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Redefining biorefinery: the search for

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unconventional building blocks for materials

Cite this: Chem. Soc. Rev., 2015,
Open Access Article. Published on 24 April 2015. Downloaded on 5/28/2020 4:43:41 PM.
44, 5821
Davide Esposito* and Markus Antonietti
Received 31st October 2014
This review discusses different strategies for the upgrading of biomass into sustainable monomers and
DOI: 10.1039/c4cs00368c building blocks as scaffolds for the preparation of green polymers and materials.
www.rsc.org/csr
Key learning points

(1) Biorefinery provides access to non-conventional building blocks and scaffolds for the preparation of new sustainable materials and polymers.
(2) Chemical strategies for the deconstruction of lignocellulosic biomass in its carbohydrate and lignin fractions can be generally classified into degradative or
non-degradative processes.
(3) Hydrothermal and solvothermal methods can be combined with catalytic processes to generate specific monomers or oligomers as sustainable scaffolds for
material science.
(4) The materials and polymers synthesized on the basis of biomass derived molecules present different and extended properties compared with the ones
conventionally obtained from fossil resources.
(5) Biorefinery can generally increase the sustainability of current (nano)technologies.
Introduction ‘‘food vs. fuel’’ competition, as well as an overall less favorable

energy balance. From an economic perspective, it is important
The core of the chemical industry is the conversion of raw materials to consider that classical fuels and energy carriers are produced
into value-added products, including fuels, platform chemicals, with the minimal leverage as methane (‘‘biogas’’), ethanol
polymers, materials and pharmaceuticals. In the last century, fossil (‘‘biofuel’’) or ‘‘biodiesel’’. However, chemists are usually aware
resources have constituted the primary feedstock for a multitude of that there is more to chemical molecules than their energy
chemical processes and transformations. However, sustainability is content, as demonstrated by the continuous search for new
becoming a global imperative, due to the considerable depletion of ‘‘materials and medicines’’. This is why attention has been
fossil resources, and major scientific and political players have slowly re-directed to the development of routes for the conversion
been promoting the paradigm of ‘‘biorefinery’’ as a solution for of lignocellulose and waste streams into an interesting platform
sustainable development. In a biorefinery, renewable feedstocks and specialty chemicals. These highly valuable and marketable
(biomass or food waste) are refined/upgraded to yield fuels and products are usually required in smaller volumes if compared
commodity chemicals by means of chemical and biological to fuels. At such scales, the existing side-products from
conversion technologies. well-established sectors (e.g. agroindustry, food sector, paper
In the past few years, many biorefinery studies, propelled by manufacturing and recycling) can efficiently serve as the renewable
the availability of specific funding schemes, have focused on feedstock for the production of specialty chemicals and materi-
the production of energy in the form of fuels. As a consequence, the als. Therefore, the upgrade of biomass waste can be performed
scientific literature has witnessed the proliferation of different in a substantially environmental friendly way, avoiding pressure
studies describing methodologies to convert biopolymers from on agriculture to switch to the production of specific crops with
lignocellulosic biomass into hydrocarbon fuels, pyrolytic bio-oils the resulting problems associated with land use changes,
and fuel additives.1 Nevertheless, after the first wave of enthusiasm, conflicts with the food markets and loss of biodiversity, which
the role of biofuels in a future energy supply scenario has been are the strongest problems associated with the production of
subjected to intensive criticisms, especially due to the so called biofuels.2 More in general, producing chemicals from waste
streams of established sectors has the potential to additionally
Max-Planck-Institute of Colloids and Interfaces, 14424 Potsdam, Germany. raise the value of the latter without altering or refocusing the
E-mail: [email protected] current production.
This journal is © The Royal Society of Chemistry 2015 Chem. Soc. Rev., 2015, 44, 5821--5835 | 5821
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Tutorial Review Chem Soc Rev
In the last decades, a considerable number of reviews have of such building blocks will be presented, with the goal of demon-
appeared in an attempt to catalogue the many different strategies strating how green and sustainable processes can positively impact
developed to convert the three major bio polymers contained in the field of material and polymer chemistry. Emphasis is placed on
biomass into conventional base chemicals. Here, the economic some aspects of the synthetic methodologies of these materials that
competition is quite high, and an effective market penetration is further contribute to the sustainability of the final products.
still uncertain, since classical fossil-based production chains are
well established and quite economical. In addition, competition is
expected to increase due the controversial shale gas revolution, General considerations on biorefinery
which seems capable of providing some of the traditional energy
carriers and platform chemicals at a very competitive price, Biorefinery has been often compared to traditional refinery,
despite the highly adverse environmental effects.3 which converts fossil crude oil into higher value products by
Besides those conventional tracks, biorefinery approaches, optimized processes capable of valorizing each fraction of the
however, have brought focus on a series of building blocks that complete crude. Some of the most relevant differences are that
are unique and potential game changing alternatives to the oil is found in nature in the form of a liquid and is characterized
present building blocks used ubiquitously by the chemical by low oxygen content, while biomass is often solid and composed
industry for the preparation of materials and pharmaceuticals. to a high extent of oxygenated molecules. Raw materials including
Such molecules do not compete immediately with petrochemicals organic crop waste, wood and straw are highly heterogeneous and
and might be used for new and innovative products. Lactic acid, are mostly composed of polysaccharides (usually accounting for
levulinic acid, 5-hydroxymethylfurfural, g-valerolactone as well as 60–80% of the weight) and the aromatic rich lignin (15–30 wt%),
lignin derivatives have received the attention of the scientific which are tightly bound in the form of a nanocomposite (Fig. 1).
community since they represent a new pool of building blocks Due to the complication of processing, the initial approach
or chemical space, which in many cases can be employed with to the biorefinery of woody biomass was focusing on a first step
minimal derivatization for the production of new materials, turning solids into processable liquids, i.e., onto the production
polymers and pharmaceuticals. The great potential of the obtained of so-called biocrude oils (e.g., pyrolysis oils, hydrothermally
products is the ability to offer alternative and improved properties derived oils), which are being already commercialized by a
with respect to the corresponding oil-derived specialty products, number of companies around the world (see for instance Licella
which in many cases even go beyond the intrinsic advantages of Ltd). However, these bio-oils are not really competitive if the
sustainability and biocompatibility. final goal is the valorization into higher products, e.g., building
This review intends to provide a short overview on the latest blocks and functional molecules. The here advised selective
developments and trends in the preparation of new materials and generation of fine and platform chemicals has proven much
polymers based on those ‘‘less traditional’’ chemicals obtained from more demanding and troublesome from a technical point of
biorefinery. We will initially describe selected examples of chemical view. Due to the high heterogeneity of biomass, any process
biorefinery approaches which allow for the recovery of valuable aimed at biomass deconstruction into its monomers acts on all
building blocks from the direct treatment of raw biomass. A of the components at any one time generating often broad
representative selection of novel materials synthesized on the basis mixtures of compounds. The cost of separating the components
Davide Esposito is currently leading Since 1993, Markus Antonietti has

