New Synthetic Routes Towards MOF Production

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New synthetic routes towards MOF production

at scale
Cite this: Chem. Soc. Rev., 2017,
46, 3453
Marta Rubio-Martinez,a Ceren Avci-Camur, b
Aaron W. Thornton,a Inhar Imaz,b
Daniel Maspochbc and Matthew R. Hill *ad
The potential commercial applications for metal organic frameworks (MOFs) are tantalizing. To address
Published on 22 May 2017. Downloaded on 8/1/2022 11:19:33 AM.
the opportunity, many novel approaches for their synthesis have been developed recently. These
strategies present a critical step towards harnessing the myriad of potential applications of MOFs by
enabling larger scale production and hence real-world applications. This review provides an up-to-date
Received 13th February 2017 survey (212 references) of the most promising novel synthetic routes, i.e., electrochemical, microwave,
DOI: 10.1039/c7cs00109f mechanochemical, spray drying and flow chemistry synthesis. Additionally, the essential topic of
downstream processes, especially for large scale synthesis, is critically reviewed. Lastly we present the
rsc.li/chem-soc-rev current state of MOF commercialization with direct feedback from commercial players.
1. Introduction the tenets of organometallic cluster chemistry with established

coordination motifs to form coordination polymers, a.k.a.
Metal organic frameworks (MOFs) have emerged as a focus of MOFs.1,2 Later reports from key instigators including Yaghi,3,4
academic fascination and commercial opportunity due to their Kitagawa,5,6 Ferey,7,8 and Long9,10 projected the potential appli-
unprecedented structures that imply a plethora of potential cations of MOFs, utilising the combination of unprecedented
applications. The initial report from Hoskins and Robson porosity with periodicity and versatile chemistries. The applications
instigated a new field of coordination chemistry, combining envisaged were largely based on separation, storage, sensing or
release characteristics.11–15 As a result, it is possible that MOFs could
a
CSIRO, Private Bag 10, Clayton South, VIC 3169, Australia have revolutionary performance in areas that include natural
b
Institut Català de Nanociencia i Nanotecnologia, ICN2, Esfera UAB, gas storage,16–18 petrochemical separation,19,20 CO2 capture,21,22
Campus UAB 08193, Bellaterra, Spain
c
or drug delivery.23,24
Institució Catalana de Recerca i Estudis Avançats (ICREA), 08100 Barcelona,
Spain
However, central to the translation of these new materials
d
Department of Chemical Engineering, Monash University, Clayton, VIC 3800, into disruptive technologies is the ability to manufacture
Australia. E-mail: [email protected], [email protected] MOFs at the required scale, purity and price for implementation.
Marta Rubio-Martinez was born Ceren Avci-Camur was born in

in Barcelona, Catalonia, Spain, Ankara (Turkey) in 1989. She
in 1982. She received her BSc received her BSc degree and MSc
degree and PhD in Chemistry degree in Chemistry from Bilkent
and her MSc in Nanotechnology University (Ankara, Turkey). She
at the Universitat Autònoma de is currently pursuing a PhD in
Barcelona (UAB) under the Material Science at the Catalan
supervision of Prof. Daniel Institute of Nanoscience and
Maspoch and Dr Inhar Imaz. She Nanotechnology (ICN2) in the
joined CSIRO Melbourne (Australia) Supramolecular Nanochemistry &
in 2013 as a Postdoctoral fellow. At Materials Group under supervision
present, she is a research scientist at of Prof. Dr Daniel Maspoch and
Marta Rubio-Martinez CSIRO focusing on extending the Ceren Avci-Camur Dr Inhar Imaz in the field of
capabilities of continuous flow metal–organic nanomaterials with
chemistry and material processing, and on scaling-up these processes special interest in developing new synthetic pathways for large scale
for large scale production of Metal–Organic Frameworks (MOFs). production of metal–organic frameworks in green conditions.
This journal is © The Royal Society of Chemistry 2017 Chem. Soc. Rev., 2017, 46, 3453--3480 | 3453
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Review Article Chem Soc Rev
For example, the potential application of the enormous natural forces, with a range of kinetic and thermodynamic products
gas reserves globally as a fuel for vehicles, adsorbed in MOFs possible, meaning that a narrow set of reaction conditions are
within the tank would immediately require megaton scale often possible for a successful synthesis. The large gap between
production of MOFs.25 Or in CO2 capture, more than 8000 million laboratory production and that required for commercial appli-
tons of CO2 are produced from coal-fired power stations annually, cation has created a strong imperative to develop efficient and
again requiring many millions of tons of MOF to capture it.26,27 In versatile means of producing MOFs at scale.
the laboratory, MOFs are most commonly produced in milligram As scale up production methods are developed, parameters
scales, with multi-day reaction times in expensive organic solvents. for assessing their viability have become important. Of these,
Their synthesis is often the balance of a number of competing the key parameter is the space-time yield (STY), a measure of
Aaron Thornton completed a Inhar Imaz was born in Hendaia

Bachelor of Mathematics and (Basque Country, France) in 1978.
Finance at the University of He received his PhD in Materials
Wollongong Australia in 2005. Science from the Université

Since then he has transitioned Bordeaux I in 2005, where he
through a PhD, contributed studied the formation of hetero-
academically to the field of metallic metal–organic architectures
membranes and adsorbents, and from tetrahedral building blocks. He
led multiple commercial projects joined the CIN-2 (ICN-CSIC) centre
at the CSIRO (Australia’s national in 2005 as a Postdoctoral fellow. At
research agency). He has established present, he is senior researcher at
a commercial relationship with Air the Catalan Institute of Nanoscience
Aaron W. Thornton Liquide and multiple academic Inhar Imaz and Nanotechnology (ICN2). His
relationships as a Visiting Scholar research interests are focused on
through secondment programs with the University of California Berkeley, controlling the supramolecular assembly of molecules, metal ions and
Chimie ParisTech, Hanyang University, University of Cambridge and the nanoscale building blocks at the macro and nanoscale for the design of
National Technical University of Athens. Dr Thornton has also served as novel metal–organic frameworks and functional supramolecular
the President of the Membrane Society of Australasia since 2014 and is architectures with interesting properties and applications in gas
currently acting as the Product Director for start-up company storage, catalysis, etc.
MOFWORX.
Daniel Maspoch was born in Matthew Hill graduated from a

