of transgenic
tobacco plants producing caffeine. Phytochemistry 2008, 69 (4), 882-
As can be seen, there are many uses for coffee waste. The
888.
applications shown are just scratching the surface. For
9. Ashihara, H.; Sano, H.; Crozier, A., Caffeine and related
example, coffee oils and solid waste can be used as feedstocks purine alkaloids: Biosynthesis, catabolism, function and genetic
for many more biorefinery materials than just PHAs or engineering. Phytochemistry 2008, 69 (4), 841-856.
carotenoids. SCG and other solid coffee waste can probably be 10. Kasongo, R. K.; Verdoodt, A.; Kanyankagote, P.; Baert,
used as an adsorbent for many other compounds due to their G.; Ranst, E. V., Coffee waste as an alternative fertilizer with soil
large amount of functional groups on the surface, not just metal improving properties for sandy soils in humid tropical
ions. As the polyphenols in coffee are more thoroughly environments. Soil Use and Management 2011, 27 (1), 94-102.
investigated, more uses for them will be discovered. As the 11. Brand, D.; Pandey, A.; Roussos, S.; Soccol, C. R.,
countries that produce and process coffee continue to develop Biological detoxification of coffee husk by filamentous fungi using
their scientific resources, they will hopefully allocate more time a solid state fermentation system. Enzyme and Microbial Technology
and money to developing innovative solutions to their unique 2000, 27 (1–2), 127-133.
issues. 12. Darken, M. A.; Jensen, A. L.; Shu, P., Production of
The use of waste associated with the coffee industry can be Gibberellic Acid by Fermentation. Applied Microbiology 1959, 7 (5),
seen as a model for many other systems, for example tea. Waste 301-303.
from manufacture of tea or the tea leaves themselves have many 13. Kawaide, H., Biochemical and Molecular Analyses of
of the same compounds as coffee, including polyphenols, Gibberellin Biosynthesis in Fungi. Bioscience, Biotechnology, and
caffeine, and cellulose. There are over 5 million tons of tea Biochemistry 2006, 70 (3), 583-590.
leaves produced per year, with this number growing every year, 14. Kostenberg, D.; Marchaim, U., Anaerobic digestion and
having been at less than 4 million tons in 2006.24 Many of the horticultural value of solid waste from manufacture of instant
solutions to coffee waste issues can be applied to tea waste, and coffee. Environmental Technology 1993, 14 (10), 973-980.
many of the countries that produce tea are developing and 15. Vortexrealm, Stages of Anaerobic Digestion. Wikipedia
could benefit from the use of a waste product. 2007.
16. Smock, D., Polypropylene Price Forecast for 2015. My
AUTHOR INFORMATION Purchasing Center 2014,
(http://www.mypurchasingcenter.com/commodities/commoditie
Corresponding Author s-articles/polypropylene-price-forecast-2015/).
* Ross Koby ([email protected]) 17. Schut, J. H., Where is Metabolix’s PHA biopolymer?
http://plasticsengineeringblog.com/2011/01/19/where-is-
ACKNOWLEDGMENT metabolix%E2%80%99s-pha-biopolymer/ 2011.
18. Mata-Gómez, L. C.; Montañez, J. C.; Méndez-Zavala, A.;
Dr. Moores and Dr. Rogers’ guidance is acknowledged. The help Aguilar, C. N., Biotechnological production of carotenoids by
and combined effort of the other editors of the McGill Green yeasts: an overview. Microbial Cell Factories 2014, 13, 12-12.
Chemistry Journal was enjoyed and much appreciated. Constructive 19. Kulkarni, M. G.; Dalai, A. K., Waste Cooking OilAn
criticism by reviewer 260584412 was appreciated greatly and Economical Source for Biodiesel: A Review. Industrial & Engineering
found very helpful. Chemistry Research 2006, 45 (9), 2901-2913.
20. Oliveira, W. E.; Franca, A. S.; Oliveira, L. S.; Rocha, S. D.,
ABBREVIATIONS Untreated coffee husks as biosorbents for the removal of heavy
SCG, Spent coffee grounds, PHA, polyhydroxyalkanoates metals from aqueous solutions. Journal of Hazardous Materials 2008,
152 (3), 1073-1081.
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W.; Jarudilokkul, S., Removal of heavy metals by adsorbent

prepared from pyrolyzed coffee residues and clay. Separation and Mechanisms in E. coli and Human Cells. In Oxidative Stress:
Purification Technology 2004, 35 (1), 11-22. Diagnostics, Prevention, and Therapy, American Chemical Society: 2011;
22. Lee, K.-W.; Im, J.-Y.; Woo, J.-M.; Grosso, H.; Kim, Y.-S.; Vol. 1083, pp 99-175.
Cristovao, A. C.; Sonsalla, P. K.; Schuster, D. S.; Jalbut, M. M.; 24. Chang, K., World tea production and trade. Current and
Fernandez, J. R.; Voronkov, M.; Junn, E.; Braithwaite, S. P.; Stock, future development. FAO Intergovernmental Group on Tea 2015, Rome,
J. B.; Mouradian, M. M., Neuroprotective and Anti-inflammatory 2015.
Properties of a Coffee Component in the MPTP Model of
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23. Hsiao, C. W.; Julia, L. B., Polyphenol Compounds as
Antioxidants for Disease Prevention: Reactive Oxygen Species
Scavenging, Enzyme Regulation, and Metal Chelation
How Green is Green? A Critical Analysis of Chemical Processes That

Utilize Citrus Waste by Employing the Principles of Green
Chemistry
Andrew Brebner*
KEYWORDS Green Chemistry; Sustainability; Citrus Waste
ABSTRACT: With ever increasing environmental concerns, the chemical industry has begun to look into more sustainable methods
for the production of various chemicals. One of the more attractive methods to achieve this is the use of waste byproducts from the
processing of other products. These processes are commonly labeled as “green” as they satisfy the principle of using renewable
resources, yet fail to address any of the other principles. This paper will review various chemical processes that utilize citrus waste
as a feedstock and use the principles of green chemistry to evaluate how sustainable they actually are. The processes will also be
compared to either traditional or alternative methods for the same product so as to determine their viability in terms of what’s
already being used.