the ‘‘Biorefinery and sustainable been the director of the Max
chemistry’’ group at the Max Planck Institute of Colloids and
Planck Institute of Colloids and Interfaces. Having his roots in
Interfaces. He graduated in 2006 polymer science, he developed his
from the University of Napoli profile into modern materials
‘‘Federico II’’ and was later chemistry, where sustainable
awarded a PhD from the ETH processes and chemicals are a
Zürich (2012). During his central theme. He has published
undergraduate and graduate around 650 papers and issued 90
studies he performed research patents, and his H-index is 117.
stays at Leiden University and at Besides being a scientist and a
Davide Esposito the Max Planck Institute for Markus Antonietti teacher, he also plays part time
Colloids and Interfaces. He has in a rock‘n’roll band.
also worked in the latter institute as a post doc before being
appointed to his current position. His scientific interests include
green chemistry, sustainable synthesis of chemicals and novel
catalytic materials.
5822 | Chem. Soc. Rev., 2015, 44, 5821--5835 This journal is © The Royal Society of Chemistry 2015
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Fig. 1 Schematic representation of woody biomass composition.
of these mixtures has been one of the major drawbacks of deconstructed at a later stage. In DD processes, catalysts or
such approaches. Hence, the development of more selective reactants are applied that can promote hydrolysis and cleavage
methodologies for the deconstruction of lignocellulose and the reactions to a higher extent. By appropriate selection of the catalytic
separation of its constituents is of crucial importance. conditions, DD processes can be optimized to generate a variety of
A convenient solution to circumvent this challenge could be to different products ranging from mixtures of partially and fully
separate the carbohydrate portion of the biomass from the lignin, depolymerized carbohydrates and lignin to well defined building
thereby producing two streams of products ready for further blocks and platform chemicals (Fig. 2). In addition, it is important
processing. Solvothermal methods, i.e., the treatment of biomass to remember that besides chemical approaches, the repertoire of
with solvents at elevated temperatures, have found broad applica- biorefinery can comprise a series of very efficient biotransformation
tion, due to their simplicity, adaptability to wet biomass, and processes, which are alternatively capable of converting NDD
environmental compatibility. Many research groups have opti- products into building blocks which complement and expand the
mized these approaches for the sole isolation of the cellulose or pool of compounds obtainable by DD processes.
lignin fraction, inspired by the knowledge on pulping processes The following describes some particularly interesting build-
developed by the paper industry. In the past few years, however, ing blocks that can be obtained via DD and NDD processes
new methodologies that allow for the simultaneous deconstruction followed by representative examples of their application in the
of polysaccharides and the partial depolymerization of lignin have field of material science. The goal will be to guide the reader
been designed. From now on we will refer to them as degradative through examples that indicate the interplay of green chemistry
(DD) and non-degradative (NDD) deconstruction processes. NDD and material sciences, while a comprehensive description of
processes are usually based on mild dissolution treatments with the field is clearly out of the possibilities of such a tutorial.
either organic solvents (‘‘organosolve’’ processes) or water, and with
the auxiliary of mild additives (catalyst, reactants or derivatization
reagents). In this kind of processes, based on the difference of Lactic acid
solubility in the chosen solvent system under the applied condi-
tions, cellulose, hemicellulose and lignin can be separated in the Lactic acid (LA) or 2-hydroxypropanoic acid is an important C-3
form of partially depolymerized substances, which can be further platform chemical targeted by biorefinery. Besides its direct
Fig. 2 A representation of degradative (DD) and non-degradative (NDD) deconstruction processes, for the valorization of biomass.
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application as a food additive or a component of pharmaceutical of mixtures of products are the subject of current research. In the
and cosmetic formulations, LA can be regarded as the precursor contest of LA production, the alkaline hydrothermal treatment of
of a series of chemicals of enormous industrial importance. cellulose has shown promising results. While the decomposition
Simple catalytic transformations which have been applied to LA of carbohydrates into LA under basic conditions has been known
include oxidation to pyruvic acid, reduction to 1,2-propandiol, or for long time, the ability of hydrothermal conditions to accelerate
esterification to generate a series of lactate esters (Scheme 1). In the formation of LA has been only rediscovered recently. The
the field of polymer science, the dehydration of LA into acrylic addition of additives during the hydrothermal deconstruction
acid has been explored, but the synthesis of di-lactide, used for of cellulose plays a crucial role in enhancing LA yield and
the preparation of the biodegradable polylactic acid (PLA), selectivity.5 Capitalizing on different studies which analyzed the
remains the most important applications of LA. Many reviews role of NaOH, ZnSO4 and NiSO4 during the hydrothermal hydro-
have recently been published summarizing the most recent lysis of glucose, a batch method was recently developed which
advances in lactic acid production and transformation.4,5 combines the use of Ni, Zn and activated carbon in NaOH
Traditionally, fermentation is the preferred option for the solutions (2.5 M) and is capable of converting cellulose into LA
production of LA in industry. This approach relies on the use of in only five minutes with a yield of 42% at 300 1C.6 Alternatively,
glucose and bacteria and, in comparison to classical chemical Ca(OH)2 was successfully used for the production of LA from corn
processes, the main drawbacks are the low space-time productivity, cobs, affording the latter in 45% yield after treatment at 300 1C.7
the cost of separation, and massive aqueous side products. Ideally, Recently, our group developed a competitive approach for the
the direct chemical conversion of raw lignocellulosic substances base catalyzed hydrothermal treatment of biomass based on
could substantially simplify and increase the sustainability of LA the use of Ba(OH)2.8 Such treatment results in the controlled
production. For this reason, several groups have recently reported depolymerization of the cellulosic portion of biomass with the
different approaches for the chemical synthesis of LA. In many preferential formation of barium lactate. These DD conditions
cases, models have been used in order to acquire a mechanistic allow for the convenient separation of the lignin contained in
understanding of the processes. Trioses in particular have been the biomass in the form of low molecular weight oligomers
identified as an intermediate in the synthesis of LA and were (B1 kDa). Thanks to its hydrophobic nature, lignin fragments
exploited as starting materials for the preparation of the latter can be easily recovered by simple filtration at the end of the
under a variety of different conditions. Although very valuable for reaction after precipitation. The decomposition of sugars under
the theoretical understanding, such approaches are penalized by basic conditions is assumed to proceed via a retro-aldol splitting
the use of expensive trioses, and for a detailed description of such of the carbon backbone (Scheme 2) resulting in the formation of
methods we redirect the reader to the literature.4 Here, the direct glyceraldehyde and dihydroxyacetone in dynamic equilibrium.
conversion of crude lignocellulosic biomass or cellulose into LA is Dehydration to methylglyoxal followed by a 1,2-hydride shift
outlined, which presents clear economic advantages. Preliminary finally affords the lactate fragment, which can be neutralized to
studies have recently showcased the value and efficacy of the corresponding LA by acids.
hydrothermal conversion of carbohydrate precursors. Additional The use of acidic conditions has also been recently proposed
investigations to unravel the fundamentals of carbohydrate decon- for the synthesis of LA in superheated water. Unlike alkaline
struction and identify specific conditions that avoid the generation treatments, such approaches bypass the need for an acidic
workup and the loss of reagents in neutralization. The group of
Dong recently reported an intriguing protocol for the preparation
of lactic acid from cellulose based on the use of lanthanide
triflates, with europium triflate showing the best activity and a
yield of ca. 63%.9 In this case, the reaction was performed at
240 1C on a 300 mg scale for 30 minutes under an overpressure of
nitrogen (20 bar). Interestingly, recycling experiments successfully
showed the possible reuse of the catalyst over at least five reaction
cycles. A second interesting report, which appeared almost
simultaneously, described the efficient preparation of LA (68%
yield) using Pb(II) ions at even milder temperatures (190 1C, 30 bar
N2, 4 h) starting from cellulose.10 The authors also reported the
possibility of converting raw biomass under the same conditions,
leading to the isolation of LA in 40% yield.
Lactic acid in material sciences