L’Escala (Girona) in 1976. He PhD in Chemistry from the
graduated in chemistry at the University of New South Wales
Universitat de Girona and obtained (Sydney, Australia) in 2006. He
his PhD in materials science at the undertook a postdoc at the CSIRO
Universitat Autònoma de Barcelona following this, along with
and Institut de Ciència de Materials secondments to the University of
de Barcelona. After postdoctoral California, Berkeley, and the
work in Prof. Chad A. Mirkin’s University of Colorado, Boulder.
group at Northwestern University, He then went on to establish a
he moved to the Centre research group at CSIRO focussed
d’Investigació en Nanociència i on the use of porous materials for
Daniel Maspoch Nanotecnologia (ICN-CSIC), thanks Matthew R. Hill storage, separation and release.
to the Ramòn y Cajal Program. CSIRO’s mission is to deliver
Since 2011 he has been ICREA Research Professor and Group Leader impact for industry, and to enable this for porous materials,
at the Catalan Institute of Nanoscience and Nanotechnology (ICN2). Matthew established flow chemistry capability for MOFs at
He is interested in controlling the assembly of molecules, metal ions CSIRO to allow access to materials at kilogram scale. In 2016,
and nanoparticles for the creation of functional nanostructured Matthew began a joint position between CSIRO and Monash
materials with empty spaces (mainly MOFs and capsules) and use University. Presently, Matthew leads several applied projects with
them in diverse areas, including energy, environment, catalysis and industry partners, alongside supervising a group of postgraduate
biomedicine. students. He is the Chief Technology Officer for start-up company
MOFWORX.
3454 | Chem. Soc. Rev., 2017, 46, 3453--3480 This journal is © The Royal Society of Chemistry 2017
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Chem Soc Rev Review Article
the amount of MOF able to be produced per unit volume of In the following, we review the novel synthesis routes
reactor in a 24 hour period. In concert with this, we recently developed to date. We also discuss important downstream
proposed that the absolute value (in g h1) is also important. processing considerations and provide a summary of recent
Many new production techniques are still in the early stages, commercial developments.
meaning that the calculated STY may be prone to over-
extrapolation. Other important factors are measures of product
quality (such as surface area and phase purity), particle size 2. Production of MOFs: from
control, yield, and the versatility of the technique. This article laboratory to industrial scale
will seek to use these criteria in describing the prospective
production methods featured herein. In 1995, Nalco Chemical Company and Omar Yaghi claimed the
There are several challenges common to the bulk of the use of solvothermal synthesis to obtain MOFs.28 Up until now,
prospective scale up methods: this synthetic approach is the most common way to obtain
(a) Use of organic solvents. At scale, their cost, toxicity and in grams of MOFs in the laboratory around the world. This
some cases flammability become significant issues. method involves mixing solutions of the inorganic salt with
(b) Anion build up. Typically, metal salts are employed as the organic linker in a sealed reactor vessel and subsequent
precursor molecules. At scale, nitrates present a safety hazard, heating to promote the growth of insoluble frameworks that
and anions such as chlorides can prove corrosive. Oxide and precipitate as fine crystals.29,30 This sealed approach allows the
hydroxide metal precursors are preferable. reaction mixture be heated up to temperatures and pressures
(c) Ligand availability. Many MOFs require bespoke organic above the solvent’s boiling point to solubilize, partially or
ligands. Production methods that could also produce these completely, otherwise insoluble reagents and form extended
starting materials are in development. networks. It has become a benchmark in MOF chemistry, and a
(d) Particle size control. Applications such as membranes large variety of MOF families such as MIL series,8,31 MOF-74,32,33
require nanometre sized particles whereas in storage applications. UiOs34–36 and PCNs37,38 have been synthesized following this
Larger particles are desired to stop unwanted movement of the principle.
MOF particles. Control of this is an important attribute. However, despite the tremendous academic interest that
(e) Activation. MOFs require removal of non-volatile solvents MOFs have generated in the last two decades, with thousands
and unreacted starting materials from their pores. This is a of new structures and with very promising applications, only
major consideration at large scale. very few of them are produced at large scale and used in real
(f) Shaping of MOF powders produced is also required for world applications.18,22,23,39–41 The main reasons for this are
using them in real industrial applications. the lack of stability of most of the structures towards temperature
All these challenges, which are specific for each MOF family and humidity, the high cost of the raw materials and, above all,
due to their different composition and coordination nature, the difficulty of scaling up the synthesis and the post-synthetic
together with their extreme porosity, make the synthesis of stages in a cost-effective way whilst maintaining the product
these materials more complex than zeolites; each MOF requires quality and reproducibility between batches. In addition, while
bespoke conditions. In recent years, a number of approaches the solvothermal approach is a well-known industrial method
for addressing these challenges have been considered, including for chemical synthesis, its application for large scale MOF
electrochemical, microwave and mechanochemical syntheses as production is not feasible as MOF synthesis relies on the
well as spray drying and continuous flow production. Electro- nucleation at a reactor vessel surface. Up-scaling the reactor
chemical synthesis of MOFs was developed by BASF and their vessel significantly decreases the surface to volume ratio and
initial purpose was to exclude anions by using metal electrodes as consequently, reduces the efficiency of the reaction. Additional
metal sources. Microwave-assisted synthesis, flow chemistry and problems include: long reaction times (hours or days), large
spray-drying synthesis allow for a faster crystallization rate and amounts of solvents used, low quality of materials obtained,
production of smaller MOF crystals. In mechanochemical synth- high complexity and cost in the up-scaling.42
esis, no external heating or solvent is needed, reducing the In order for any production MOF process to be industrially
washing and activation labour after the synthesis. viable a number of key aspects have to be considered: (i) a
Given the rapid progress in the development of these techniques, versatile method is crucial in order to accommodate the maximum
there has been a recent rise in commercial entities that seek to number of MOF structures with the same piece of equipment; (ii)
utilise and/or produce MOFs. This review seeks to provide an the possibility to avoid harsh processing conditions such as high
update on progress of these companies, with direct input from temperature and pressure will reduce capital and operating costs
them. BASF pioneered large-scale, bespoke solvothermal techniques and alleviate safety concerns; (iii) a switch from batch to continuous
primarily for use in vehicular natural gas storage. Following processing would be beneficial offering higher output per unit time
this, spin-out companies have been established, often based and a continuous steady-state operation leading to significantly
upon novel reaction techniques originally developed in a reduced downtimes, labour costs, reactor volumes, as well as
research setting. Some spin-out companies also seek to develop constant and consistent production; and (iv) a high space-time-
MOF-based products in addition to the broader supply of MOFs yield (STY) parameter which measures the amount of MOF
to the research community. produced per m3 of reaction mixture per day.
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Fig. 1 Timeline of the most common synthetic approaches patented for the synthesis of MOFs.28,45,46,48,49,205–210
All these factors make the scale-up of MOF production MOF synthesis directly during the reaction by controlling the
challenging and have motivated many researchers and engineers passed current or applied voltage. Furthermore, the electro-
to explore and develop novel and commercially viable routes to chemistry method offers the possibility to synthesize homogeneous
produce MOFs in an efficient, reproducible and cost-effective thin films or coatings.52
way.43,44 Fig. 1 shows the timeline of the most common synthetic Electrosynthesis of MOFs can be classified in two main
processes developed in the last two decades. In this review, we methods: (i) the anodic dissolution, which was the first route
will focus on energy-efficient processes with reduced reaction patented by BASF; and (ii) the cathodic deposition. In the
times that facilitate the up-scaling and the continuous operation. anodic deposition, an applied electric potential induces the
In the following sections, we will describe in detail the advances release of metal ions from the electrode, which then react with
in electrochemical,45 microwave46 and mechanochemistry47 an organic linker present in the solution leading to the formation
approaches and the more recent routes, the spray dryer48 and of a MOF film. In this case, the use of a metallic electrode
flow chemistry.49 (instead of metal salts) as the source of metal cations avoids
the formation of any corrosive anions (mainly, nitrate and acetate
2.1 Novel synthesis routes anions) or any by-products. The anodic dissolution is typically
2.1.1 Electrochemical synthesis. Electrochemistry can be carried out in a two-electrode set-up without a reference electrode,
defined as the study of interconversion between chemical and and the use of protic solvents is usually needed to ensure the
electrical energy. It combines electricity and chemistry and deals evolution of hydrogen and avoid the reduction of metal ions at the
with chemical changes caused by an electrical current. counter electrode. In addition, the use of a sacrificial compound
Taking advantage of the potential of electrochemistry to (e.g. acrylonitrile, acrylic or maleic esters) that are preferentially
synthesize materials and their large experience in the domain, reduced or a counter electrode with a suitable overpotential for
the company BASF first patented the use of electrosynthesis to hydrogen evolution is recommended.53 In the cathodic deposition,
produce MOFs in 2005.50 The synthesis consisted on immersing a solution containing the organic linker, the metal ions, and a
a copper plate in a solution containing the organic linker, 1,3,5- so-called probase is contacted with a cathodic surface. In this
benzenetricarboxylic acid (BTC), and an electrolyte. The copper approach, the MOF film deposition results from increasing the
plate, which acts as the electrode, was used as the source of pH near the cathodic surface, where the electrochemical
Cu(II) ions. When a certain current or voltage was applied, the reduction of the probase occurs. An example of a probase is
Cu(II) ions were released from the copper electrode to the the nitrite ions coming from the reduction of nitrates, which are
solution and reacted with the dissolved linker. In this patent, able to deprotonate the organic linker and form the MOF.54
a powder of electrochemically produced HKUST-1 that consisted Since the electrochemical synthesis of HKUST-1 by BASF
of octahedral crystals (size: 0.5–5 mm) could be fabricated using the anodic dissolution was reported, there have been many
after applying a voltage of 12–19 V and a current of 1.3 A for efforts to understand and optimize this new route (Fig. 2a).
150 minutes. The surface area of this synthesized HKUST-1 was Fransaer et al. recently proposed a mechanism for the anodic
1820 m2 g1, which is higher than that reported for the dissolution synthesis of HKUST-1 that consists in four phases:
solvothermally synthesized HKUST-1 (1550 m2 g1).51 (i) initial nucleation; (ii) growth of HKUST-1 islands; (iii) inter-
Since this first patent, electrochemical synthesis of MOFs growth; and (iv) crystal detachment.55 When an electric potential
has attracted great attention because it can offer many advantages. is applied, the oxidation of the anode starts and the Cu(II) ions are
One of them is the possibility to run the synthesis of MOFs in a released into the solution. The nucleation of the HKUST-1 phase
continuous way. It also allows their synthesis under milder starts once the critical ion concentration on the surface of
conditions than typical solvothermal or microwave syntheses, the anode is reached. The nucleation is progressive and the
reducing the reaction time. Indeed, while solvothermal synthesis dimensions of the crystals depend on the synthesis time and
might take hours or days, electrochemical methods can produce choice of the solvent. The HKUST-1 layers grow at the MOF–solution
the MOF material within minutes or hours. In addition to these, interface confirming that Cu(II) ions, which are dissolved at the
the electrochemistry method provides the ability to control the interface, diffuse through the HKUST-1 crystals before they react
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nucleation theory.57 In the same line, Gascón et al. observed

better results in terms of HKUST-1 coverage of the electrode
when square wave functions were used instead of a continuous
mode.58 Denayer et al. found that the frequency of these square
wave functions does not influence the HKUST-1 coating of the
copper electrode.59
Solvent media is also influencing the electrochemical crystal-
lization of HKUST-1. De Vos et al.57 and Denayer et al.59 observed the
formation of larger crystals when the amount of water (from 10 to
50% in volume) was increased in the electrolyte water/ethanol
solution because it slowed down the reaction by the hydration of
the Cu(II) cations. In addition, detachment of HKUST-1 crystals from
the electrode was observed for water contents higher than 50%.
Under these conditions, Gascón et al. detected the formation of a
secondary phase consisting of a catena-triaqua-m-(1,3,5-benzene-
tricarboxylate)-copper(II) compound.60 More recently, Deyaner et al.