INTRODUCTION second method which is similar to the first, will exclude the
The subject of green chemistry is an ideology which waste originating from the citrus, as it is already considered a
promotes the design of chemical reactions in which waste from a past process and water, as it is the preferred
environmental impact is minimized, while also being solvent. Gases used for anaerobic conditions, such as carbon
economically viable and feasible on an industrial scale. The dioxide and nitrogen, will be excluded since the amount
concept was made popular in 2000 when the book “Green needed cannot be specified due to its dependence on reservoir
Chemistry, Theory and Practice” was published which defined size as well as the volume of solution in the tank. This second
green chemistry in detail by setting its standards with the calculation will determine the actual amount of waste
twelve principles of green chemistry1. produced from the reaction and if the process is water
intensive. Other compounds may also be excluded from the
With increasing environmental concerns as well as depleting second calculation if the process states that the compound will
resources, green chemistry has become more attractive for the be recycled. Rather than providing an actual estimation of
chemical industry. The application of the green chemistry energy consumed, only the process conditions present will be
principles can be seen as both environmentally friendly as well listed simply due to the lack of data available to provide such a
as a more economically viable solution. By emphasizing the calculation.
design of more efficient reactions, minimizing power
consumption as well as using less toxic compounds, this
translates into a reduction of waste management costs and
potentially makes accidents significantly less hazardous.
DISCUSSION
Citrus production has been a major part of the food industry, Hydroxymethylfurfural. Hydroxymethylfurfural (HMF) is a
producing up to 50 million metric tons of citrus product compound that has great potential usage in various fields. The
annually2. Of this amount, almost half if discarded as waste most notable being as a potential source of biodiesel6, as well as
from the juicing industry in the form of citrus peel, pulp and its medical potential as an inhibitor for sickling of red blood
seeds. This waste is sometimes dried into pellets which can be cells7.
sold as cattle feed, but since this process tends to yield very The utilization of citrus waste in HMF production, as
little profit, the waste tends to end up in landfill. The waste can described by Yi and co-workers8 is a simple process consisting
accumulate and harm the environment due to its high of the preheating of a mixture containing chromium trifluoride
fermentation ability and its high acidity3. As the composition (CrF3)(0.1 g), 1-methyl-3-octylimidazolium chloride
of citrus waste consists mainly of oils, cellulose and various ([OMIM]Cl)(4 g), and 0.3M hydrochloric acid (HCl)(5 mL) to
simple sugars such as glucose and fructose, there has been an 130°C for 15 minutes. The pre-dried citrus peel (0.5 g) and ethyl
increasing interest in the use of citrus waste as a renewable acetate (1 mL) are then added and left to process at 130°C for 16
feedstock for many different high value compounds. The hours8.
compounds can either be extracted directly from the peel, as in Separation and yield quantification incorporated high
the case of oils such as limonene, or used directly in synthesis. pressure liquid chromatography (HPLC) with different ratios
Processes that successfully utilize citrus as a feedstock have of water and methanol as the mobile phase. The yield was
often been labeled as green as they utilize a renewable quantified to be 24.2% weight of the dried citrus peel or 0.121 ±
feedstock that was originally a waste byproduct, thereby 0.011 g.
employing one of the principles of green chemistry. This label, The procedure is a simple process consisting of only two
however, may be premature as only one principle is considered steps, yet energy intensive due to the long residence time at the
while the other principles are either overlooked or simply aforementioned temperature. The compounds being used
ignored. Potentially this could lead to a false conclusion as the however are of concern with the most notable being the CrF3
process may still utilize harmful reagents, large quantities of catalyst. According to its MSDS, it is a very toxic and a highly
solvent or even be very energy intensive. corrosive compound that can potentially cause significant
This review will consist of analyzing different chemical environmental damage. The other potential environmental
processes to determine just how sustainable they actually are. hazard would be the [OMIM]Cl ionic liquid. Ionic liquids are
This will be established by utilizing the twelve principles of generally favorable alternatives to traditional solvents due to
green chemistry, with the greatest emphasis on; solvent usage, their interesting properties as well as their low volatility. They
energy intensive conditions, reagent toxicity, as well as waste are also commonly assumed to be non-toxic, which is a false
production of the process. These processes will also be assumption as some are capable of decomposing into harmful
compared to alternative methods in order to determine if the compounds9. The ionic liquid present in this process is one
utilization of citrus waste is more sustainable than what is such case as it has been found to have some short term negative
currently being done. effects on soil microbial populations10, as well as being toxic to
algae populations that live in lower salinity environments11.
An alternative process to produce HMF described by
MATERIALS AND METHODS Hanson and colleagues12 utilized microwave radiation to heat a
The chemical processes will be analyzed and compared using solution of 27 wt. % fructose (2.7 mL) and 0.1M HCl (0.3 mL)
criteria similar to what is found in the paper “Green Chemistry to 200 °C for about 60 seconds12. This solution was also
Measures for Process Research and Development”4. For analyzed using HPLC but with a mobile phase of H2SO4.
simplicity, this paper will only focus on the following criteria; The yield is commonly quantified to be approximately 53%
the number of chemistry steps, list of process conditions such which in this case, translates to 0.319 g of HMF.
as heating and high pressure, environmental safety, compound Comparing the two reactions (Table 1), the alternative
toxicity and the amount of waste produced. microwave synthesis using fructose appears to be beneficial in
The amount of waste will be calculated two ways. The first most aspects. There are no toxic compounds present as well as
will be the E-factor which calculates the amount of waste (in there being much less waste generated. The added benefit of it
kg) created in order to produce a kilogram of product5. The being less time consuming can also be noted which can greatly