A major segment of the annual LA production is dedicated to
Scheme 1 Possible transformation of LA into fine chemicals and material the synthesis of di-lactide, the cyclic dimer of self-condensation
precursors. of LA which is in turn the starting material for the synthesis of
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Scheme 2 Mechanism of LA formation via basic hydrolysis of sugar in water. Reproduced with permission from ref. 8. Copyright 2013, Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim.
high molecular weight PLA (Scheme 1). Although PLA can also raw biomass with very strong inorganic acids), and it was one of
be directly obtained via polycondensation of LA, this reaction the first platform chemical targeted for commercial applica-
only leads to lower molecular weight polymers. Such oligolactides tions (see the Biofine process). Nowadays, this commodity is
are usually the precursor of dilactide via catalytic backbiting. The practically obtained via acid catalyzed hydrothermal hydrolysis
preparation of PLA has been extensively covered in previous of cellulose, which proceeds with the simultaneous formation
reviews, as well as its application in the packaging, pharmaceutical of stoichiometric amounts of formic acid, together with inso-
and biomedical sectors.5 PLA is characterized by relatively limited luble carbonaceous condensation products called humins. LEV
thermal and mechanical properties, and different research groups represents a promising candidate for the generation of a series
have been recently working on the preparation of blends and of other platform chemicals, and possible conversion strategies
copolymers of LA as well as composites with improved properties. have been extensively discussed.1 Among others, LEV has been
In order to preserve the green footprint of the final material, proposed as a starting material for the synthesis of useful
copolymerization of LA with monomers or compounds which can esters, pyrrolidones, diols and cyclic lactones, some of which
be as well obtained from biomass via DD and NDD processes are are depicted in Scheme 3. Among all possible products obtainable
currently under investigation. In this regard, the preparation of from LEV, g-valerolactone (GVL) has received the most attention
PLA composites with cellulose nanowhiskers represents a very for its role as renewable solvent and sustainable fuel additive.13
interesting example. Ahmed and Thielemans recently reported the This compound is characterized by a very low toxicity and it has a
preparation of PLA fibers whose tensile modulus increases of similar polarity to dimethylformamide, which makes it a remark-
about 45% via addition of cellulose nanowhiskers at their ably good medium for the synthesis of macromolecules as well as
surface using polyvinyl acetate as the binding agent.11 This for the deconstruction, fractionation and hydrolysis of biomass
particular treatment additionally confers to the PLA fiber surface polymers. Different approaches have been recently proposed to
an increased roughness and hydrophilic character. Moreover, increase the efficiency of GVL preparation. In many cases, new
the nanocomposite showed improved biocompatibility and func- catalyst preparations are sought that are characterized by
tioned well as support for cell proliferation, anticipating the improved stability towards strong acidic environments. In this
application of this class of composites for biomedical uses. way, the direct processing of crude LEV feeds obtained by
Besides cellulose fibers and whiskers, lignin is another potential hydrolysis of biomass is facilitated, although very often the
biomass component for such composites. The groups of Sattely use of rare transition metals has been required. Alternatively,
and Waymouth reported an interesting study on the preparation emphasis is given to the development of green protocols for the
of PLA–lignin copolymers obtained by grafting PLA onto lignin selective extraction of LEV from acidic aqueous solutions. This
during organocatalyzed lactide ring opening polymerization. The approach allows performing the successive hydrogenation in
obtained copolymers display expanded thermal properties compared the absence of acid and enables the use of commercially
to commercial PLA. In addition, due to the UV active aromatic available catalysts based on non-rare transition metals.
motifs introduced by the lignin fragments, the final material was Besides its potential as green solvent, GVL represents an
characterized by improved optical properties.12 interesting scaffold for the preparation of polymers, since it can
be further functionalized affording polymerizable monomers.
Among other strategies, a-methylenation is exploited to prepare
From levulinic acid towards materials methylene-g-valerolactone (Scheme 3), which is amenable to
radical polymerization and could mimic the reactivity of more
Levulinic acid (LEV) is a g-keto acid obtainable via DD of classical petrochemical (meth)acrylates.
cellulosic materials. LEV is one of the most studied products In the past, similar vinyl butyrolactones were already con-
in the contest of biorefinery, both in academia as well as in sidered as suitable candidates to potentially expand the family
industry (it was obtained over the past century by treatment of of methyl methacrylate polymers. The presence of a locked ring
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Scheme 3 Potential routes for the conversion of levulinic acid into building blocks, solvents and monomers for synthetic polymers.
structure in such monomers increases the reactivity in free resulting g-valerolactone in the presence of silica supported
radical polymerizations. In addition, vinyl butyrolactones derived barium acetate.15 The main drawback of this approach is the
polymers show a higher refractive index and higher glass transi- recurring deactivation of the catalyst during the reaction. For
tion temperatures, which can be considered advantageous. this reason, the solution phase methylenation of GVL could
a-Methylene-g-butyrolactone (MBL), for example, is a natural represent a valuable alternative. Molinari et al. recently intro-
vinyl monomer which can be extracted from tulips. Different duced a scheme for the acid catalyzed DD of biomass aimed at
methodologies have been applied for the preparation of polymers the formation of LEV, followed by RANEYs Ni catalyzed
based on this compound, which performs well in radical and reduction of LEV to g-valerolactone, which is made possible by
anionic polymerization. Poly-a-methylene-butyrolactone is char- an extractive protocol performed in methyl tetrahydrofuran.16
acterized by a glass transition temperature of 195 1C and proved Such organic feeds could be in principle used as the starting
to be stable up to 320 1C, while offering improved solvent material for the solution methylenation of GVL using paraform-
resistance if compared to poly(methyl methacrylate) due to the aldehyde under basic conditions. The products isolated via this
presence of the lactone ring that increases chain rigidity.14 approach are expected to be amenable to radical solution and
Nevertheless, direct extraction of MBL from plants can only be heterophase polymerization opening the way to strategies for the
performed with low yields. Currently, materials based on this preparation of high molecular weight latexes under a variety of
compound can only be obtained by synthesizing the monomer different conditions (Fig. 3). Interestingly, MGVL polymers have
on the basis of oil derived platform chemicals. In contrast, already been reported in the literature previously. Stille et al. for
MGVL could become available on the basis of a sustainable instance, described the synthesis of MGVL from non-sustainable