investigated the effect of other organic solvents (e.g. methanol,
ethanol, 2-propanol, acetonitrile, N,N-dimethylformamide (DMF),
and dimethylsulfoxide (DMSO)) in the electrochemical formation of
HKUST-1 (Fig. 2c).61 They observed that the crystal size increases
when increasing the water content in methanol and ethanol; less
dense and uniform HKUST-1 layers are obtained in 2-propanol;
HKUST-1 crystal morphology is different when using acetonitrile
instead of methanol or ethanol; octahedral crystals are generated
in DMF; and the amount of water does not influence the synthesis
of HKUST-1 in DMSO, as it does in methanol or ethanol.
Fig. 2 Electrosynthesis of MOFs by anodic dissolution. (a) Schematic Because of the low conductivity of the reaction media, electro-
illustration showing the anodic dissolution cell (left) and the formation of lytes that enhance charge transport in solution are generally
HKUST-1 on the anode electrode (right). (b) SEM image of HKUST-1 on a used. Tributylmethylammonium methyl sulfate (MTBS) is usually
copper electrode. (c) SEM image of HKUST-1 on a copper mesh. (d) SEM recommended for syntheses carried out in organic media and,
image of ZIF-8 particles on a zinc electrode. (e) SEM images of flower-shaped
MOF-5 on a zinc electrode. (r Elsevier, American Chemical Society and Royal
indeed, it showed a positive role on the HKUST-1 synthesis. For
Society of Chemistry, reprinted with permission from ref. 57, 59, 65 and 68). example, increase of conductivity by increasing the concentration
of MTBS in the electrolyte solution reduced the ohmic drop of
the solution and increased the production yield of HKUST-1.
with the organic linker. This migration of ions is accompanied However, Deyaner et al. found some disadvantages related to the
by the creation of voids at the substrate–HKUST-1 interface, use of MTBS in the electrochemical formation of HKUST-1 thin
resulting in the formation of fragile layers of HKUST-1 crystals films. They observed structural damages of the copper mesh
that are easily detached from the substrate. Simultaneously, and the generation of non-adhesive HKUST-1 crystals at the
van der Veen and Domke et al. described this anodic dissolution surface of the anode. On the contrary, they could get more
mechanism from a more chemical point of view.56 These control over the synthesis in the absence of MTBS because of
authors identified that chemical species involved in the electro- lower current density in the system.62 Another disadvantage of
synthesis of HKUST-1 are initially Cu(I)2O, which results from using MTBS was reported by Hartmann et al., who observed a
the oxidation of the copper plate in the presence of H2O or O2. decrease in the surface area of HKUST-1 that was attributed to
Then, Cu(I)2O is further oxidized to Cu(II)O that can react with the the presence of the electrolyte salt in its pores.63
organic linker and lead to the formation of HKUST-1 crystals. Beyond the archetypical HKUST-1, the syntheses of other
To date, it is known that small variations of the applied MOFs have been envisaged using anodic dissolution. Remarkably,
electric potential and passed current, the nature of the solvent Gascón et al. demonstrated the possibility to electrochemically
and its conductivity, and nature of the electrolyte have a strong synthesize ZIF-8, MIL-53 and MIL-100(Al).58 Since then, De Vos
influence on the anodic dissolution synthesis of HKUST-1. For and Fransaer et al. optimized the quality of the synthesized
example, the applied electric potential is important due to the MIL-100(Fe) by performing the electrochemical synthesis under
direct influence on the generation of Cu(II) ions from the high pressure and high temperature.64 Also, Attfield and Dryfe
copper electrode. As observed by De Vos et al., higher voltages et al. improved the synthesis of zeolitic imidazolate frameworks
applied by square wave functions provided higher concentration (ZIF) (e.g. ZIF-4, ZIF-7, ZIF-8, ZIF-14, and ZIF-67) coatings
of Cu(II) cations because of the higher dissolution rate of the (Fig. 2d) by increasing the reaction times (a proxy for higher
copper metal (Fig. 2b). These conditions led to the formation of metal ion concentration), the organic linker concentration
coatings with smaller crystals of HKUST-1 in agreement with the and the reaction temperature.65 With this anodic dissolution,
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luminescent rare earth based MOFs were also prepared by Fransaer resource. In this cathodic deposition, the metal salt, which is
et al. on electrically conductive solid substrates.66 Here, Tb-BTC dissolved in the electrolyte solution together with the organic
and Gd-BTC layers were electrochemically synthesized on terbium linker and the probase, is used as the metal precursor. To show the
and gadolinium metal foils by immersing the foil in a water–ethanol potentiality of this approach, Dinca et al. showed the synthesis of
solution containing the organic linker, the electrolyte (MTBS) and HKUST-1 and MOF-5 in only 15 min at room temperature (Fig. 3b).
applying a constant current of 1 mA cm2. For it, they used fluorine doped tin oxide (FTO) as the working
Within this variety of MOFs, the electrochemical synthesis of electrodes, Ag/Ag(cryptand) as the reference electrode, and a DMF :
MOF-5 has also been largely investigated. Cao et al. reported the water (100 : 1) (v : v) mixture containing the organic linkers and the
anodic dissolution electrosynthesis of thin films of rod-like metal salts as the electrolyte solvent. In these syntheses, it was
MOF-5 crystals.67 They could generate dense and thick MOF-5 found that the nature of the metal salt plays a crucial role. This
films by using zinc electrodes in an aqueous solution containing importance is due to the nature of the counteranions, which act as
H2BDC and ammonium fluoride as the electrolyte salt and applying a probase and can inhibit or favour the formation of the desired
voltage (2 V) at 65 1C. Liang et al. synthesized MOF-5 in the form MOF.71 For example, as the synthesis of MOF-5 starts with the
of flower shape by using molten salt in the electrolyte solution formation of Zn5(OH)8(H2O)2(NO3)2, the use of chlorine anions can
and 1-butyl-3-methylimidazole (BMiM) bromine as a template inhibit its formation due to the formation of Zn5(OH)8(Cl)2(H2O)2.
(Fig. 2e).68,69 This MOF-5 was synthesized using a zinc plate as On the contrary, the use of nitrate anions can help on its formation
the anode, a titanium plate as the cathode, and a DMF and since they can act as the probase and participate in the formation
BMIM bromide mixture containing H2BDC and zinc nitrate of the intermediate specie.
hexahydrate as the electrolyte solution. The reaction was done The aptitude of the cathodic deposition to favour the formation
in atmospheric conditions and applying a current density of films was also exploited by the same authors to form more complex
0.025 A cm2 for 2 hours. biphasic MOF thin films at room temperature from single
As state above, the second main route for the electrochemical deposition baths using potential bias as the main user input.72
synthesis of MOFs is the cathodic deposition. In 2011, Dinca In this case, bilayer structures of MOF-5 and (Et3NH)2Zn3(BDC)4
et al. first investigated the cathodic deposition of MOFs70 to (applied potential: 1.7 V) (Fig. 3c), mixed structures of MOF-5
resolve two major limitations of the anodic dissolution (Fig. 3a): and (Et3NH)2Zn3(BDC)4 (applied potential: 1.1 V), and layers of
(i) the deposition surface (anode surface) is used to produce the only (Et3NH)2Zn3(BDC)4 (applied potential: 1.5 V) were fabricated
metal cations and thus, it is eroded in a continuous manner tuning the applied potential.
throughout the synthesis; and (ii) the selection of the anode Later innovations on the electrochemical synthesis of MOFs
metal is limited since the anode is also used as the metal have been centered on the development of new methodologies
such as electrophoretic deposition,73,74 galvanic displacement,75
anodic–cathodic deposition76 or bipolar electrochemistry.77 For
example, Ameloot et al. combined both anodic and cathodic
deposition to perform the modulated synthesis of UiO-66
simultaneously on both anode and cathode surfaces.76 For this
synthesis, zirconium films were used as electrodes and H2BDC
was dissolved in a mixture of DMF, nitric acid (electrolyte),
water and acetic acid (AA). AA was used as a modulator to
increase the amount of linker defects and therefore, the BET
surface area. However, increase of AA also decreased the crystal-
linity because of the increase of the competition between BDC
and AA. It was found that denser packed films with smoother
surfaces were formed on the anode when an AA concentration of
0.5 M or 1 M was used, and that larger octahedral UiO-66
crystals were obtained for AA concentrations higher than 5 M.
In this process, when the AA concentration increased, the
complexation of released Zr(IV) ions also increased leading to
a decrease of the anodic deposition. On the contrary, when the
concentration of AA decreased, the concentration of released
Zr(IV) ions increased, thereby increasing the deposition on the
cathode.
Another interesting example was reported by Bradshaw and
Fig. 3 MOF synthesis by cathodic deposition. (a) Schematic illustration Kuhn et al. who used bipolar electrochemistry (BE) to produce
showing the cathodic dissolution cell (left) and the reaction that takes
Janus-type MOF composites inducing the site selective ZIF-8 or
place on the cathode electrode (right). (b) SEM images of MOF-5 deposited
on the cathode surface. (c) SEM images of bilayer structures of MOF-5 and
HKUST-1 crystallization on a polarized metallic wire under an
(Et3NH)2Zn3(BDC)4. (r Royal Society of Chemistry and American Chemical electric filed. In BE, a conducting object is exposed to an electric
Society, reprinted with permission from ref. 71 and 72). field established between two electrodes in a solution this
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induces a positive and negative polarization between the two Several studies have been performed comparing conventional
opposite sides of the object and a redox reactions can occur.77 electric (CE) heating, MW and ultrasound (US) methods in order
2.1.2 Microwave synthesis. Microwave (MW) irradiation is to understand the accelerated US and MW syntheses.87–90 For
a widely used method in organic chemistry. In recent years it example, in 2009, Haque et al. performed a kinetic study on the
has been used for the synthesis of inorganic nanomaterials – synthesis of MIL-53-Fe.91 They found that the crystallisation rate
zeolites and MOFs, among others.78–81 The method is based on (both nucleation and crystal growth) decreased in the order:
the interaction of electromagnetic waves with any material US 4 MW c CE. These results suggested that physical effects,
containing mobile electric charges, such as polar molecules such as hot spots, are more important than chemical effects in
in a solvent or conducting ions in a solid. Contrary to classical the accelerated syntheses performed under US and MW conditions
solvothermal methods, where thermal energy is transferred (see Fig. 4). A similar study was performed by Chalati et al. where the
from the heat source to the solution through the reaction synthesis of iron fumarate MIL-88A nanoparticles was compared
vessel, in MW synthesis the irradiation interacts directly with with the classical solvothermal, MW and US methods.92 With the
the reactants, resulting in more efficient and faster heating. CE heating a polydesperse sample of 200 nm nanoparticles was
Additionally, in MW synthesis crystallisation occurs at the hot obtained, whereas 100 nm monodisperse nanoparticles but with
spots that form due to the direct heating of the solvent, in very low yields were obtained with the US method and o100 nm
contrast to the wall of the reactor vessel as with conventional monodisperse nanoparticle with high yields were obtained with the
heating methods. Consequently, it is much faster and results in MW method.
a smaller particle size. In this section, we describe some The zeolitic imidazolate framework, ZIF-8, has been synthe-
remarkable examples of the preparation of MOFs via microwave sized with MW irradiation and CE heating at 140 1C in 4 hours
irradiation. and 20 hours respectively.93 In addition to the reduced reaction
The pioneering work on MW synthesis of MOFs by Jhung time, the ZIF-8 obtained by microwave heating had a larger
et al. reported the water-based synthesis of the chromium surface area and micropore volume compared with the ZIF-8
trimesate MIL-100 MOF in the presence of hydrofluoric acid.82 synthesized with CE heating.
The synthesis was performed in a microwave oven at 220 1C for There are a few reports available showing the effectiveness of
1, 2 or 4 hours with the reaction mixture in a sealed Teflon MW irradiation for the synthesis of lanthanide–organic frame-
autoclave. The results showed the presence of unreacted metallic works. For example, Silva et al. obtained quality single-crystals
chromium species for reaction times less than 2 hours. The of the microporous cationic [Ce2(pydc)2(Hpydc)(H2O)2]Cl (where
crystal yield obtained after 4 h was 44%, which is comparable pydc corresponds to the 2,5-pyridinedicarboxylic acid) by applying
to the 45% achieved in the conventional synthesis in 4 days. MW heating for 20 min at 200 1C.94 In 2014, Vileda et al.,
Two years later, the same group reported the synthesis of synthesized a series of lanthanide (Eu, Gd and Tb) bispho-
spherical nanocrystals of chromium terephthalate MIL-101 sphonates using conventional hydrothermal synthesis (180 1C,
MOF.83 In this work, they showed that crystal size increases 3 days), MW-assisted heating (40 1C, 5 seconds) and US-assisted
with increasing irradiation time, ultimately allowing the isolation
of particles with a high surface area.
The MW synthesis of IRMOF-1, IRMOF-2, and IRMOF-3 was
reported by Ni et al. who obtained microcrystals with a relatively
uniform size and identical cubic morphology in less than
2 minutes.84 They showed that the crystal size can be varied
from micrometer to submicrometer by manipulating the
concentration of the starting material. The same synthesis
was conducted by Choi et al. who investigated how the power
level, irradiation time, temperature, solvent concentration and
substrate composition affected the crystallinity and morphology
of MOF-5.85 The microwave irradiation lead to crystals after only
30 min of reaction time while 24 h were necessary with the
conventional method. The optimum microwave conditions lead
to uniform cubic crystals with average size of 20–25 mm and with
a BET surface area of 3008 m2 g1.
MW irradiation is an attractive method to synthesize MOFs
with biomedical applications, such as iron-carboxylate MOFs,
because uniform nanocrystals are easily achievable. For instance, Fig. 4 SEM images of synthesis of MIL-53(Fe). Synthesis at 70 1C with (a)
in 2009, Lin and co-workers described the MW synthesis of ultrasounds for 35 min, (b) microwave for 2 h, and (c) conventional electric
heating for 3 days (d) comparison crystallization curves for the synthesis of
200 nm nanoparticles of iron-MIL-101 MOF and its amino
MIL-53(Fe) in two steps by (a) microwave, (b) microwave and conventional
functionalized version.86 The starting materials were dissolved electric heating, (c) conventional electric heating and microwave and
in DMF and then rapidly heated to 150 1C and held at this (d) conventional electric heating.91 (r Elsevier, reprinted with permission
temperature for 10 minutes. from ref. 80).
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synthesis (room temperature, 5 minutes).95 Under CE heating, be needed and may require a solvent.106 Nevertheless this
microcrystalline materials were obtained which did not possess synthesis approach is the most environmentally friendly process
any significant catalytic activity, whereas the application of MW to produce MOFs, and hence could reduce significantly the cost
and US resulted in nanocrystals that exhibited relatively high of production.107,108
catalytic activity and excellent selectivity to 2-methoxy-2-phenyl- The three different mechanochemical approaches used for
ethanol (100% yield within 48 hours of reaction time). A recent MOF production are Solvent-Free Grinding (SFG) which is the
work by Cao and co-workers showed the gram scale production simplest method and avoids the use of solvent; Liquid-Assisted
of nine isostructural microporous lanthanide MOFs via a micro- Grinding (LAG) which is more versatile, and quicker, as it uses
wave over 5 min.96 The same synthesis but under conventional catalytic amounts of liquid phases which increase the mobility
solvothermal reaction required seven days to produce the same of the reagents; and finally, Ion-and-Liquid Assisted Grinding
materials with a similar yield. Moreover, with the solvothermal (ILAG) which uses a catalytic liquid with traces of salt additives
method only 10 milligrams of quality material could be obtained to accelerate the MOF formation. Using these techniques, the
while MW synthesis yielded up to 2 grams. synthesis for almost all families of MOFs has been demonstrated,
In recent years, zirconium-based MOFs have attracted great and selected studies will be explained in this section.109
attention due to their exceptionally high thermal and chemical A first work by James and co-workers employed the SFG
stability. In 2013, D’Alessandro and co-workers reported the method, milling a dry mixture of copper acetate and isonicotinic
efficient synthesis of MIL-140A, MIL-140B and MIL-140A-NH2 acid (Hina) powder for 10 minutes resulting in the formation of
frameworks using MW irradiation.97 They obtained products copper(II) isonicotinate MOF with acetic acid and water molecules
with purer phase and higher quality in significantly less time occluded in the pores (see Fig. 5a).110 Using the same approach,
than the CE heating method. Recently, a process optimisation the same group performed a screening study, grinding sixty