decrease the energy consumption of the reaction. The waste separation. The main issue for both processes is the quantity of
produced is also much lower due to it being much less solvent solvent required, with the majority being from the utilization
intensive. Overall, the process utilizing citrus waste does not of ethanol in the extraction process at an amount that is double
appear to be sustainable when compared to the alternative the solvent necessary for the actual reaction. Although ethanol
method reviewed. is preferable according to its calculated life-cycle assessment15,
Table 1. Comparison between HMF processes. it is still known as a VOC and its usage should be minimized.
Different extraction processes should be studied in the future
Citrus Waste* Fructose in order to find one where the amount of solvent can be
significantly reduced or replaced with less volatile solvents
(Microwave)**
that are more easily recycled.
Number of steps 2 2
The process however, is more sustainable in comparison to
Process conditions 130°C 200°C traditional methods which utilize glucose as a feedstock as the
16.25 hours 1 minute procedure is identical and is replaced by a waste. An interesting
finding that was observed by Bilanovic and colleagues14 was
Safety concerns Crf3, [OMIM]Cl -
that even though the concentration of simple sugars was lower
E-factor (kg/kg) 86.2 11.1 in the citrus medium, the yield was actually larger than that of
Modified E-factor 41.8 1.70 the glucose medium. This was found to be caused by the
(kg/kg) bacteria being able to digest other compounds present in the
waste such as pectin and hemicellulose.
* Values generated with data from Yi et al.8
**Values generated with data from Hansen et al.12 Carbon Dots. The production of carbon quantum dots (CQD)
is a somewhat recent topic that has become of great interest to
Xanthan Gum. Xanthan gum is a polysaccharide that is researchers. With interesting properties such as multi-
produced by specific bacteria such as Xanthomonas wavelength fluorescence, low toxicity, aqueous solubility and
campestris13. It is most commonly used as a thickening agent high biocompatibility, they have great potential in bioimaging
for various manufactured foods and cosmetic products. as well as photocatalysis16.
The process consists of a stock culture of xanthan producing The production of CQDs is relatively simple, with most
bacteria in a medium containing carbohydrates, phosphorus processes being a one-pot synthesis with a single reaction step.
and other nutrients. The carbohydrate source has traditionally There are currently a large number of different methods in
been glucose but citrus waste may be a possible alternative due which CQDs can be produced with the most cost effective one
to its high concentration of soluble sugars14. being hydrothermal treatment17.
The procedure described by Bilanovic and collegues14 begins The process utilizing citrus waste by Prasannan and co-
with neutralizing dried citrus waste (95 g) with sodium workers18 begins with a drying step. This dried waste (2g) is
hydroxide (NaOH) to a pH of 7.2. Potassium hydrophosphate washed in 0.1 M sulfuric acid (H2SO4)(100 mL), rinsed with
trihydrate (K2HPO4*3 H2O)(5 g), yeast (5 g), citrus and water and dried again. The waste is then added to 60 mL of
magnesium sulfate trihydrate (MgSO4*3H2O)(0.2 g) were then sodium hypochlorite for 4 hours and washed. The solids are
added and diluted with 1 L of water. The stock culture was placed in an autoclave with water (25 mL) for 12 hours at 180
inoculated at this point and shaken at 220 rev/min at 28 °C and °C and washed with dichloromethane (25 mL). The separation
allowed to ferment for 4 days. process consists of centrifuging the solution at 5000 rpm for 15
The xanthan is extracted from the solution with the slow min and then drying the CQDs to acquire a yield of 12.3%
addition of ethanol (3 L) to induce precipitation. The sample is (0.246 g)
centrifuged for about 20 minutes and the product dried in an The reaction does not appear to be very toxic as it uses
oven at 105°C. compounds that have very little impact when properly
The traditional synthesis utilizes the same procedure in disposed of. The washing step however, utilizes
which the citrus waste is replaced with glucose (22.5 g). dichloromethane which is a VOC as well classified as a harmful
air pollutant in the US.
The yield was determined to be about 14 g and 10 g for the
citrus and traditional processes respectively. Also of note was the inclusion of 3 drying steps which seems
inefficient as well as unnecessary. The pretreatment process
Table 2. Comparison between the Xanthan Gum processes. could probably do away with the drying steps, by simply
washing the citrus waste with the sulfuric acid and sodium
Citrus Waste* Traditional Glucose* hypochlorite and of course washing with water in between to
Number of steps 3 3 prevent the production of sulfur dioxide. The sample drying
Process conditions 105°C 105°C could simply just be done at the end. Further experimentation
should be done in order to confirm if this is possible.
for drying for drying
The alternative traditional method19 consists of heating
Safety concerns - - octadecene (15 mL), 1-hexadecylamine (HAD)(1.5 g) and citric
E-factor (kg/kg) 247.0 339.0 acid (1 g) to 300 °C in an argon atmosphere for about 5 minutes.
Modified E-factor 170.0 239.0
Purification consisted of precipitating the dots with acetone
(kg/kg) for filtration yield 0.1 g of CQDs.
The comparison of the two methods (Table 3) suggest that
* Values generated with data from Bilanovic et al.14 the procedure utilizing citrus waste is less toxic to the
The results summarized in Table 2 suggest that the reaction environment, with only the dichloromethane used for
is simple in both instances, consisting of only 3 steps including separation being a concern. The HDA used in traditional

synthesis however, is a significant hazard to the aquatic Table 4. Comparison between limonene extractions.
environment being toxic in relatively small amounts according
to its MSDS. Microwave and scCO2**
There appears to be an apparent trade-off between toxicity Steam Distillation*
and waste/energy consumption. The synthesis utilizing citrus Number of steps 2 2
waste is very energy intensive, needing multiple drying stages Process conditions 500W 12.5 MPa
as well as a 12 hour reaction period at high temperatures. It does
microwave radiation
appear favorable however, as the synthesis could be altered by
reducing the number of drying steps as well as further research 6 minutes 20 minutes
to determine if the 12 hour reaction time is actually necessary. Safety concerns - -
It may also be possible to replace dichloromethane with a more
E-factor (kg./kg) 32.8 267.05
environmentally friendly alternative such as ethyl acetate or
acetone. Modified E-Factor 0.0 242.92
(kg/kg)
Table 3. Comparison between the CQD processes.
* Values generated with data from Sahraoui et al.21
Citrus Waste* Alternative**
**Values generated with data from Mira et al.22
Number of 4 2
steps
Process 180°C 300°C, Ethanol Production. The use of ethanol as a biofuel is
conditions 12 hours, 5 minutes currently of great interest to potentially replace traditional
fossil fuels. At present the main crop that is used for ethanol
multiple drying steps production is sugar cane and corn due to their high sugar
Safety concerns CH2Cl2 HDA contents. The direct usage of crops does bring up concerns,
E-factor 907.4 221.4 mainly potential food shortages as well as land availability if
(kg/kg) crops are to be used to satisfy both food and fuel demand23.
Modified E- 34.2 221.4 The potential use of citrus waste as a feedstock for
factor (kg/kg) bioethanol production does not raise these concerns as it is a
waste product. The only drawback to citrus waste is from its
* Values generated with data from Prasannan et al.18 high limonene content which can be toxic to the bacteria used
**Values generated with data from Wang et al.19 for fermentation. Because of this, the limonene must be
extracted beforehand24. This is not that much of a drawback
however, as limonene extraction can be incorporated into the
Limonene Extraction. Limonene has widely been used in process.
industry as a solvent as well as a potential use as a biofuel. Many ethanol designs have already been done, with some
Citrus waste is already being used as a source for industrial being able to produce a wide range of products from the citrus
limonene production with steam distillation as the extraction waste including ethanol, methane, pectin and limonene in a
process. Currently, there are two main procedures being single process24.
looked into as more sustainable extraction methods. The first The process as described by Lohrasbi et al.24 begins with the
pairing the traditional steam distillation with microwave acid hydrolysis of a slurry consisting of fresh citrus waste (1.5
irradiation21 and the second using supercritical carbon dioxide kg), water (0.5 kg) and H2SO4 (8.5 mL) at 150 °C for 6 minutes.
(scCO2) as an extraction solvent22. Heating was performed through steam injection. The slurry is
The procedure utilizing microwave radiation (500 W) then explosively discharged to an expansion tank to cool down
places the citrus waste (100 g) into a cartridge and is subjected and centrifuged for 10 minutes in order to separate the solids
to microwave radiation while water vapor (14 g/min) is being which were taken and washed with distilled water (200 mL).
passed through the cartridge which is then collected via a The steam used for hydrolysis was collected and condensed
condenser. The process was done for a period of 6 minutes as it contained 99% of the total limonene available.
followed by the drying of the sample. The product was The supernatant was filtered into a precipitation chamber
characterized to contain 5.43 g of limonene at 96% purity. along with an equal volume of ethanol in order to precipitate
The optimal scCO2 procedure consisted of citrus waste (120 the pectin present in solution. The solution was centrifuged for
g) at 35°C and 12.5 MPa with a flow rate of 58.3 g/min for 20 an hour and washed with ethanol and dried with the ethanol
minutes yielding about 4.8g and 99.5 % purity. being collected and recycled.
The process using microwave radiation appears to have been The remaining solution is neutralized and fermented with a
able to acquire higher yields, all while using much less solvent yeast solution (50 mL) in a fermenter at 30 °C, 200 rpm at a pH
than the process utilizing scCO2 (Table 4). The tradeoff for this of 5 for 24 hours with a steady stream of nitrogen gas (600
is a slightly lower purity of the limonene product which may be mL/min) to ensure anaerobic conditions. The ethanol was
a significant factor in certain cases such as if analytical grading boiled off and collected while the remaining solution was
is desired. Energy usage consists of a large amount of heating placed into a digester with the filtered solids, adding 400 g of
for a small period of time whereas the process using scCO2 inoculum for every 200 g of solution being used as a substrate.
requires a longer time with high pressures and thus isn’t a good The reactor was incubated for 30 days at 55 °C to produce
method in comparison. methane.
The paper concluded that an industrial scale process would
be capable of producing 39.6 L of ethanol, 8.9 L of limonene,