biorefinery process (Scheme 3). Routes to access MGVL are still precursors (propylene oxide and 1-bromovinyl trimethylsilane)
subject of research, as the a-methylenation of g-valerolactone followed by examples of radical and ionic polymerization of
has not yet been systematically optimized. Recently, Manzer MGVL, which afforded amorphous polymers characterized by
reported the preparation of MGVL from levulinic acid using a very high Tg (211–220 1C).17 More recently, the group of Jones
two-step approach, consisting of a Ru/C catalyzed hydrogena- reported the emulsion and microemulsion polymerization of MGVL
tion, followed by the gas phase (340 1C) a-methylenation of the as a convenient way to obtain high molecular weight polymers.18
Fig. 3 Scanning electron micrographs of PMGVL latexes prepared with KPS (PDL, left) and AIBN (ADL, right); the bars indicate 200 nm.
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As anticipated, this class of materials has the potential to expand salts, these methods are still undergoing continuing development,
the range of applicability of acrylates, due to the improved and the quest for cheaper ILs and less toxic catalysts is still
thermal stability. ongoing. Finally, it is worth mentioning that although the conver-
sion of fructose into HMF appears to be quite robust and reliable,
the direct use of raw cellulosic biomass is preferred, due to the
5-Hydroxymethylfurfural and related higher costs of fructose compared with raw cellulosic materials. In
products and materials this regard, the development of catalysts for the effective isomeriza-
tion of glucose into fructose will play a pivotal role. Examples from
Besides LEV, acid catalyzed DD processes offer convenient the field of zeolites have appeared. The group of Davis for instance,
opportunities for the preparation of 5-hydroxymethylfurfural has recently reported the development of tin-based zeolites capable
(HMF) as a direct dehydration product of carbohydrates. of converting glucose into fructose under very mild conditions with
Obtained also as a byproduct during the hydrolysis of biomass high efficiency.22 Nevertheless, these processes go beyond the scope
into LEV, the selective production of HMF has only been achieved of this review and will not be discussed in detail.
more recently, because of its tendency to generate condensation HMF conveniently conserves the 6-carbon backbone com-
of byproducts and humins as insoluble precipitates, especially for mon to its carbohydrate precursor, but is at the same time
reactions at high starting concentrations. Similar mechanisms characterized by half of the oxygen content. The pendant
have been evoked in the genesis of hydrothermal carbon from hydroxyl as well as the aldehyde functionality can be easily
lignocellulose and have been reviewed elsewhere.19 During DD modified by means of catalytic transformations. In general,
processes of biomass, HMF is generated as the product of derivatives of HMF have found application either as monomers
dehydration of the intermediate fructose, formed in situ via for polymers, or as fuel additives and fuel precursors if the
glucose isomerization. In practice, as the quantitative isomeriza- oxygen content is appropriately further reduced, as shown in
tion of glucose to fructose is rather complicated, HMF is often Scheme 4. The types of transformations which are commonly
synthesized in high yields using fructose as the starting material. applied on HMF usually involve reduction and oxidation reac-
Fructose can be obtained as the product of enzymatic upgrade of tions. The development of new sustainable catalytic procedures
starch and inuline. A number of different solutions have been for the upgrade of HMF, which are compatible with industrial
proposed to convert fructose into HMF, with most methods implementation, is currently a very active area of research.
relying on the use of organic solvents. In general, such transfor- Particular emphasis is given to the engineering of new catalysts
mations can be performed with high yields (90% to quantitative) which are based on abundant and inexpensive metals, with the
under rather mild conditions, usually not exceeding temperatures intention of replacing the more classical rare transition metal
of 120 1C, and in short times (B2 h). based catalysts. Examples of approaches leading to the genera-
Among different solvents, dimethyl sulfoxide (DMSO) has tion of more sustainable catalysts will be briefly given in the
shown the highest performance for the solvolysis of sugars into next section. Here, we would like to recall some general features
HMF. It has been speculated that DMSO can act as an effective of representative and established catalytic schemes for the
stabilizer for the furanose form of fructose, which is the active derivatization of HMF which have recently appeared in the
species undergoing dehydration to HMF.20 For this reason, the literature (a more general review on this topic has been recently
reaction can be performed also at higher concentrations, albeit published by Corma et al.1). HMF oxidation can occur on both
excessive loadings (50 wt% solutions) result in a considerable its alcohol and aldehyde functionalities, with the possibility of
decrease in the yield (B50%). The alternative use of DMSO in forming intermediate mono-oxidation products, resulting for
the mixture with other solvents (e.g., acetone), or the use of instance in monoacid species. One of the most interesting and
different solvents systems based on dimethylformamide has well-studied derivatives of HMF is the so called 2,5-furandicarboxylic
shown good results. In combination with such a solvent system, acid (FDCA, Scheme 4). This di-carboxylic acid was identified as
a variety of acidic catalysts have been evaluated. In general, a potential substitute of terephthalic acid for the preparation of
sulfonic acid based catalysts have shown very promising PET analogs, due to structural similarity. Several different
results, in both their homogeneous and heterogeneous form. methods for the oxidation of HMF into FDCA, which rely on
Also the use of zeolites and heteropolyacids has been explored the use of noble metals have been proposed. Initially, Pd, Pt
and details in this direction can be found in ref. 20. An and Au based catalysts have provided good results, but a
alternative approach for the generation of HMF is based on bimetallic catalyst prepared by the addition of a second metal
the use of ionic liquids (ILs). In this contest, imidazolium based to these well studied systems proved in many cases to show
ionic liquids proved particularly effective in promoting the superior activities.23 The reactions are usually performed in
formation of HMF, with ethyl methyl imidazolium chloride water at temperatures between 25 and 100 1C, using dioxygen as
being one of the best solvents.21 These ionic solvents showed the oxidant.24 The latter has the role to regenerate the metal
their best performance in combination with chromium salts. Such surface by scavenging electrons, thereby forming hydroxide and
systems could even enable the direct conversion of glucose and peroxide ions. The reaction has also shown to be pH depen-
cellulose into HMF with reasonable preparative yields (ca. 45%). dent, in a basic environment promoting the efficient formation
Nevertheless, due to the high cost of production of ILs and the of FDCA. Due to the possible disproportionation of HMF under
high environmental impact associated with the use of chromium basic conditions via Cannizzaro reactions, stringent pH control
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All materials and polymers prepared on the basis of the