for the UiO-66 MW assisted synthesis was presented by Taddei different combinations of twelve different divalent metal salts,
and co-workers.98 The optimized synthesis required 15 minutes composed of copper, nickel and zinc together with five different
of pre-mixture of the initial solutions and 15 minutes at 120 1C. carboxylate organic linkers for 15 minutes.111 As a result several
The reaction yield was 83% and no significant negative effects crystalline structures, including two microporous metal–organic
on morphology, crystal size, or defects were found from the use frameworks HKUST-1 and Cu(INA)2 were obtained.
of MW assisted heating in comparison with those synthesized One important advantage of this approach is the possibility
by CE heating. One exciting area that it has been explored with to synthesize MOFs with only water as a by-product allowing the
MW in the last 2 years is the defect engineering of UiO-66. complete elimination of the purification stage. This is achieved
Babarao and co-workers presented an experimental and theoretical by using hydroxides or oxides as the metal source which then in
study showing the correlation between the defect concentration combination with the protons generated from the organic
composition in UiO-66 and their carbon dioxide adsorption ligand forms H2O.
properties.99 They presented a detailed MW-assisted solvothermal Following this strategy, Tanaka and co-workers presented
synthesis protocol to prepare pure phases of high-quality crystal- the mechanical dry conversion of zinc oxide and an imidazole
line UiO-66 frameworks with different defect concentrations. ligand into ZIF-8.112 The process was investigated for reaction times
Highly crystalline UiO-66 octahedral shaped crystals were obtained of 3 to 240 hours, yielding the best BET surface area (1480 m2 g1) at
in a short reaction time of 5 minutes using hydrochloric acid and 96 hours. The decrease of the BET surface area after 96 hours
formic acid as modulators. was due to the formation of amorphous domains during the
2.1.3 Mechanochemical synthesis. Mechanosynthesis is a mechanochemical reaction. The same year, Balema and co-workers
well-known technique in metallurgy and mineral processing reported the preparation of the yttrium based MIL-78 MOF under
but within the last few decades it has expanded rapidly into completely liquid-free conditions and using a metal hydride for
many areas of chemistry such as catalysis, inorganic chemistry the first time as a starting material and forming hydrogen as a
and pharmaceutical synthesis.100–103 The central concept behind by-product.113
this synthesis method is to promote chemical reactions by Very recently, Xu and co-workers reported the synthesis of
milling or grinding solids without any or with only minimal MIL-101(Cr) without the addition of solvent and hydrofluoric
amounts of solvents.104,105 With this approach the conventional acid.114 The chromium salt and the terephthalic acid were ground
solvothermal MOF reactors are substituted by a mortar and pestle for 30 minutes at room temperature and then transferred into an
or in a mechanical process by automated ball mills. In general, autoclave at 220 1C for 4 hours, yielding a material with a BET
the mechanical milling process is higher in energy and ensures surface area of 3517 m2 g1 and with a reduced particle size
the reproducibility between batches. In addition to the solvent- compared to the batch process.
free conditions, this approach leads to a faster and more efficient In 2006, Braga and co-workers demonstrated for the first
synthesis of MOFs obtaining quantitative yields and allows to use time how the addition of small amounts of solvent to the powder
MOF precursors with low solubility such as oxides, hydroxides mixture precursors could effectively improve the crystallisation of
and carbonates. However, the big limitation lies in up-scaling the compounds and accelerate the synthesis.115 They synthesized
mechanosynthesis, it is essentially a batch processing technique the CuCl2(dace) (where dace is the trans-1,4-diaminocyclohexane)
with a relatively low rate of production. Furthermore, it should be one-dimensional coordination polymer by grinding the starting
noted that despite a ‘solvent-free’ synthesis, purification may still materials for 5–10 minutes in the presence of water or DMSO
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Fig. 5 Mechanochemical synthesis of MOFs. (a) Neat grinding, (b) liquid-assisted grinding (c) ion- and liquid-assisted grinding, exploiting the catalytic
effect of nitrates and sulphates (d) twin screw extruder with key parts highlighted. (e) Table of space time yields (STYs) and BET surface area for the
synthesis of MOFs synthesized by extrusion methods (r The Royal Society of Chemistry, reprinted with permission from ref. 106 and 107).
which was then removed by thermal and vacuum treatment. In (see Fig. 5b).119 The acetic acid and H2O by-products occluded
2009, Friščić and Fábián demonstrated the ability to selectively in the pores were removed by thermal treatment and the
and quantitatively build different metal–organic architectures by interpenetrated structure was refined using Rietveld methods.
simply changing the amount and type of solvent using the same In 2015, Prochowicz et al. described the ‘‘SMART’’ (SBU-
starting materials. In this specific work, they presented the based Mechanochemical Approach for pRecursor Transformation)
formation of four coordination polymers and two porous structures strategy for the synthesis of IRMOFs.120 The successful mechano-
by grinding zinc oxide and fumaric acid in the presence of different chemical synthesis was performed by mixing pre-assembled
types of solvents.116 In 2010, Klimakow et al. synthesized the oxo-zinc amidate clusters with terephthalic acid in the presence
well-known HKUST-1 and its benzenetribenzoate-based analogue of microlitres of N,N-diethylformamide (DEF) over 60 minutes.
MOF-14 via the LAG approach. The MOFs were obtained by Additionally, the study showed the importance of the acid–base
grinding the copper acetate monohydrate salt with the corres- relationship between reagents in this type of approach.
ponding organic linkers for 25 minutes. Acetic acid was formed Recent work by Friščić and co-workers presented the synthesis
as a by-product, which blocked the micropores and consequently of UiO-66 and UiO-66-NH2 at gram scale by adding different
resulted in a smaller BET surface area compared to other amounts of N,N-dimethylformamide (DMF) and methanol to the
synthetic approaches.117 James and co-workers showed that by solid mixtures of the reactants as well as exposing the powder
adding small amounts of liquid by-products, generated via the mixture to methanol vapours at 45 1C for 3 days and 1 week
SFG method, before the mechanical process, that the synthesis respectively.121 The best BET surface area obtained for UiO-66
could be accelerated.118 By adding small amounts of acetic acid was 1020 m2 g1 with 75 minutes grinding, and 945 m2 g1 for
into the precursor mixtures, the formation of Cu(INA)2 MOF was UiO-66-NH2 after 90 minutes grinding, both in the presence of
dramatically accelerated, while for HKUST-1, due to the lower methanol, for the materials exposed to methanol vapours.
solubility of the trimesic acid, no improvement was reported. In The third mechanochemical methodology, ILAG, was demon-
2010, the same group studied by X-ray diffraction the structural strated to be highly efficient for the synthesis of pillared-layered
properties of [Zn2(fma)2(bipy)], where fma corresponds to fumaric MOFs. For example, the zinc pillared material based on terephthalic
acid and bipy to 4,4 0 -bipyridine, prepared by mechanosynthesis acid and dabco (1,4-diazabicyclooctane) was synthetised after
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45 minutes reaction by adding catalytic amounts of an alkali soaps and detergents, and many other products.125 More
metal or ammonium nitrate salt into the mixture (Fig. 5c).122 recently in history, SD has extended its use to the encapsulation
Using the same starting materials, but replacing the ammonium and miniaturization of multiple species,126–128 with the idea of
nitrate with sulphates, yielded the same pillared-layered structure protecting them, controlling their release, and increasing their
but on a hexagonal grid. A second example was presented, solubility and dispersability. It has also been employed for
showing the mechanochemical ILAG approach for the room- preparing very homogeneous mixtures of reactants,129,130 a crucial
temperature synthesis of ZIF-8, using zinc oxide as the starting step that has facilitated the fabrication of certain materials.
material and stoichiometric amounts of ammonium salts.123 In Beyond the use of SD in these applications, the local heating
this case the use of salts enabled synthesis with imidazole of micro- and submicrometer droplets that occurs during the
enabling the selective ZIF topology formation by changing the SD process can also be used to conduct chemical reactions.
type of ammonium salt and adjusting the reaction times. Thus far, this concept has mainly been utilized for discovering
Mechanochemistry is a versatile method that allows the and isolating metastable phases of materials that can be only
synthesis of most of the common MOF structures, however so reached thanks to the fast drying conditions of the SD method.131
far all examples described a production at less than one gram scale. In 2013, Maspoch et al. expanded this concept to the synthesis
As an alternative, extrusion techniques have been explored for the of supramolecular materials and, in particular, MOFs.132 The
up-scaling of MOF production under solvent-free conditions. main principle of the process was based on the fast drying
Extrusion is one of the major continuous manufacturing processes of atomized microdroplets of a solution that contains the
used in industries such as food, metallurgy, plastics and phar- MOF precursors (Fig. 6a and b). Thus, the process starts with
maceuticals and has shown very promising results for the synthesis atomization of a solution of the MOF precursors into a spray of
and shaping of MOFs. In 2015, James and co-workers showed microdroplets. This step is accomplished by simultaneously
the synthesis of HKUST-1, ZIF-8 and aluminium fumarate MOF injecting one or more solutions, at a certain rate, (hereafter,
with twin-screw extrusion (TSE) at the gram scale. Fig. 5d shows feed rate) and compressed air or nitrogen gas, at another
the TSE used for the synthesis of MOFs which consists of a feed certain rate (hereafter, flow rate). Thus, each precursor droplet
port where the MOF precursors were introduced into a heatable contacts – and is suspended by – a gas stream heated to a
barrel containing the screw and an exit port which a die can be certain temperature (hereafter, inlet temperature), causing the
attached to shape the final material. HKUST-1 was synthesized solvent to be heated and evaporated and inducing the MOF
by extruding copper hydroxide and trimesic acid in the presence precursors (e.g. metal ions and organic ligands) to react forming
of methanol. The extrudate was stirred in ethanol and dried at
150 1C for 2 hours yielding a N2 BET surface area of 1738 m2 g1.
In the case of ZIF-8 the synthesis was performed by a single screw
extrusion (SSE) where the zinc carbonate and the 2-methylimidazole
ligand were extruded at 200 1C without the addition of any solvent.
In this case, the activation was carried out by stirring the material in
methanol and drying the material at 150 1C yielding a N2 BET
surface area of 1738 m2 g1. A last example was obtained by
introducing a mixture of aluminium sulphate, sodium hydroxide
and fumaric acid into the twin extruder at 150 1C. In this case the
by-product was removed by washing the extrudates with water
and N2 BET surface area obtained was 1010 m2 g1. Extrusion is
an efficient way to produce MOFs solvent free with high with very
promising space-time-yield (STY) (see Fig. 5e). Kilogram scale
production could be achieved by using a large-scale equipment
and paired with a more detailed knowledge and understanding of
the MOF synthesis by this methodology.
2.1.4 Spray-drying synthesis. Spray-drying (SD) process has
been a well-established method in industry for decades. The
basic idea behind this method is the production of dispersed
powder from a liquid or slurry that is rapidly evaporated with a
hot gas. The development of the SD method evolved over a
period from 1870s through early 1900s. SD was first patented in
1872 by Samuel Percy,124 but it was not until the World War II Fig. 6 Spray-drying method for the production of MOFs. (a) Photograph
when it gained importance due to transportation needs. SD was of the spray-dryer while it is used to fabricate HKUST-1. (b) Schematic
illustration of the spray-drying synthesis of MOFs. The MOF precursor
used to reduce the weight of food and other species by removing
solution can be introduced into the spray drier using a: (c) two-fluid
their liquid content (mainly, water). Since then, SD has been nozzle; (d) three-fluid nozzle; (e) T-junction; and (f) continuous flow rector
widely used for the production of dried pharmaceuticals, bone coupled to a two-fluid nozzle. (r Springer Nature and The Royal Society
and tooth amalgams, beverages, flavors, milk and egg products, of Chemistry, adapted with permission from ref. 132 and 134).
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MOF nanoparticles inside each droplet. At this moment, the two-fluid nozzle.132 This two-fluid nozzle allows the simultaneous
newly formed MOF nanoparticles accumulate and merge into injection of this precursor solution at a certain feed rate and
compact or hollow spherical MOF superstructures/beads while compressed air or nitrogen gas at another certain flow rate. In
the solvent is fully evaporated. These MOF superstructures/ general, this method is very useful to synthesize MOFs that are
beads are finally collected inside a collector located at the end built up from mononuclear metal ions or smaller metal clusters
of the spray drier instrument. or secondary building-units (SBUs). An archetypical class of
Table 1 lists all MOFs – together with the optimized conditions MOFs that can be fabricated using this approach is the large
and yields – that have been synthesized using the SD method so family of MOFs constructed from Cu(II) paddlewheel units and
far. Besides the optimization of the synthesis parameters such as polycarboxylate linkers. For example, HKUST-1 (also known as
type of reagents/solvents, feed/flow rates and inlet temperature, a Cu-BTC or Basolitet C300) can be synthesized by spray-drying a
very important aspect that needs to be carefully selected when one solution of Cu(NO3)22.5H2O and trimesic acid (H3BTC) (3 : 2
wants to synthesize a specific MOF by SD is how the precursor molar ratio) in DMF, ethanol and water (1 : 1 : 1) with a feed rate
solution is introduced into the spray drier (Table 2). To date, there of 4.5 mL min1, a flow rate of 336 mL min1 and an inlet
are four major modes for introducing the MOF precursor solution: temperature of 180 1C. They could be obtained as hollow
(i) use of a two-fluid nozzle (Fig. 6c); (ii) use of a three-fluid nozzle spherical MOF superstructures (size: 2.4 0.4 mm) or nano-
(Fig. 6d); (iii) use a T-junction (Fig. 6e); and (iv) use a continuous particles (size: 75 28 nm) (Fig. 7a).
flow coupled to a reactor (Fig. 6f). Second and third routes for introducing the MOF precursors
The use of two-fluid nozzle is the simplest process. It is inside the spray drier instrument are very similar.132 They are
based on the preparation of a homogeneous solution or suspension based on using multi-fluid nozzles, to independently atomize the
that contains all MOF precursors, which is then injected through a solutions containing the MOF precursors, or additional channels,
Table 1 Electrochemical synthesis of MOFs with different routes and conditions
MOF Substrates Solvent Electrolyte BET surface area (m2 g1) Ref.
Anodic deposition
HKUST-1 Copper electrode MeOH — 1820 50
Copper electrode EtOH:H2O MTBS — 57
Copper mesh EtOH:H2O — — 59
Copper electrode EtOH:H2O MTBS 1440 58
Copper electrode EtOH:H2O, organic solvents MTBS — 61
Copper mesh
Copper electrode EtOH, EtOH:H2O MTBS 1309 63
ZIF-8 Zinc electrode AcN:H2O MTBS 1600 58
Zinc electrode DMF:H2O MTBS 1730 65
ZIF-4 Zinc electrode DMF:H2O MTBAMS 75 65
ZIF-64 Cobalt electrode DMF:H2O MTBAMS 1521 65
MIL-53(Al) Aluminium electrode DMF:H2O KCl or NaCl 1200 58
MIL-100(Al) Aluminium electrode EtOH:H2O — 969 58
MIL-100(Fe) Iron electrode EtOH:H2O MTBS — 64
Tb-BTC Terbium foil EtOH:H2O MTBS — 66
Gd-BTC Gadolinium foil EtOH:H2O MTBS — 66
MOF-5 Zinc plate EtOH:H2O NH4F — 67
Zinc plate and titanium plate DMF BMIM 914.7 68 and 69
MOF Substrates Method Ref.
Cathodic deposition
MOF-5 FTO Cathodic 70
UiO-66 Zirconium foil Anodic and cathodic 76
MOF-5 FTO Cathodic 71
MOF-5/(Et2NH2)2Zn3(BDC)4 FTO Cathodic 72
Others
ZIF-8 Zinc wire BE 77
UiO-66 FTO Electrophoretic deposition 74
HKUST-1 FTO Electrophoretic deposition 73
Glass Galvanic displacement 75
Porous stainless steel Electrophoretic deposition 73
Cu bead BE 77
MIL-53 FTO Electrophoretic deposition 74
NU-1000 FTO Electrophoretic deposition 74
Abbreviations: MTBS, methyltributylammonium methyl sulfate; MTBAMS, methyltributylammonium methyl sulphate; BMIM, 1-butyl-3-
methylimidazole; FTO, fluorine doped tin oxide; BE, bipolar electrochemistry.
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Table 2 MOFs synthesized by spray-dryer with different introducing modes and conditions
MOF Metal salt/ligand/solvent Feed rate (mL min1) Inlet T (1C) Yield (%) BET (m2 g1) Ref.
Two fluid nozzle
HKUST-1 Cu(NO3)22.5H2O/BTC/DMF:EtOH:H2O 4.5 180 70 1260 132
Cu-BDC Cu(NO3)22.5H2O/BDC/DMF 4.5 180 70 543 132
NOTT-100 Cu(NO3)22.5H2O/BPTC/DMF:H2O 4.5 180 54 1140 132
MOF-14 Cu(NO3)22.5H2O/BTB/DMF:EtOH:H2O 4.5 180 30 — 132
Zn-MOF-74 Zn(NO3)26H2O/DHBDC/DMF:H2O 4.5 180 50 — 132
Mg-MOF-74 Mg(NO3)26H2O/DHBDC/DMF:EtOH:H2O 4.5 180 35 — 132
Ni-MOF-74 Ni(NO3)26H2O/DHBDC/DMF:EtOH:H2O 4.5 180 40 — 132
MIL-88B FeCl3/2-amino-BDC/DMF:MeOH:H2O 4.5 180 27 — 132
Three fluid nozzle