38.8 kg of pectin and up to 45 000 L of methane for every ton of for. However, it is not adequate to simply settle with satisfying
citrus waste. one of the principles of green chemistry in order to label a
As shown in Table 5, the process is quite complex as there process sustainable.
are multiple products being manufactured. The process is The most prominent factors that were noted in this review
energy intensive with heating required in almost every step in were the high energy inputs as well as the large amounts of
order to optimize bacterial activity for fermentation. The solvent required. Another interesting observation was that a
production of methane required about 20 to 30 days with significant portion of these resources were used in the
heating for the entire process for optimal methane yield. pretreatment of the waste which would have been unnecessary
The amount of waste produced was low, with most of it if raw chemicals were used.
being from the large amounts of inoculum required for the The processes mentioned demonstrate that the chemical
methane fermentation. The nitrogen and CO2 gas were not industry needs to focus on the big picture if they wish to
included as they are only used for anaerobic conditions and implement green chemistry. Processes need to be analyzed as a
thus won’t require as much to meet industrial scales in terms whole, and take into account multiple variables, and have set
of proportions. The chemicals are all relatively safe with the priorities. Some of these citrus waste processes were found to
most concerning compound being the sulfuric acid which is be beneficial when compared to alternative methods such as in
easily treatable and used in very small amounts. the case of xanthan fermentation. Further experimentation
The economic viability of similar processes have also been should still be done in order to see if the process can be
analyzed and it has been found that the use of citrus waste for improved.
a source of these compounds could be a profitable strategy for
plants that are capable of processing citrus waste on a scale of AUTHOR INFORMATION
a hundred tons per year24. Corresponding Author
Table 5. Environmental Analysis of Ethanol Fermentation. *Email address: [email protected]
Citrus Waste* Corn** ACKNOWLEDGMENTS

Number of steps 9 6 The author wishes to express his gratitude to Audrey Moores and
Process conditions 150°C, 6 mins Drying step Robin Rogers for professional guidance and to fellow classmates
for advice on the topic.
96°C distillation 96°C distillation, 3
drying steps times ABBREVIATIONS
HMF, hydroxymethylfurfural; CrF3, chromium trifluoride;
Safety concerns - - [OMIM]Cl, octylimidazolium chloride; HCl, hydrochloric acid;
HPLC, high pressure liquid chromatography; NaOH, sodium
E-factor (kg/kg) 33.1 53.1
hydroxide; K2HPO4*3H2O, potassium hydro-phosphate
Modified E-factor 21.7 2.4 trihydrate; MgSO4*3H2O, magnesium sulfate trihydrate; VOC,
(kg/kg) volatile organic compound; CQD, carbon quantum dot; H2SO4,
sulfuric acid; scCO2, HAD, 1-hexadecylamine AD, super critical
* Values generated with data from Lohrasbi et al.24 carbon dioxide.
**Values generated with data from Pimentel et al.25
With the overall complexity and wide range of products
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Development in the Commercial Methods of Recycling
Poly(Ethylene Terephthalate)
Corey S. Braun
KEYWORDS: Polyethylene Terephthalate, PET, Sustainability, Recycling, Green, Solvolysis, Applications
ABSTRACT: Green chemistry and sustainability are important topics in modern chemistry. The sustainability of the plastics
industry therefore, should be of considerable concern. Polyethylene terephthalate (PET) is a common high volume thermoplastic
polyester resin, which is used broadly in plastic packaging, textiles and beverage bottles. Development in the commercial methods
of recycling PET has therefore been investigated in the context of green chemistry and sustainability. It has been observed that the
progress made in the commercial recycling methods of PET has resulted in a not very green and unsustainable system for the
production and effective removal of PET from the environment.
INTRODUCTION [2] and is broadly used in plastic packaging, textiles and most
Sustainability and the term “green” given to certain products notably, beverage bottles [3]. As a result, over the past three
and processes are becoming increasingly popular in society and decades, recycling of used plastics across the world has risen
chemistry as the difficulties posed by the finite supply of global greatly [4]. The recycling of plastics has had its difficulties
resources is becoming more and more apparent. Plastics are a however, where it was expected to be inefficient, impractical
very common material used worldwide, thus their and not economically viable [4]. This is due to the low value of
environmental impact and sustainability are becoming recycled PET and its monomers in addition to the costly
important subjects of concern [1]. Due to the broad nature of procedures of recycling. Even so, the relative amount of PET
the subject, focus is made on polyethylene teraphtalate (PET), waste occupying landfills has decreased since its use
which is a common, high volume thermoplastic polyester resin commercially [4]. Therefore, development in the processes of

PET recycling and new applications for recycled PET are acetate [10]. The products of the methanolysis reaction are
suspected to have been developed. DMT and EG.
Methods of Recycling PET Glycolysis is similar to methanolysis such that high