monomers described before are essentially low carbon materials.
In this direction, the first idea for sustainable polymers based on
furan derivatives came with the preparation of polyethylene
furanoate (PEF) as a potential replacement for polyethylene
terephthalate (PET), since terephthalic acid has been recently
added to the list of potential human endocrine disruptors. This
new type of polyester presents considerable advantages in terms
of gas permeation (e.g., oxygen permeation) compared to PET.
The success of this application has boosted the proliferation of

an intense area of research aimed at the synthesis of additional
classes of polymeric compounds based on sustainable furans.

Examples of different polyesters, followed by polyurethane and
polyamides, are currently appearing in the scientific literature.27
A comprehensive description of this exciting and rapidly developing
area however goes beyond the scope of this tutorial presentation.
Cellulose derived materials

Many of the primary products from non-degradative treatments
of biomass can be conveniently upgraded into different materials
by straightforward transformations. Cellulose represents a very
well established and consolidated example in this direction. The
paper industry has applied NDD processes known as ‘‘pulping’’
since long time. Such processes (e.g., soda pulping, Kraft-process,
Scheme 4 Schematic of HMF synthesis and derivatization into useful
etc.) which commonly make use of relatively mild conditions
building blocks and fuel additives.
are at the basis for the production of cellulose based fibers like
viscose and cellophane. A more detailed description of such
needs to be applied, and generally the use of two equivalents of pulping approaches will be given in the next section. Here, we
base represents a reasonable compromise. Besides oxidation would like to underline the fact that in the past, despite a
products, reduced derivatives of HMF have also been proposed considerable initial success, the production of cellulose based
and reported recently. Simple catalytic reduction of the aldehyde materials was hampered by the development of analogous and
on HMF can be performed to generate 2,5-dihydroxymethylfuran more economical materials obtained on the basis of oil pre-
(DHMF), a versatile diol which can serve as a useful building cursors. Recently, the necessity of eliminating non-renewable
block in the preparation of polyesters. DHMF can be prepared resources from the production chains of some commodity
using conventional strategies,1,21 which rely on the use of materials as well as the establishment of the biorefinery para-
supported transition metals in combination with a reducing digm have newly stimulated research aimed at the preparation of
agent. Novel catalyst preparation based on alloys has also been new cellulose based materials characterized by novel properties.
recently reported and showed an excellent activity.25 Such alloys In the previous paragraph for instance, we mentioned how
were prepared excluding the use of rare transition metals, with cellulose nanowhiskers have been recently exploited in the field
a clear advantage in terms of sustainability. Interestingly, the of polymer composites.11 As excellent studies have been already
presence of additives can significantly alter the selectivity of done describing these developments, we only mention this
hydrogenation resulting in the alternative formation of decar- branch for completeness.
bonylation products, deoxygenation affording 2,5-dimethylfuran Besides polymer composites, another traditional usage of
(DMF) or even the fully saturated dimethyl tetrahydrofuran cellulose is carbonization for the synthesis of biocarbons and
(DMTHF). In this regard, the group of Rauchfuss has recently activated carbons. These carbons are practical and cheap
highlighted the versatility of palladium on carbon for such choices to support metal nanoparticles affording in this way
transformations, whereby the selectivity towards DMF and catalysts that can be successfully applied in the field of hydro-
DMTHF can be tuned by selection of the solvent and additives, genolysis and hydrogenation. Such processes are actually crucial
using formic acid or molecular hydrogen as the hydrogen donor for the success of biorefinery, since many of the primary products
respectively.26 Such reduced derivatives are characterized by of DD as well as NDD treatments of biomass can be upgraded
excellent solvent properties and have great potential as a diesel by straightforward catalytic transformations, as discussed above.
substitute and fuel additives. DMF has been also recently Unfortunately, very often these transformations rely on very
exploited for the synthesis of para xylene in combination with expensive catalysts based on rare metals from the platinum-
shale gas derived ethylene.3 group. In addition, such supported catalysts are often subject to
View Article Online
Fig. 4 Schematic representation of carbon supported FeNi nanoparticles obtained by carbothermal reduction of cellulose. Figure adapted from ref. 25,
r 2014.
leaching and passivation when in contact with real biomass Table 1 Conversion, selectivity and optimized temperature for the hydro-
hydrolysates. The use of inexpensive and abundant elements, genation of different functional groups using CFP supported FeNi alloy.a
for example iron and nickel, in combination with cheap and Reproduced from ref. 25, r 2014
accessible supports prepared by cellulose carbonization can
Conversion–
result in an optimal combination for the preparation of hetero- Entry Substrate Product selectivityc (%–%) T (1C)
geneous catalysts. Such catalysts have the potential to mitigate
the costs for the production of sustainable chemicals from 1a 499–499 50
biomass. Cellulose paper has been recently used as a structure
precursor for the preparation of carbon electrodes under pre-
servation of the macro- and microtexture.28 Inspired by such an 2a 499–499 50
approach, carbon supported alloys have also been prepared by
simple impregnation of cellulose filter paper with nickel and
iron nitrates, followed by carbothermal reduction.25 This form 3a 499–499 100
of reductive treatment is particularly indicated for the genera-
tion of carbon encapsulated nanoparticles (Fig. 4).
The encapsulation of FeNi nanoparticles into graphene 4a 499–499 100