ZIF-8 Zinc acetate/MiM/H2O 4.5 180 10 941 132
Cu-PB Cu(NO3)2/K3Co(CN)6/H2O 4.5 180 20 617 132
SIFSIX-3-Co CoSiF6/pyrazine/MeOH 2.4 85 44 136
SIFSIX-3-Ni NiSiF6/pyrazine/MeOH 2.4 85 — 136
SIFSIX-3-Cu CuSiF6H2O/pyrazine/MeOH 2.4 85 55 136
SIFSIX-3-Zn ZnSiF6xH2O/pyrazine/MeOH 2.4 85 57 136

SIFSIX-1-Zn ZnSiF6xH2O/4,4 0 -bipyridine/MeOH 2.4 85 40 1300 136
TIFSIX-1-Cu Cu(NO3)22.5H2O/4,4 0 -bipyridine/MeOH 2.4 130 79 1650 136
T junction
MIL-88A FeCl3/fumaric acid/DMF:MeOH:H2O 4.5 180 40 — 132
MOF-5 Zinc acetate/BDC/DMF 4.5 180 60 1215 132
IRMOF-3 Zinc acetate/2-amino-BDC/DMF 4.5 180 70 — 132
MPM-1-TIFSIX TiF6(NH4)2/Cu(NO3)22.5H2O/H2O:MeCN 2.4 150 74 805 136
MOF Metal salt/ligand/solvent Feed rate (mL min1) T1 (1C) Inlet T (1C) Yield (%) BET (m2 g1) Ref.
Continuous flow
UiO-66 ZrCl4/BDC/DMF:H2O 2.4 115 180 70 1106 134
UiO-66-NH2 ZrCl4/2-NH2-BDC/DMFH2O 2.4 115 180 67 752 134
UiO-66-NH2 ZrOCl2/2-amino-BDC/DMF:H2O 2.4 90 180 83 1150 211
UiO-66-NO2 ZrCl4/2-nitro-BDC/acetic acid:H2O 2.4 115 180 62 679 134
UiO-66-Br ZrCl4/2-bromo-BDC/DMF:H2O 2.4 115 180 68 527 134
UiO-66-(OH)2 ZrCl4/2,5-dihydroxy-BDC/DMF:H2O 2.4 115 180 81 401 134
UiO-66-acetamido ZrCl4/2,5-dihydroxy-BDC/DMF:H2O 2.4 115 180 51 586 134
UiO-66-1,4-NDC ZrCl4/1,4-NDC/DMF:H2O 2.4 115 180 45 431 134
UiO-66-2,6-NDC ZrCl4/2,6-NDC/DMF:H2O 2.4 115 180 49 557 134
Fe-BTC/MIL-100 Fe(NO3)39H2O/BTC/DMF 2.4 135 180 78 1039 134
Ni8(OH)4(H2O)2(L)6 Ni(CH3COO)24H2O/ 2.4 100 180 60 377 134
1H-pyrazole-4-carboxylic acid/DMF:H2O
Abbreviations: BTC, trimesic acid; BDC, 1,4-benzenedicarboxylic acid; BPTC, biphenyl-3,3 0 ,5,5 0 -tetracarboxylic acid; BTB, 1,3,5-tris(4-carboxyphenyl)-
benzene; DHBDC, 2,5-dihydroxyterephthalic acid; DMF, dimethylformamide; EtOH, ethanol; MeOH, methanol; MiM, 2-methyl imidazole; NDC,
naphthalenedicarboxylic acid.
to independently inject them. Both approaches enable mixing promote the SBU formation and nucleation. Here, the residence
of the precursor solutions just before they are heated into the time of the precursor solution in the coil flow reactor is
atomized droplets. In the first approach, mixing occurs inside controlled by the rate of the pump (the feed rate). Since the
the drying chamber, thanks to the coalescence of the atomized outlet flow of the reactor is connected directly to the nozzle of
droplets, whereas in the second one, mixing is done through a the spray-dryer, the pre-heated solution is automatically injected
connector inserted before the two-fluid nozzle. Using either into the spray-drier at the same feed rate. The solution is then
variation decreases the probability that unwanted species or atomised using a two-fluid nozzle, and is dried at a certain inlet
micrometre-sized MOFs will form in the precursor solution temperature and flow rate, such that the MOF growth is confined
before it is spray-dried. They also enable the use of reagents to the atomised microdroplets.
(e.g. bases) to accelerate MOF formation, thus increasing yields In most of the cases, this last continuous process enables
and purities and enabling the synthesis of new hollow MOF the collection of dried MOFs shaped in the form of compact
superstructures and related nanocrystals. To date, both approaches micrometre superstructures/beads instead of the hollow ones
have allowed the synthesis of several MOFs, including MIL-88A,132 usually obtained in the first three strategies. This difference is
ZIF-8132,133 and Fe-BTC/MIL-100133 (Fig. 7b and c). attributed to the formation, inside the reactor, of a suspension
In the last approach, the MOF precursor solution is passed containing a primary nucleus. In a general spray-drying process,
through a continuous-flow reactor just before the entrance of the the atomised droplets are exposed to hot air, the solvent evaporates
spray dryer.134 This process begins by injecting the precursor and consequently, the droplet surface shrinks. During this process,
solution into a continuous coil flow reactor encased in a thermo- hollow superstructures are formed when there is a non-linear
static oil tank, where it is heated at a certain temperature (T1) to change in precursor concentration at the droplet: specifically, it
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modify MOFs;135,136 the synthesis of multivariate or multi-