temperatures and pressures are required (453K-523K, yet the
PET is a material that is robust to atmospheric and biological reaction is performed in excess ethylene glycol and methanol is
means of degradation [5-7]. Zhang, J., et al. (2004) studied the not part of the cycle [10]. In addition, an esterification catalyst
biodegredation of PET with exposure to microbes and lipase. is also used and is most commonly zinc acetate [9-10]. An
The conclusion was that there were only cracks on PET fibers interesting aspect of glycolysis is that partial glycolysis can be
after accelerated degredation. Therefore, recycling is the only performed, resulting in oligomers of lower chain lengths
method to achieve significant PET degradation and reuse. known as glycolyzates [10]. The products of what is known as
Generally, there are four discernable methods of plastics deep (more complete) glycolysis of PET is BEHT and EG [10].
recycling: direct reuse, chemical reprocessing, mechanical Much of the research done in chemical processing using
reprocessing, and finally, energetic recovery [4]. Energetic glycolysis is not in development of improved methods of
recovery is where the plastic is combusted to yield thermal chemical processing, rather research in applications of the
energy [4]. Due to the reasonable assumptions that reuse and glycolyzates obtained from glycolysis and many are described
energetic recovery yielded no significant development, where in [10]. An unfortunate outcome is this has caused stagnation
the former offers no potential application of chemistry and that in the improvement of commercial chemical recycling
the latter is fundamentally unsustainable, focus is made on processes of PET. This is made apparent since glycolysis and
developments in chemical and mechanical reprocessing. methanolysis were proposed as recycling processes since the
first commercial uses of PET in the 1950s [10]. Nonetheless,
Chemical Reprocessing there has been a reported attempt of improving glycolysis
methods by Troev, K., et al. (2003), who researched the
Chemical reprocessing is the most lengthy and expensive development of a more effective glycolysis catalyst. They
form of plastics recycling as it often involves depolymerization proposed use of titanium (IV) phosphate rather than the
and re-polymerization often following purification, which can commonly used zinc acetate catalyst and proved more rapid
include distillation, recrystallization and additional chemical depolymerization of PET. A more recent example of improving
reactions [4]. PET belongs to the group of plastics known as the chemical recycling of PET was done by Bartolome, Leian et
polyesters and is commonly synthesized through the al. (2014), which involves the use of superparamagnetic γ-Fe 2
polycondensation reaction of terephthalic acid (TPA) or O 3 nanoparticles as a catalyst, which is easily removed.
dimethylterephthalate (DMT) and ethylene glycol (EG) [9].
Either pair of reagents first form the monomer Other methods of solvolysis have been considered, such as
bis(hydroxyethyl)terephthalate (BHET). After the addition of hydrolysis [3. 10] and aminolysis [15], but have never made it to
certain stabilizers and additives, the pre-polymer (BHET) the commercial scale.
undergoes polycondensation to form PET and release n-1 moles
of EG in the reaction scheme: Mechanical Reprocessing
Scheme 1. Polycondentsation of BHET This method of reprocessing involves actions such as the
grinding, melting, reforming and extrusion of PET waste [4, 16].
nBHET ↔ PET + (n-1) EG This process is subject to specific concerns however involving
the purity of the recycled PET and its structural integrity [4,
Depolymerization therefore involves the breaking of the 16]. Mechanically recycled PET may include contaminants,
bonds formed in the polycondensation reaction. This is making it unsuitable for food containers [17, 18]. In addition,
generally accomplished by what us known as by solvolysis [10]. post-consumer PET experiences a loss in inherent viscosity
The depolymerization processes that have reached the level of when recycled mechanically due to hydrolysis reactions in the
commercial applicability are glycolysis and methanolysis [10- melting process, resulting is shorter chain length [16]. Chain
12]. Presumably, glycolysis involves depolymerization in the length and inherent viscosity are important parameters in
presence of EG and methanolysis involves depolymerization in plastic polymers because they are direct measurements of the
the presence of methanol. These two depolymerization strength of the polymer. Significant loss in polymer strength
processes are fall under the term alcoholysis and progress as may result in the inapplicability of the recycled polymer for its
follows: former uses. This is one of the main draw backs of mechanical
processing. Recycled PET can be blended with virgin polymer
Scheme 2. Alcoholysis of a Dimer of PET of longer chain length in attempt to prevent this [4], but this
reduces the effectives of this recycling process in terms of
sustainability.
In attempts to use only recycled PET in mechanical

reprocessing, groups such as Awaja, F., et al. (2004) at RMIT
university have made processes for chain extension of PET
using a “reactive extrusion process”. This process involves the
chemical reaction of PET with pyromellitic dianhydride
(PMDA), a known chain extending and branching polymer
agent [19, 20]. This reaction is perfromed during the extrusion
process to afford PET of increased inherent viscocity (increased
Methanolysis is performed in excess methanol at high chain length). The experiment proved that the use of a
pressure and temperature (2-4MPa and 453K-553K) along commercially available extruder with a reactive concentration
with a transesterification catalyst, which is usually zinc of PMDA ranging from 0.15-0.31%wt of PET polymer is possible
[16]. Also, the addition of the PMDA during extrusion and the virgin PET. In addition, the recycled PET and its monomeric
subsequent increase in viscocity of the extruding PET put a units have a low market value, which is why new high market
pressure on the die of the extruder within standard safety value recycled PET based products is the desired focus of
limits and the reaction itself occuring in the extruder was research. This is detrimental to the sustainability of the PET
proven to be able to be controlled reasonably [16]. Therefore, industry since there is no cyclic nature of the production and
using very small amounts of %wt. PMDA, in a processe recycling of PET. To elaborate, the amount of PET in landfills
applicable to existing recycling faclities, recycled PET can has been diminishing, but it is simply being transformed into
maintain its inherent viscocity and thus its chain length other non-biodegradable materials. Crudely put, this can be
resulting in higher tenisle strenght than regular recycled PET. seen as just simply spreading the PET waste around, giving it
Regular mechanicaly recycled PET exhibits both lower impact different names and making it look like it is not there. What
and tensile strengtht han virgin PET [16]. Chains extendeded happens to these new recycled PET derived products after their
mechnically using recylced PET can thereofore be potentially lifetime? Do they undergo further chemical processing
used for a wider range of applications much like virgin polymer resulting in more waste and energetic burden? Or, do they
blended recycled PET, whle using a reagent (PMDA) that only simply make their way back to landfills? Therefore, the only
consists of leass than 1%wt of the recycled PET polymer. way for PET to be sustainable is if it were to be chemically
recycled and reformed specifically back into PET to be reused.
Applications of Recycled PET Although this is impossible due to the economic aspects
previously mentioned. Moreover, there is the societal
As stated earlier, chemical reprocessing involving the responsibility of individuals to properly dispose of their PET
glycolysis of PET result in what are known as glycolyzates. The waste and provide it recyclers, which is a separate issue entirely
majority of the research in chemical reprocessing has gone into in itself.
applications for these oligomers [10]. For example, their use has
been reported many in the production of polyurethanes, by With regards to green chemistry, the actual commercial
which products such as foams and paints have been produced chemical processes (solvolysis) involved in chemical
[10, 21]. Some other applications researched is that of recycled reprocessing have elements of greenness, but also possess areas
Pet involved in the creation of polymer concrete and polymer of considerable concern. Inherently, solvolysis reactions can be
mortar using polymer resins derived from recycled PET [10]. seen as the reverse of the ester bond formation of the
polycondenstaion reaction of PET. This is illustrated nicely in
DISCUSSION scheme 2. if the alcohol were ethylene glycol. It is common fact
that reverse reactions often require a lot of energy to proceed
Unfortunately, however developed the current commercial and solvolysis is of no exception. As stated both commercial
mechanical processes become, there will be a point when the methods (glycolysis and methanolysis) require very high
recycled PET cannot be reprocessed any further and will once pressure and temperature reaction conditions in order to
again reoccupy landfills, potentially spliced with many other proceed. This can be seen as not a green aspect of these
substances such as chain extenders, plasticizers and other processes since minimization of energy consumption is
plastics. All of these compounds will potentially persist and important in green chemistry. In addition, glycolysis and
harm the environment. However, mechanical processes from a methanolysis often leave behind harmful EG residues [5, 9] and
green chemistry perspective are greener than chemical the use of solvent (the alcohols) is an innate feature of these
processes since there are no or potentially very minimal reactions. The minimization of toxic byproducts and solvents
stoichiometric reagents (minimal in the case of chain are also important in green chemistry. Glycolysis and
extenders) and they can be performed with or without solvent. methanolysis however, in terms of the reagents used bear some
Although mechanical processes require considerable energy green aspects. For instance, the alcohol is only partially
input as it is a physical conversion, when compared to chemical consumed in the glycolysis reaction, illustrated in scheme 2.
reprocessing, mechanical reprocessing can be considered This makes PET generally the only fully stoichiometric reagent.
roughly on par. This is because of the substantial energy Plus, the reaction is mediated by a catalyst. Finally, if the
requirements of solvolysis, represented by the high alcoholyzed PET was used to regenerate PET, in the end, PET
temperature and pressure requirements of the reactions. Not to and the alcohol can be considered as not really stoichiometric
mention, the energetic and chemical requirements of the reagents, since they are regenerated in the polycondensation
purification steps involved in chemical reprocessing. Therefore reaction. From this perspective of the general overview of the
with regards to green chemistry, mechanical reprocessing can reaction (not considering purification, phase changes etc.),
be seen as greener than chemical reprocessing, but its products depending on the green aspects of concern, glycolysis and
will end up having a negative environmental impact due to methanolysis can be seen as somewhat green methods of
their unsustainability. chemical PET reprocessing. Though, the non-green aspects of
glycolysis and methanolysis are inherent to the solvolysis
Taking into account the direction in the development of reaction and so if commercial chemical reprocessing were to be
commercial chemical recycling methods of PET from a green made greener, then commercially applicable improvements of
chemistry and sustainability perspective, the PET industry has these methods or potentially new methods of chemically
taken a wrong turn from the beginning. As stated, the basis of recycling PET would need to be researched. Albeit, this is
the commercial methods (solvolysis) of chemical reprocessing problematic due to the general focus of previous and more
for PET have remained mostly unchanged since PET started current research. Considering everything learned, it can be
becoming of commercial use. The majority of research and concluded that the current commercial methods of PET
development has gone into potential methods for applications recycling are in some important aspects not green and do not
of recycled PET, where the resulting products of these methods provide a sustainable system of PET production and removal
are just more polymer resins and other non-biodegradable from the environment.
synthetic products. This research direction is heavily
influenced by economic incentive, since the cost and effort of
recycling PET will always be greater than the production of