layers provides a highly stable yet very active material, which
was successfully tested as a catalyst for the continuous hydro-
genation of different molecules, including compounds obtained
5a 499–56 125
by the DD treatments of biomass (Table 1).
The catalyst showed high activity for the reduction of HMF
for instance, but also for molecules like glucose and xylose which in
industry are traditionally converted into the corresponding alditols 6a 499–90 150
using RANEYs nickel. Interestingly, the carbon supported NiFe
alloy showed a prolonged stability on stream (ca. 80 h).
Besides catalytic materials, an array of different functional 7a 499–84 150
materials can be prepared by using cellulose as base. A particularly
noteworthy example is the preparation of magnetic paper based on
nano-cellulose.29 In this case the cellulose fibrils act as a polymeric 8a 499–88 150
dispersant for ferromagnetic nanoparticles, which are incorporated
into or constructed onto the support via simple sol–gel techniques.
The resulting paper can function as a simple actuator in the 9b 84–499 150
presence of a magnetic field.
10b 99–60 150
Lignin and lignin derivative

procurement 11a 499–40 150
Lignin is one of the main products obtainable via NDD treatments

Conditions: 0.1 M solution of starting material in EtOH. a 1 mL min 1,
of biomass. This polymeric substance, being a major component 10 bar (H2). b 0.3 mL min 1, 50 bar (H2). c Determined by uncorrected
of woody biomass, has been historically produced by the paper GC-MS analysis.
industry, usually as a side product of pulping processes, converted
into energy by incineration. In recent years, lignin has received are common to the three most abundant building blocks of
attention as a potential source for aromatic building blocks. lignin, namely coumaryl, coniferyl and sinapyl alcohols (Fig. 5).30
Lignin is biosynthesized in plants via the random interconnection The condensation of these building blocks into a polymeric structure
of substituted phenyl propane units. Phenyl propane backbones via a combination of phenol radicals is mediated by peroxidases.
View Article Online

Fig. 5 Schematic representation of lignin and its constituting building blocks.
The resulting framework is rather heterogeneous, also considering approaches have been presented in the literature, mostly focusing
the occurrence of additional building blocks contained in lower on reductive and oxidative methods.30 Recently, the hydrogenolytic
amounts (e.g. phenylcoumaran), and it is characterized by the cleavage of aryl ethers linkages promoted by a nickel-based catalyst
presence of several aryl ether and carbon–carbon bonds with has received considerable attention. This exciting reaction, which
different bond energies (usually classified as 4-O-5, b-O-4, b–b).30 has been initially evaluated on model molecules that reproduce the
The most abundant functional groups present in lignin are generally most common aryl-ether linkages found in lignin, has shown great
aliphatic and phenolic alcohols, together with methoxy groups. potential in both its homogeneous and heterogeneous variations.
Lignin of different compositions can be accessed by For instance, a new nickel–titanium nitride composite has been
proper selection of the biomass. Interestingly, hardwood, softwood developed which catalyzes the cleavage of molecules like diphenyl
and grass lignin incorporate the same pool of monomers, although ether and substituted analogs thereof under relatively mild
the relative content of all building blocks is quite different. conditions in the presence of gaseous hydrogen. Such reaction
Softwood lignin is built up to a large extent of coniferyl alcohol, converts diphenyl ether into a stoichiometric mixture of benzene
for instance, while hardwood lignin is characterized by the and cyclohexanol, while preliminary experiments performed on
presence of both coniferyl and sinapyl alcohols in comparable a real alkali lignin sample demonstrated the occurrence of
amounts. An additional factor which greatly influences the depolymerization.32 Similar results have been achieved also
composition of the lignin is the typology of the processing using nickel deposited on silica as the catalysts.33 Transfer
strategy (NDD) that is utilized to separate it from the crude hydrogenation methodologies that bypass the necessity of work-
biomass. The characteristics of the most common industrially ing with gaseous hydrogen have also been proposed. Here, lignin
applied pulping methods for the isolation of lignin have been depolymerization using formic acid as the hydrogen donor in the
described before.31 Some of the general features of such treatments presence of Ni deposited on a zeolite support (Al-SBA-15) has
are detailed in Fig. 6. The different chemistries underlying these shown promising results.34 Alternatively, isopropanol has been
treatments provide lignin fragments with different degrees of exploited as the hydrogen donor in combination with RANEYs
polymerization and may promote an alteration in the distribution Ni for the processing of organosolv lignin, resulting in the
of functional groups. In addition, the presence of additives generation of non-pyrolitic, non-gumming bio oils. Such crudes
employed during the pulping process often results in the intro- contained lignin fragments with a very low degree of polymeriza-
duction of functionalities which are originally not present in the tion and in which the main backbone has been decomposed to a
native lignin structure. For instance, in the case of Kraft and great extent into mono aromatic units and aliphatic residues.35
Sulfite pulping the isolated lignin incorporates a considerable A further development of this method was accomplished by Rinaldi
amount of sulfur in the form of thiol groups. All pulping et al. who utilized a combination of an organosolv treatment with a
processes usually afford lignin in the form of low molecular simultaneous transfer hydrogenation in one pot, for the direct
weight polymers or even oligomers. conversion of biomass. By treating wood with 2-PrOH–H2O water
The further depolymerization of such fragments can be mixtures at 180 1C in the presence of RANEYs Ni they were able
achieved by a second processing step and in this regard different to deconstruct the biomass recovering phenol rich non-pyrolitic
View Article Online