metallic MOFs;132,137 and the mixture of MOFs with other
materials to make composites.132,138 With this aim, the use of
SD has been extended to the synthesis of porous materials that
are not based on coordination bonds but on hydrogen bonds.136
For instance, MPM-1-TIFSIX, a porous material based on the
hydrogen-bonded assembly of [Cu2(ade)4(TiF6)2] (ade = adenine)
paddlewheels (Fig. 8a), was synthesized by spray-drying an
aqueous solution of Cu(NO3)22.5(H2O) and TiF6(NH4)2 along
with a solution of adenine in water/acetonitrile mixture using a
2-fluid nozzle and an inlet temperature of 150 1C. Moreover, SD
was also very recently found to be a fast method to post-
synthetically modify MOFs using conventional covalent chemistry
(Fig. 8b).135 To perform this modification, a suspension of pre-
synthesized MOF crystals are spray-dried together with the
desired reagent. With this simple method, two MOFs, the amine-
terminated UiO-66-NH2 and the aldehyde-terminated ZIF-90, were
rapidly post-synthetically modified with aldehydes and amines,
Fig. 7 SEM and TEM images of several MOFs synthesized by spray-drying. respectively, using the well-known Schiff-base condensation
(a) Hollow spherical superstructures of HKUST-1 synthesized using a two-fluid
nozzle. Inset shows a TEM image of a single HKUST-1 nanoparticle. (b) Spherical
reaction and achieving conversion efficiencies up to 20% and
superstructures of MIL-88A synthesized using a T-junction. Inset shows a SEM 42%, respectively. Moreover, it was demonstrated that the
image of MIL-88A particles. (c) Superstructures of ZIF-8 synthesized using a aldehyde groups of ZIF-90 could be cross-linked using a diamine
three-fluid nozzle. Inset shows a TEM image of a single ZIF-8 nanoparticle. (d) molecule with a conversion efficiency of 70%.
Compact superstructures/beads of UiO-66 synthesized using a continuous Another advantage of SD as a synthetic method in the MOF
flow reactor coupled to a two-fluid nozzle. Inset shows a SEM image of a single
bead. Scale bars: 10 mm (c), 5 mm (a and d), 2 mm (b, inset d), 200 nm (inset b),
field is the possibility to synthesize multi-metallic and multi-
and 50 nm (inset a and c). (r Springer Nature and The Royal Society of variate MOFs. From an experimental point of view, the synthesis
Chemistry, reprinted with permission from ref. 132 and 134). of these multi-component MOFs does not require technological
changes. Its main principle is based on mixing different metal
ions or organic linkers in the MOF precursor solution that is
causes the formation of an impermeable shell and the generation spray-dried. With this approach, Wang et al. showed the synthesis
of gas at the core. However, in this latter case, uniform precursor of lanthanide-based MOF nanoparticles in which the ratio
concentration and droplet temperature are reached, owing to the of Tb(III)/Eu(III) was controlled (Fig. 8c).137 They proved that
presence of the uniformly-distributed nuclei in the droplet. The the resulting MOF nanoparticles could be used as promising
rate at which the nucleus can be brought to the surface by nanothermometers with high detection sensibilities, spatial
diffusion is lower than the rate at which the nucleus can grow resolutions and short acquisition times. Similarly, multi-variate
during the drying–evaporation process. This difference favours a UiO-66s were synthesized by mixing different ratios of two
linear change in precursor concentration and temperature at (benzenedicarboxylic acid and 2-bromobenzenedicarboxylic acid)
the droplet, and consequently, drives the formation of dense or three (benzenedicarboxylic acid, 2-aminobenzenedicarboxylic
superstructures. acid and 2-bromobenzenedicarboxylic acid) organic linkers in the
The main advantage of this last SD approach is that it allows MOF precursor solution (Fig. 8d).134 The resulting UiO-66 materials
the synthesis of MOFs assembled from high-nuclearity SBUs. showed tunable pore surface area. For example, the surface area
Indeed, numerous members of the family of UiO-66 (e.g. UiO-66- decreased with increasing equivalents of 2-bromobenzene-
NH2, UiO-66-Br, etc.) as well as Fe-BTC/MIL-100 and [Ni8(OH)4- dicarboxylic acid: 818 m2 g1 for 0.6; 678 m2 g1 for 1.3; and
(H2O)2(L)6]n (where L = 1H-pyrazole-4-carboxylic acid) series 570 m2 g1 for 2.3.
were synthesized using the resulting spray-drying continuous Finally, SD is also a very simple and fast method to produce
flow-assisted synthesis. For example, UiO-66 was synthesized MOF-based composites. As above, these MOF-based composites
using ZrCl4 and BDC as reagents, DMF and H2O as solvents, can be created by just mixing other materials – pre-synthesized
an initial concentration of 0.1 M for both reagents, a final molar or their precursors for in situ synthesis – in the MOF precursor
ratio (Zr/BDC/H2O/DMF) of 1 : 1 : 30 : 135, a T1 of 115 1C; an inlet solution. With this basic idea, Maspoch et al. demonstrated
temperature of 180 1C, and a flow rate of 336 mL min1. Under that different substances such as magnetic inorganic nano-
these optimized conditions, in which the amount of water, the particles (Fig. 8e),132 inorganic salts (NaCl, CaCl2 and LiCl)132,139
feed rate and the coil temperature were found to be very important, (Fig. 8f) and fluorescent molecules132 can be combined with
UiO-66 was fabricated with a space-time yield of 19.6 kg m3 day1 MOFs, thereby creating different types of composite materials
(Fig. 7d). that combine the intrinsic properties of MOFs and these other
Lastly, the innovations of using SD in the MOF field have materials. Finally, the same authors showed that SD method can
been centered on the use of new chemistries to build and/or be also used to combine MOFs with organic polymers.138 In this
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Fig. 8 Spray-drying method for building and/or modifying MOFs. (a) Crystal structure and SEM image of MPM-1-TIFSIX. Scale bar: 20 mm and inset:
5 mm. (b) Schematic illustration of the post-synthetic modification of MOFs using spray-drying and 13C MAS-NMR spectra that confirms the formation of
the CHQN imine group. (c) SEM image of a multi-metallic lanthanide-based MOF and excitation spectra of it. Scale bar: 10 mm and inset: 2 mm. (d) SEM
image of a multi-variate UiO-66 and NMR spectra confirming that both BDC and BDC-Br are forming the UiO-66 structure. Scale bar: 10 mm.
(e) HKUST-1 coupled with magnetic nanoparticles. Scale bar: 200 nm. (f) SEM image of UiO-66 coupled with CaCl2 and XRD pattern of the composite
material showing the presence of both components. Scale bar: 20 mm. (r Springer Nature and The Royal Society of Chemistry, reprinted with permission
from ref. 132, 134–137 and 139).
specific case, pre-synthesized HKUST-1 nanocrystals were encapsu- researchers have started to use flow chemistry to synthesize MOFs
lated into polystyrene spheres to improve the hydrolytic stability of (Table 3). In the last year, numerous works have been reported in
HKUST-1. the literature and in this review we will classify such reports
2.1.5 Flow chemistry. Flow chemistry is a continuous pro- into three different categories: (a) microfluidic reactors (MR),
cessing technology used in the pharma and agrochemical sectors which manipulate the reagents in channels that are geometrically
over the last two decades. Recently, its application to the synthesis of constrained at the microscale; (b) plug flow reactors (PFR) where
functional nanomaterials such as inorganic nanoparticles, quantum the reagents are pumped through a tube or pipe and consumed
dots, metal oxides and MOFs has shown great promise. Contrary to as they flow down the length of the reactor and (c) stirred tank
batch reactions, in a flow chemistry setup, the chemical reactions reactors (CSTR) where the MOF precursor are introduced into a
occur in a continuously flowing stream in a tube or pipe rather than tank reactor while products are continuously removed. Table 3
in a reaction vessel. This results in several main advantages: (a) the lists all MOFs – together with the optimized conditions and
surface area-to-volume ratio for a reaction mixture in a flow reactor space-time-yields – that have been synthesized using the flow
is much higher than in a batch-type reactor giving inherent chemistry method so far.
improvements to heat and mass transfer leading to a much rapid In 2011, Ameloot and co-workers were first to show that
syntheses; (b) flow chemistry allows for precise control over the microfluidics could be used for the synthesis of metal–organic
reaction parameters which facilitates the synthesis optimization and materials.140 They synthesized metal–organic crystals in a micro-
the reproducibility between batches; (c) harsh reaction conditions scale reactor, in which the reagent phases were injected into an
can be safely reached due to excellent transport intensification immiscible carrier fluid, causing the spontaneous formation
properties of the reactors; (d) typically less solvent is used and the of droplets where the reaction occurs (Fig. 9b). In this case,
energy consumption is lower; (e) downstream processes and quality the immiscibility of the water and oil phases was exploited as
control methods can be easily integrated in the flow processes and a template for the controlled formation of hollow metal–
(f) these type of reactors are readily scaled-up. Flow chemistry is thus organic copper trimesate HKUST-1 microcapsules. The authors
a cost-effective method that follows the green principle and satisfies described the crystallisation process as a dynamic on-going
the requirements for industrial production. Not surprisingly, several process of nucleation and crystal growth that resulted in the
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Table 3 MOFs synthesized by flow chemistry with different approaches and conditions
Method MOF Residence time Temperature (1C) STY (kg m3 day1) SA BET (m2 g1)
MF HKUST-1140 — RT — 620
HKUST-1141 1 min 90 5.8 1105
MOF-5141 3 min 120 — 3185
IRMOF-3141 3 min 120 — 2428
UiO-66141 15 min 140 — 1509
MIL-88b137 4 min 95 — —
ZIF-8143 15 s RT 210 000 1770
Ce-BDC142 30 s 230 — —
UiO-66144 0.44–2.2 min 120 — 922–1206
PFR HKUST-1149 1.2 min 85 4533 1805