AUTHOR INFORMATION [10] Paszun, D. and T. Spychaj (1997). "Chemical Recycling of
Poly(ethylene terephthalate)." Industrial & Engineering
Corresponding Author Chemistry Research 36(4): 1373-1383.
Corey Braun [11] J. Scheirs, "chapter No 4: Recycling of PET" in: Polymer
[email protected] Recycling, Wiley Series in Polymer Science, J. Wiley & sons,
Sussex (1998).
Author Contributions
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All authors have given approval to the final version of the
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Review of Polychlorinated Biphenyls Treatments in Water and Soils:
from Supercritical Fluid Extraction to Rhizoremediation
Sheena Louisia
KEYWORDS. PCBs, activated carbon, supercritical fluid extraction, rhizoremediation, aerobic and anaerobic organisms, earthworms
ABSTRACT: After the significant use of polychlorinated biphenyls (PCBs) in the chemical industry between the 1930s and 1970s,
the need for treatment has become a relevant research interest. An approach to analyze the overall impacts at a biochemical level,
followed by a proposal of solutions to remediate PCBs contamination, is suggested here. The proposed solutions are based on a
critical analysis of previous work done on bioremediation processes and chemical treatments for PCBs in soils and water.
Although the toxicity of some PCB samples was assessed in

INTRODUCTION 1966 and that it was later confirmed with the Yusho incident
Polychlorinated biphenyls (PCBs) were intensively in 1968, the production of PCBs is observed to hit its
produced and used from 1960 to 1975. At the time, chemical maximum in the 1970s.7 Records from 1929 until now report
industries significantly increased their production due to the about 1.5 million metric tons produced worldwide. 8 It is only
high demand from the army. Technological advances were until the Stockholm Convention on Persistent Organic
critical for many countries during the World War II which Pollutants in 2001 was implemented, that the world-wide
justifies for the multiple applications found for PCBs.2 production of PCBs started to decrease to reach a less
Because of their numerous physicochemical properties, their dangerous amount.9 This reduction correlates with a
industrialization became one of the most developed, noticeable decline in the concentration of PCBs found in the
especially in the United States.3 The most common environment. The urge to banish such production is
applications for PCBs include hydraulic fluids, plasticizers, supported by the many evidences of high toxicity caused by
adhesives, pesticide and extenders.4-6 such chemicals. All high organisms, and indeed the entire