Fig. 6 An overview of the most common NDD methods for the preparation of lignin.
bio-oils as the result of the lignin depolymerization (Fig. 7).36 In liquid to dissolve cellulose or in some cases even the whole
addition, the residual pulp showed high susceptibility to enzymatic lignocellulosic biomass. Ionic liquids are also efficient media for
hydrolysis for the production of glucose. different types of nanoparticle catalyzed reactions and in addi-
In recent years, novel alternative processing methods for the tion have been used for nanocatalyst structuration.38 For this
isolation of lignin based on the use of ILs have been proposed. reason, ionothermal extractions of lignin from biomass are
The group of Welton for instance, has recently reviewed the promising candidates to be integrated with procedures in which
possible use of ionic solvents for the selective extraction of the successive catalytic upgrading or depolymerization of lignin
lignin from biomass.37 The approach has shown promising is performed using the same ionic liquid exploited for the
preliminary results and is based on the ability of ionic extraction, in order to increase compatibility. The main concern
Fig. 7 Speciation of the products obtained from the catalytic biorefining of poplar wood in the presence of RANEYs Ni at 180 1C for 3 h (2-PrOH/H2O,
7 : 3, v/v). Reproduced with permission from ref. 35. Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
View Article Online
associated with this kind of strategy is the relatively high price

and non-sustainability of current commercial ionic liquids,
although an intense area of research is emerging which focuses
on the development of novel sustainable ionic liquids.39
Despite the efficiency of the treatments aimed at the isolation
of lignin, one the main drawbacks is still the lack of efficient and
robust methods for the separation of the single families of the
aromatic compounds contained in the processed lignin fraction. Fig. 8 General structure of urushiol (A) and an example of lacquerware (B).
Nevertheless, the phenol rich matrixes isolated via NDD treat-
ments of biomass and subsequent depolymerization represent a

unique pool of building blocks for the preparation of renewable the basis of lignin, as discussed above. Cardanol, for instance,
colloids and polymers, which can be often utilized for this which can be isolated from cashew nut shell liquid, presents
purpose in the form of semi-crude mixtures. In the following, interesting structural similarity to urushiol. Recently, an intriguing
an interesting representative examples of materials prepared on review has appeared which summarizes the most important
the basis of lignin fragments will be discussed. application of cardanol to the synthesis of polymers and
additives.42
Phenols in modern polymer technology are the primary
Lignin derived materials and colloids components of phenol-resins, such as resorcinol-formaldehyde
(RF)-resins. Such macromolecules are nowadays commonly
The direct use of lignin for the generation of polymer particles employed for the preparation of advanced mesoporous sorption
and nanocomposites as well as the repolymerization of lignin materials,43 electrodes and also materials for energy storage.44
fragments as a strategy for the formation of reconstituted In addition, bisphenol derivatives are an essential part of poly-
polymers, glues, resins, and binders is indeed thought to be carbonates and epoxy-resins, although their use has been the
one of the hot areas of green polymer science. subject of a controversial debate due to toxicity issues. For
Work based on the use of lignin to reinforce polyesters was instance, bisphenol-A (BPA) is known for its severe adverse effect
already mentioned above,12 but also the direct generation of on the human endocrine system.45 In this regard, lignin bioraffinate
monodisperse polymer filler particles as biobased polymer products with lowered health impact as replacement for BPA and
beads replacing traditional petrochemical polymers is highly analogous molecules are a safe bet for one of the first blockbusters
interesting and directly applicable.40 The most exciting and from modern biorefining schemes. As an example, being one of the
direct use of lignin as the active material in a polymer battery classical lignin related building block, vanillin has been proposed as
and a supercapacitor was however reported by Inganäs et al.41 a platform for the preparation of different monomers that could
In their report, they demonstrated that lignin, in a mixture with a substitute non-sustainable phenol derivatives.46,47
cationic conducting polymer used to provide electronic conductivity, Even more excitingly, resorcinol analogs, which incorporate
can serve as an electron storing material, with an overall perfor- natural metabolites like dopamine or dihydroxy-L-phenylalanine,
mance exceeding the one of traditional, non-sustainable materials by have been shown to be an integral part of advanced biomimetic
a factor of 3–5. Compared to other petrochemical derived materials, glues48 binding for instance to leather (as known from the
lignin is not only increasing the sustainability of the final device, but traditional art of ‘‘tanning leather’’ with tannic acid derivatives),
also shows the potential to bring clear advantages in performance cellulose fibers, paper and cotton (known from lignin binding in
for a highly relevant and valuable application. This showcases wood), or even to minerals in the presence of water, as in the
how sustainable molecules open up pathways to materials for case of natural mussel adhesives.49 For all these cases, depoly-
sustainable technologies and applications, which do not come merized lignin phenols seem to be a perfect choice to generate
with compromised or reduced properties, but in turn have the analogs of dopamine or dihydroxy-L-phenylalanine on a high
potential to modify the market as such. scale, otherwise too difficult to obtain on a sustainable basis.
Substituted phenols from the decomposition of wood lignin or However, it has to be mentioned that beside the lignin depoly-
other properly-selected biowaste have of course much broader merization, biorefinery schemes should include a robust strategy
applications. The traditional Japanese art to produce lacquerware for the demethylation of phenols, considering the high percen-
which goes under the name of ‘‘Urushi’’ is based on urushiol, the tage of phenyl methyl ethers in the native lignin structure
common name for a mixture of monomers sharing a catechol unit (Fig. 9).30 Demethylation increases the number of phenolic
functionalized with alkyl tails of different lengths (Fig. 8). These groups enabling the application of lignin derivatives in redox
compounds are obtained from the resin of the lacquer tree. processes. Solutions to this problem are currently appearing in
It is clear from our cultural heritage that such lacquer the literature and are usually based on catalytic hydrodeoxygena-
objects are extremely durable and come with a high trade value tion methods.50 As an alternative, building blocks that do not
(although they are allergenic). Substrates which conserve the require such demethylation treatments could be identified. In
functionality of urushiol but are characterized by lower aller- this regard, we should mention the tannin derivative gallic acid,
genic effects could be in principle the product of a specialized which has been recently described as a promising candidate for
biorefining scheme which aims at the preparation of lacquer on the preparation of bio-based epoxy resins.51
View Article Online