UiO-66149 10 min 130 1186 672
NOTT-400149 15 min 85 1078 741
Al-Fum150 1 min 65 97 159 1054
HKUST-1148 5 min 60 — 1673
MIL-53(Al)147 20 min 250 1021 919
MIL-53(Al)147
20 min 250 1300 1010

STA-12(Cd)151 5–20 min 70 — 134
ZIF-8146 o5 s 100 11 625 1806
ZIF-8146 o5 s 100 — 1780
CAU-13151 20 min 130 3049 401
CPO-27145 o5 s 300 1501 1030
HKUST-1147 20 min 250 730 1554
HKUST-1145 o5 s 300 4399 1950
UiO-66151 45 min 120 428 1263
STA-12151 20 min 70 428 134
HKUST-1153 1 min 360 W 64 800 1550
MIL-53(Al)153 4 min 200 W 3618 1376
UiO-66153 7 min 200 W 7204 1052
MOF-74(Ni)152 o1 s 150 2160 840
CSTR UiO-66154 8–40 h 100–120 — 810

MOF-5155 5h 140 1000 2302
formation of crystalline MOF membranes with a uniform wall In addition, D’Arras and co-workers demonstrated the possibility
thickness. of synthesizing new structures using microsystems.142 They reported
Two years later, Faustini et al. reported the solvothermal and the structure of a new cerium(III)–terephthalate MOF which was
hydrothermal synthesis of MOFs and MOF-composite super- synthesized flow-type reactor at high temperature and pressure with
structures using oil microdroplets as a reactors.141 Four a very short residence time.
representative MOF structures, copper trimesate HKUST-1, zinc The latest MR studies were reported by Polyzoidis et al. and
terephthalate MOF-5, zinc aminoterephthalate IRMOF-3 and Tai et al., where they synthesized ZIF-8 and UiO-66 nano-
zirconium terephthalate UiO-66, were synthesised, yielding particles respectively in a PFA (perfluoroalkoxy) microreactor
substantially faster kinetics in comparison to the conventional showing that by varying the residence time and the molar ratio
batch processes (see Fig. 9a). In addition, they reported the of the reactants. They were able to modify the size and shape of the
possibility of creating MOF heterostructures using imidazolate final crystals from a few nanometres to several micrometres.143,144
frameworks (ZIFs) in a two-step process. Firstly, the iron oxide These two last examples demonstrate that microfluidic systems are
precursor solution and the oil phase were injected and reacted ideal for reaction optimisation and screening experiments within
in a microreactor at 80 1C for 2 minutes. Then, the resulting the laboratory. However, in order to synthesize large quantities of
iron oxide particles were transported downstream to a second MOFs, it is better to use reactors with larger channel dimensions,
microreactor, where they merged and reacted with a mixture of as these are more suitable for large volumetric throughput.
ZIF-8 precursor (zinc nitrate and 2-methylimidazolate in methanol, Moving to the PFR reactors the first work was reported in
and polystyrenesulphonate). This lead to the creation of core–shell 2012 by Gimeno-Fabre et al. showed the synthesis of HKUST-1
Fe3O4@ZIF-8 composite superstructures. and Ni-CPO-27 in a counter current mixing reactor where the
The same year, Coronas and co-workers demonstrated the MOF precursors were mixed with a preheated supercritical water
feasibility of the droplet-based microfluidic approach for the stream at high pressures.145 The high temperatures were used
crystallisation of the iron fumarate MIL-88B MOF. In this study, they in order to increase the rate of crystal growth, with a limitation
confirmed that the size of the resulting crystals was dependent of in that heating beyond 300 1C could lead to the formation of
the temperature and residence time. They observed a continuous metal oxides as a waste-product. Three years later, the same
increase in particle size with average sizes increasing from 90 to reactor was used to demonstrate the large scale production
900 nm with higher residence times and/or higher temperatures. of ZIF-8 and the control of the size and shape of the crystals
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In 2013 Chang et al. reported the proof-of-concept mesoscale