population of our biosphere, are greatly affected by long term proven for water treatment, has also been observed in
exposure to PCBs.10 Health effects such as immune sediments and soils. Experiments have studied the very
deficiencies, reproductive or nervous system difficulties, and successful removal of PCBs using activated carbon in Histosol
an increased risk of getting cancer were observed in and Alluvial soils, which are organics-rich and sediment-rich
populations subject to continuous exposure to PCBs.11 soils, respectively. In marine sediments, not only is AC shown
The cessation of the production of PCBs resulted in a to be very effective without being affected over time, but it
significant reduction of its concentration found in fresh also maintains an unperturbed system thanks to a stable
water, soils and oceans. Still, the persistence of PCBs, binding between AC and PCBs. Some studies have evaluated
explained by their low water solubility, makes them very hard the effectiveness of two types of activated carbon, namely
to completely remove. More importantly, urban areas granular activated carbon (GAC) and powdered activated
concentrate the greatest amount of PCBs on the surfaces of carbon (PAC). The data reported by Vasilyeva et al is
buildings and industrial infrastructures. Altogether, the presented in Table 1.
remediation of PCBs in our environment, both natural and
anthropological one, represents an important health concern. Table 1. GAC and PAC chemical properties (based on data
Many researchers have looked at the problem and came up reported by Vasilyeva et al.) 17
with various solutions.12-14 However, there are two categories Characteristics GAC PAC
standing out overall, namely the chemical direct treatment
and the biological indirectly initiated treatment. In this work, Carbon source Coal Peat
the viability of the different techniques reported in both Particle diameter, µm 400-1500 1-100
categories is to be evaluated based on the twelve principles of Elemental carbon, % 84 85.1
Green Chemistry as defined by Anastas.15 Eventually, two Specific surface area, m2/g 880 1000
final preferred techniques are compared on the basis of life
cycle assessment to suggest the greenest and most realistic Total pore volume, cm /g3 0.86 0.78
solution for long-term PCB remediation. Micropore volume, cm3/g 0.36 0.43
Fe content, % 1.4 0.65
CHEMICAL REMEDIATION. Thermal desorption
represents one of the most efficient methods to decompose
PCBs in contaminated soil, at efficiencies exceeding 95% Although no difference of success was reported between
decomposition. Unfortunately, many disadvantages are the two forms of AC, it was confirmed that PCBs could be
associated with such a technique. First, it requires very high successfully removed from historically contaminated soils
temperature and therefore a significant amount of energy. over a long period of time, down to 95% reduction. 17
Then, in spite of a very high degradation yield, it forms other The recovery of PCBs from contaminated soils was reported
toxic products known as polychlorinated dibenzofurans to be successful, using hexane and acetone. These solvents
(PCDFs). The thermal desorption is found to even increase dissolve AC effectively based on its significant
the toxic equivalency quantities (TEQ) of PCDFs. This hydrophobicity, predictable from its chemical structure as
technique is not only costly in terms of energy consumption presented in Figure 1. However, hexane is known to possess
and in financial means, but it also presents dangerous toxicity adverse health effects. While its effects in the atmosphere are
that doesn’t make it a viable technique to pursue in the long minimal and it is not even considered a greenhouse gas, the
term. Furthermore, it has no potential in being performed in presence of hexane in water does have dangerous effects on
situ, which means that it is geographically limited to certain the ecosystem. Nevertheless, it can be said that well managed
areas such as the Arctic where PCB contamination has and recycled solvents, in spite of their toxicity, represent a
dangerous impacts on the fragile and scarce ecosystem. negligible risk for the environment and do not go against the
Thermal and chemical oxidation technologies present the twelfth green principle that advocate the preference for safer
same byproducts and inconveniences. The excavation and chemical procedures. 15
destruction of PCBs by incineration is another technique that
has been extensively used. The summit of Resolution Island,
Nunavut, has been successfully decontaminated using this
technique by 96%. The PCB removal in this area was
especially successful considering that a long term plan was
also implemented in order to continue the pollutant control
after excavation. A permeable reactive barrier was set up,
preventing the remaining contaminated soils from spreading
into the ecosystem. Nonetheless, this overall process took
about 7 years and cost $20 million. In addition, the removal of
PCBs was not absolute and well-controlled over time16, in
spite of the presence of a preventive barrier. In the perspective
of making such removal more economic and viable in the long
term, the development of an in situ removal process has been
studied17.
Figure 1. AC chemical structure responsible for its
hydrophobicity (based on structure as proposed by Mochida)
Activated Carbon. Activated carbon (AC) has long been 19
used to treat waste water, drinking water and ground water On the other hand, the carbon source for GAC is more
by removing organic pollutants. Its high hydrophobicity, high harmful than for PAC as they come from coal and peat,
specific surface and microporous surface makes it a good respectively. The production of coal is known to have many
adsorbent for this type of chemical. 18 Its effectiveness, already

Scheme 1. Dioxygenase of a PCB by aerobic organisms (as reported by Vrchotová) 1
polluting impacts on the environment20. The air, soil, and disadvantages associated with this solvent are therefore
water pollution it generates is often poorly controlled and added to this technique.
creates many health hazards for populations living nearby. In
addition, coal mining results in excavation and destruction of
the landscape that are rarely recovered and where vegetation BIOLOGICAL REMEDIATION. The less harmful way to
is poorly restored20. Similarly, even if peat production is not treat PCBs, that would also require less effort and energy, is
as harmful as coal industry, it is not totally harmless. It is in to do it in situ. Finding the way to degrade them, where they
fact responsible for a serious upheaval of the environment and are found in the environment, consists in the most sustainable
more specifically swamp ecosystems21. The risk of fire and way to properly, and eventually completely remove them.
erosion is significantly increased by the disruption of the Rhizoremediation. The capacity of certain roots to enhance
hydrology in swamps which is caused by peat extraction. In the activity of some pollutant-degrading bacteria is also
both cases, the remediation of PCBs, although very efficient, known as rhizoremediation; this method belongs to
can somehow represent another risk for the environment. As phytoremediation which regroups all plants presenting the
a result, the sources from which GAC and PAC are obtained same ability. All roots do not possess the same
need to be well-regulated in order to ensure that the rhizoremediation properties, as reported by Slater et al.
13When evaluating the effect of two plants, Salix alaxensis
environmental improvement they can provide is not counter-
balanced by another negative impact. (willow) and Ricea glauca (spruce), on the reduction of PCBs
toxicity in soils, they observed that only willows were
rhizoremediating PCBs. More interestingly, the presence and
Supercritical fluid extraction (SFE). A study done by production of salicylate were found to have no effect on PCBs
Reutergardh et al. reported the use of supercritical carbon to reduction while biphenyls did. Nonetheless, the toxicity
extract three planar PCBs (PCB-77, PCB-159, PCB-126) and associated with biphenyl-treatment was found to be much
three mono-ortho PCBs (PCB-105, PCB-156, PCB-189) from higher than with willow roots only. Unfortunately, their
three types of tropical soils. 12 These six PCBs are put under identity and detailed mechanism of removal have not been
study as they are considered as the most toxic ones of their reported yet. 23 Nevertheless, a list of biphenyl-utilizing
kind; their structures are given in Figure 2. bacteria that could be responsible for such remediation has
been proposed and studied by other groups. 24 It is reported
that polychlorinated biphenyl is degraded by dioxygenase
attack before being metabolized to chlorobenzoic acid. The
rough mechanism of a dichloro-PCB is presented in Scheme 1.
The degradation of PCBs is debated to be either due to
oxidative degradation by aerobic microbes (grow in oxygen-
rich environment) as given in Scheme 1, or to dechlorination
by anaerobic ones (grow in deoxygenated environment).
These bacteria include multiple gram-negative genera such as
Figure 2. Six different PCBs extracted using supercritical Pseudomonas, Alcaligenes, and Acinetobacter, and gram-
carbon positive genera such as Rhodococcus, Corynebacterium, and
Bacillus. 25-26
The use of supercritical fluids to extract organic molecules
is known to be not only an effective but also a selective All of the above use biphenyl as a source of carbon and
extraction method. In this particular case, the use of carbon energy, and co-metabolize PCBs with the same enzymes used
dioxide (CO2) is one of the most popular green media used in for biphenyls. This mechanism explains why addition of
chemical extraction. It has moderate critical pressure, 74 bar, biphenyl in soils with PCBs yielded an important PCBs
and temperature, 31°C; it is a safe medium to handle as it is removal. Four general concepts were withdrawn from
neither toxic nor flammable22. This study yields good numerous studies on PCBs depletion and are given as
extraction of all types of PCBs from tropical soils. The success reported by Furukawa and Fujihara: (i) the decrease in
of the extraction varied in function of the soils properties but biodegradability is correlated with an increase in chlorines;
most importantly with the structure of the PCB extracted. (ii) PCBs with only one chloro-substituted phenyl will
Mono-ortho PCBs revealed a more significant extraction degrade faster than those with both rings chloro-substituted;
yield than their planar congeners. The extraction is found in (iii) double ortho-substituted PCBs are poorly degraded; (iv)
all cases to be relatively fast, about 40 minutes. Finally, while bacterial strains is responsible for the rate of degradation as
the moisture of the soils has effects on the final yields, the well as which ring is to be first attacked27.
temperature has little impact on these extractions. 12 In the same range as for willows rhizoremediation, this
In the same manner as for AC, the isolation and recovery of group reported an effective degradation percentage of about
the extracted PCBs required the use of n-hexane. 12 The same 40% with Cucurbita and Cucumis species. The list of plants