Fig. 9 Schematic aspects of the chemical modification of a lignin building block for its incorporation into polymers and materials.
Beyond lignin and cellulose Glycerol derived dimethylacetal dihydroxyacetone carbonate has
been successfully reported as building blocks for the preparation
Up to now, we have restricted our attention to molecules which can of polycarbonates by the group of Waymouth, for instance.53 In
be generated from the main constituents of lignocellulosic biomass, parallel, unsaturated fatty acids have been investigated in the
namely cellulose and lignin. It is worth mentioning that a variety of last years as starting materials for the production of monomers
additional platform molecules and building blocks can be obtained via cross metathesis reactions. Such building blocks have been
by extraction of plant metabolites contained in the biomass. For already successfully applied for the synthesis of polyesters,
instance, nuts as well as seeds and plant leaves (such as the olive polyamides and polyacrylates,54 and their discussion has been
kernels and leaves), which are often accumulated as waste streams of already well-covered in the literature.
agroindustry, contain large amounts of special lignin-like molecules. Finally, it is worth mentioning that besides lignocellulosic
In case of the olive, for example, the pharmaceutically active and biomass marine biomass has also shown significant potential to
cosmetically relevant hydroxytyrosol, a component of Oleuropein, is contribute to the diversification of the products obtainable via
a well-known example (Fig. 10).52 In analogy to other lignin-like biorefinery. Excellent results have been achieved for instance by
fragments discussed above (see the case of cardanol),42 this and the group of Maschmeyer in the processing of marine algae for the
similar compounds would represent chemicals that are directly formation of enriched crude bio-oils via hydrothermal liquefaction.55
suitable for polyurethane chemistry. The upgrade of such biocrudes, which are generated from biomass
Analogous transformations could be considered for many lacking lignin and with high proteic contents, may result in the
families of compounds including tannins,51 polyphenols wide- identification of products which expand the spectrum of sustainable
spread in the vegetal kingdom, or the well-studied triglycerides, building blocks. For more details on this interesting topic, we
the main component of vegetable oils. The latter, in particular, have redirect the reader to more specialized works.
been subject of intense study in the context of biorefinery for the
production of biofuels, as discussed above. Interestingly, the main
components of such abundant vegetal feedstock, namely glycerol
Summary
and fatty acids, have already found application as platform This tutorial review explored the potential of biorefinery to become
molecules for the preparation of polymers and new materials. a game changer for the field of polymer and material science.
Fig. 10 Schematic processing of vegetable residues for the extraction of hydroxytyrosol.
View Article Online
In particular, the ability of biorefinery to provide building 10 Y. Wang, W. Deng, B. Wang, Q. Zhang, X. Wan, Z. Tang,
blocks and platform chemicals which are alternative to the Y. Wang, C. Zhu, Z. Cao, G. Wang and H. Wan, Nat.
conventional ones obtained via oil refinery was highlighted. Commun., 2013, 4, 2141.
Interestingly, such a pool of ‘‘biorefined’’ compounds can be 11 K. M. Z. Hossain, M. S. Hasan, D. Boyd, C. D. Rudd,
used for the synthesis of polymers and materials with novel I. Ahmed and W. Thielemans, Biomacromolecules, 2014,
interesting properties expanding the field of classical polymers. 15, 1498–1506.
Increased biocompatibility, lower health risks, improved bio- 12 Y.-L. Chung, J. V. Olsson, R. J. Li, C. W. Frank, R. M. Waymouth,
degradation and recyclability, and in some cases expanded S. L. Billington and E. S. Sattely, ACS Sustainable Chem. Eng.,
thermal and optical properties are only some of the advantages 2013, 1, 1231–1238.
coming with materials prepared on the basis of sustainable 13 D. M. Alonso, S. G. Wettstein and J. A. Dumesic, Green
building blocks. In this review, we mainly focused on lignocellu- Chem., 2013, 15, 584–595 and references therein.
losic biomass and summarized the most promising degradative 14 M. K. Akkapeddi, Macromolecules, 1979, 12, 546–551.
and non degradative processing strategies which are currently 15 L. E. Manzer, Appl. Catal., A, 2004, 272, 249–256.
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Redefining biorefinery: the search for

unconventional building blocks for materials

Key learning points

Introduction ‘‘food vs. fuel’’ competition, as well as an overall less favorable

Tutorial Review Chem Soc Rev

Davide Esposito is currently leading Since 1993, Markus Antonietti has