with similar potential goes on and on, all able to perform pressing issue. It is suggested that techniques such as AC
phytoextraction and rhizoremediation with an efficacy of 30- followed by planting of rhizoremediating plants are
40%.28-30 Over about 200 days, soils planted with those considered sufficient interventions for the level of toxicity
species producing the adapted bacteria were observed to being faced.
present a much lower PCB content and significantly Eventually, the use of rhizoremediating plants in tandem
decreased toxicity. with earthworms would represent the most sustainable and
In spite of a longer amount of time to remediate PCBs cheapest PCBs remediation. However, in spite of their
content, the impact on the environment of these plants is potential production costs, both GAC and PAC have the
beneficial. It can be debated that the ecosystem in question capacity to remain efficient over time and do not need to be
could be disturbed by the presence of inappropriate species. renewed. The combination of AC and a rhizoremediation-
However, the diversity of plants with the ability of favored environment appears to be the most realistic and
performing rhizoremediation of PCBs has been found to be flexible application no matter what type of environment is to
sufficiently important to find the best-suited plant for a be treated. This tandem strategy will allow efficient PCBs
specific biosphere. Finally, such system doesn’t require the removal and ensure a reduction in soil toxicity. In contrary,
use of any solvents for further treatment, and would only the use of SFE is neither a realistic nor a practical PCBs
require manual labor. As in the Nunavut case presented remediation technique for isolated spaces. Although it is one
previously, this could represent an employment opportunity of the fastest techniques, it requires more labor and expertise
to plant and maintain the remediating plants. Although the when considering larger volume of contaminated soils. An
plants with the highest remediation efficiency haven’t been economic analysis was however performed on the use of SFE
yet determined, an effort in engineering plants generating as a PCB removing technique. It is reported, that with its
more efficient PCB degrading enzymes is currently being $170-200 per cubic meter cost, SFE would be economically
developed. 30-31 preferable in comparison with excavation where
transportation costs can become significantly excessive.33
Though SFE can be considered interesting for PCB
Earthworms’ contribution. The efficiency of the remediation in urban soils, it still doesn’t present a cost-
phytoremediation performed by the plants presented benefit ratio attractive enough when applied to remote and
previously can be further controlled and enhanced in function vast areas.
of the management of the soils. The participation of
earthworms in the gas diffusion within soils was proven to To conclude, because their efficacy does not decrease over
contribute in an increase in PCBs bioremediation. time, AC and rhizoremediation ensure the prevention of
Furthermore, the presence of earthworms allowed not only a further pollution of PCBs. Due to their stability in soils, in
better removal of PCBs but also a more uniform distribution case of another chemical spill, both bacteria and AC will still
at all depths. The increase of PCB-degrading bacteria was have the potential to degrade PCBs. Consequently, industrial
increased from 39% to 55%. Allowing better aeration and areas with chemical risks could plant species with the
deposition of nutrient rich casts, the presence of earthworms potential to phytoremediate the dangerous chemicals
allows a better metabolic activity of the PCB-degrading produced or used by the industry concerned. Although this
bacteria. This study raised the importance of parameters such paper has essentially focused on PCBs, it is interesting to
as PCB bio-availability but also conservation of aerobic mention that other applications, such as 2,4,6-trinitrotoluene
favored conditions. The selectivity of the enzyme responsible (TNT) could degradation, can be performed using both AC
for the degradation of PCBs is not good enough to obtain and some phytogenerated bacteria34. Further studies on the
yields higher than 30-40%. However, the addition of behavior and chemistry of the enzymes used by PCBs-
earthworms in the equation increased those yields up to 65%. degrading bacteria could in the future provide a superior and
Once again, this method is harmless to the environment. In more efficient solution to achieve a 100% degradation of
addition, introduction and culture of earthworms have been historically PCBs contaminated soils. Overall, the use of a
proven to be limited in terms of financial costs.32 solvent-free and in situ remediating technique is preferable.
ABBREVIATIONS
CONCLUSION PCBs, Polychlorinated biphenyls; AC, activated carbon; GAC,
The principal advantages of the two in situ controlled granular activated carbon; PAC, powdered activated carbon;
chemical treatments are their high degradation efficacy in PCDFs, Polychlorinated dibenzofuran; TNT, 2,4,6-
addition to relatively fast kinetics. Bioremediation, on the trinitrotoluene; SFE, Supercritical fluid extraction
other hand, presents two principal weaknesses, namely
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The McGill Green Chemistry Journal

Vol.1 – December 2015

A super-critical review of supercritical fluids: can SCFs replace traditional solvents?

Carbon dioxide copolymerization: how green is it?

Green alternatives for the synthesis of metal nanoparticles

Current developments in green chemical extraction techniques of lignocellulosic materials:

Endangered Element: A Review on Palladium

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 2

The ugliness of the personal care industry

A methanol economy based on renewable resources

On the effectiveness and sustainability of large-scale CdTe photovoltaic cell use

Waste Reduction and Repurposing

Development in the commercial methods of recycling poly(ethylene terephthalate)

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 3

•Design of more sustainable reactions and chemicals

•Chemistry to reduce waste production

•Analytical techniques for hazardous chemicals

•The societal effects of green chemistry

•Evaluation of the sustainability of current chemical processes and methods

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 4

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 5

KEYWORDS: Supercritical CO2, Textile Industry, Polyester, Waterless, Sustainable

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 6

THE WATERLESS SOLUTION

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 7

THE CURRENT COMMERCIALIZATION

The commercialization of scCO2 polyester dyeing has begun, CONCLUSION

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 8

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 9

INTRODUCTION necessary and in some cases may hinder optimal reaction

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 10

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 11

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 12

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 13

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 14

Carbon Dioxide Copolymerization: How Green Is It?

KEYWORDS Copolymerization; Carbon Dioxide; Epoxides; Catalysts; Polycarbonates; Organometallic Complexes

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 15

Β-diiminate Zinc Catalysts. Since the first catalyst discovered

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 16

Figure 2. Comparison of epoxides used, (2a) Cyclohexene

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 17

with a high yield and high selectivity.

Figure 3. Example of a Simple Iron-Corrole Catalyst.16

Scheme 2. First reaction in the process to obtain the lactone

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 18

Catalyst Carbon Pressure needed Renewability Renewability Biodegradability

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 19

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 20

KEYWORDS: Biogas, organic waste, Canada, biomethane, green chemistry.

1. INTRODUCTION hydrocarbon, methane is also a fuel. Natural gas is a commonly

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 21

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 22

Figure 2: Schematic diagram of anaerobic digestion processes.

McGill Green Chemistry Journal – Vol. 1, Dec. 2015 – Page 23

Manure Produced Total Dry Matter

Table 2: Overview of biogas potential by feedstock source.

Biogas Potential per Total Biogas Potential Total Biogas potential