flow production of HKUST-1 using 5 minutes as a residence
time and with a surface area of 1673 m2 g1.148 The particle size
of the MOF could be adjusted by changing the relative ratios of
the solvents and reaction temperatures from 150 nm to 4 mm.
To demonstrate the versatility and efficacy of flow reactors to
produce MOFs, Rubio-Martinez and co-workers used a PFA
reactor to synthesize the copper trimesate HKUST-1, the zirconium
terephthalate UiO-66 and the scandium biphenyl-tetracarboxylate
NOTT-400, all with different reaction requirements (see Fig. 9).149
The materials were obtained in 5, 10 and 15 minutes, respectively,
without loss in yield or product quality. It was demonstrated that
the results could be up-scaled 30-fold using a bench-top reactor,
allowing a production rate greater than a kilogram per day and
a STY of 4533 kg m3 day1 using a bench-top reactor. The
successful up-scaling of this process was demonstrated in a

second publication where the production of the aluminium
fumarate MOF was proved in 4 different stainless-steel tubular
flow reactors: a 10 mL coil tubing at laboratory scale, two
intermediate stages with 107 mL and 374 mL reactor volume, and
a pilot-scale 1.394 L reactor, delivering unprecedented production
rates and STYs (97 159 kg m3 day1) while maintaining the product
quality.150 To our best knowledge, this is the highest reported value
of STY for a MOF produced by continuous methods. Additionally,
the reactor design used in this work demonstrated the possibility to
readily translate reaction parameters from the laboratory scale to
pilot scale without any re-optimization of the reaction conditions,
while maintaining the STY values within the same range.
The last work using PFR comes from Stock and co-workers
who presented the synthesis of UiO-66, CAU-13 and STA-12 – a
new cadmium phosphonate network using a 16 mL PTFE reactor
yielding a STY of 428 kg m3 day1 and 3049 kg m3 for UiO-66
and CAU-13, respectively.151 One year later, the same was group
reported the water-based synthesis the zirconium fumarate and
UiO-66-NH2 starting from a slurry of the starting solutions.
In a slightly different reactor design, two recent works
Fig. 9 Flow chemistry methods for the production of MOFs. (a) Schematic reported the combination of microwave assisted heating with
representation of a continuous flow microfluidic device for producing MOF a PFR system. The first study from 2015 by Albuquerque et al.
crystals (top). Optical and SEM images of HKUST-1 crystals obtained via
the microfluidic approach at different residences time. (b) Schematic
reported on a system where the microwave reactor was attached
representation showing the continuous flow synthesis of HKUST-1, UiO-66 to the flow reactor in order to accelerate the nucleation of the
and NOTT-400 of MOFs. (c) Reaction profile of the solvothermal synthesis of MOFs and to improve the reproducibility of the synthesis.152
MOF-5 crystals with its corresponding X-ray pattern diffraction and BET The MOF precursors of MOF-74(Ni) were introduced first into
surface area value. (r The American Chemical Society, Springer Nature and the nucleation zone that consisted of a microwave reactor and
Elsevier, reprinted with permission from ref. 141, 149 and 155).
consequently the material was introduced into a PFA coil for
8 min to growth the final crystals. As a result, they obtained a
by adding ammonium hydroxide or trimethylamine in the better crystallinity in a shorter reaction time and achieved a
reaction mixture.146 The STY obtained in this process was STY of 2160 kg m3 day1. The second work by Taddei et al.
11 625 kg m3 day1 and with a surface area of 1800 m2 g1. presented the synthesis of UiO-66, HKUST-1 and MIL-53(Al) in a
Retaining the use of supercritical water and an ethanol stream, 6.2 and 53 mL PTFE flow reactors heated by microwave.153 The
Bayliss et al. developed a system to produce MIL-53(Al) and materials were obtained in 7, 1 and 4 minutes of residence
HKUST-1 under continuous flow conditions obtaining a STY of time, while maintaining the product quality and resulting
1300 kg m3 day1 and 730 kg m3 day1, respectively.147 These in high STY of 7204 kg m3 day1, 64 800 kg m3 day1 and
last two methods produced high quality materials with high 3618 kg m3 day1 for UiO-66, HKUST-1 and MIL-53(Al)
STY, however high temperatures and pressures were still respectively.
required, which increase the overall cost of the process and The use of stirred CSTR was showcased by two groups,
could limit the practicality of the technique at industrial scale. synthesizing NH2-UiO-66 and MOF-5. The first work in 2013
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by Schoenecker and co-workers who synthesized the amine- Once the MOF slurry has been cleaned of the excess linkers
functionalised UiO-66 in DMF by convention heating.154 In this and by-products, the activation stage is the next step of the
system the MOF precursors were pumped into a pre-mixing tank process in order to obtain the highest porosity and BET surface
over 15 min and then introduced into a 2 litre flow crystallisation area of the framework. Several strategies exist to remove the
reactor over 8 to 40 hours during which time small aliquots of the unreacted and solvent molecules trapped in the pores of the
intermediate product were collected at different times to bulk MOFs without collapsing the framework.157 The most common
reaction kinetics. The product obtained had good crystallinity but procedure is a simple heating of the MOF to certain temperature
the BET surface area and the yield were below the values reported under vacuum. Each MOF has its optimal protocol in order to
in batch. A later study by McKinstry et al. presented the synthesis obtain the highest surface area but generally the temperature
of MOF-5 in a CSTR at atmospheric pressure obtaining the desired should be between the boiling point of the solvent and the
quality and with a STY of 1000 kg m3 day1 (see Fig. 9c).155 decomposition temperature of the structure. However, in most
cases this strategy leads to a lower surface area, or to a collapse of
the structure due to the high surface tension and capillary forces
3. Downstream processes imposed on the structure by the liquid-gas phase transition of the
trapped solvent molecules. An alternative strategy is to exchange
After any MOF synthesis, careful processing is required to obtain the solvent used for the synthesis with one that has a lower-
the final functional material. Directly after the synthesis, the boiling point such as methanol, chloroform or acetone prior to
product slurry needs to be washed with the reaction solvent to heating the sample under vacuum. This strategy is laborious as
remove any unreacted and by-products, e.g. using a centrifuge or generally most MOFs require soaking for a long period of time to
a Buchner filter. Subsequently, an activation process is required ensure that the new solvent infiltrates. For example, in the case of
to remove guest molecules, trapped within the framework, to MOF-74 and UiO-66 both MOFs require a soaking in daily
obtain the expected surface area of the structure. Depending on refreshed methanol for 3 and 7 days respectively to ensure the
the MOF structure, these two stages can be the most time- complete removal of DMF (solvent used for the synthesis and
limiting stages of the process and become hugely significant in washing stage) from the pores.36,158 Some frameworks, such as
the large-scale production. The last stages of the process consist ZIF-8 and MIL-53(Al) require a solvent exchange process with
in drying and shaping the MOFs as well as a heat activation step methanol with an additional thermal treatment, 300 1C for 2 hours
before testing. Fig. 10 shows a diagram of the typical down- and 330 1C for 72 hours respectively to obtain the BET surface
stream processes for the synthesis of a MOF. areas of 1630 m2 g1 and 1590 m2 g1, respectively.31,159
Despite promising advances in MOF synthesis, there are still An attractive substitute for the solvent exchange method is
challenges remaining related to the downstream processing. the use of supercritical CO2. This relatively new strategy consists
On the laboratory scale these processes are well established and of exchanging the synthetic solvent for a one that is miscible with
sufficient to obtain milligram amounts of quality materials. liquid CO2 such as ethanol or methanol and then subsequently
However, these conventional downstream methods are not exchanging this second one for liquid CO2 at high pressure and
well-suited to high production rates. The first stage, the washing temperature for several hours. The difference here is that the CO2
and separation of the small crystals from the mother liquid still supercritical phase eliminates surface tension and capillary forces
is a major obstacle for the large scale production MOFs. There making this activation method much milder than the conventional
are many well established types of equipment for solid–liquid and solvent exchange methods. There are several MOFs that have
separation such as centrifuges, cyclones, settling chambers, been effectively activated with this strategy. For example, MOF-200
classifiers or filters, in addition to the direct evaporation of and MOF-210, where a simple solvent exchange followed by pore
the mother liquor. However, the small size of the MOF particles, evacuation under vacuum was not effective, were successful acti-
their low concentration in the solvent, as well as their density vated, without losing the porosity, by a full solvent exchange with
approaching that of the solvent (due to the high porosity), liquid CO2.4 The surface areas obtained were 4530 and 6240 m2 g1,
makes separation via most conventional methods inefficient respectively. Another example is the supercritical CO2 activation of
or expensive at an industrial scale.156 bio-MOF-100 were the DMF solvated samples were soaked in
Fig. 10 Continuous MOF process. Schematic representation of the different stages of the continuous process for MOFs production: synthesis, washing,
activation, drying and shaping.
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ethanol for 48 hours, and a an exchange/activation with CO2 handled and can potentially contaminate pipes during charge/
liquid over a period of 8 hours yielded a BET surface area of discharge cycles. For other applications such as functional
4300 m2 g1.160 In a variant of this method the sample is placed textiles,164 alternative shaping and/or integration methods that
in a column and the supercritical CO2 flows through the sample process MOFs into paper sheets,165 fibers,166 membranes,167,168
instead of using static CO2 exchange. This method was presented foams169 or coatings170 are also needed (Fig. 11).
by Koh and co-workers who activated UMCM-9 microporous Considering the potential adsorption-related applications of
coordination polymers via supercritical CO2 flow activation MOFs, most of the efforts done in shaping MOFs have been
yielding a surface area BET of 4970 m2 g1.161 dedicated to their densification. The objective of densification
Later novelties on the activation have been based on freeze- is to pack the maximum amount of an active MOF on a certain
drying activation techniques which uses thermal cycling and volume without losing its integrity and adsorption capacity.
the vacuum sublimation of solvents (benzene and cyclohexane) Dailly et al. calculated that doubling the density of HKUST-1
at low temperatures to avoid the impact of capillary forces on powder would result in an adsorbent with performances comparable
porous structures in order to control the stability of frameworks of those of the state-of-the-art carbons at intermediate pressures
and improve its porosity.162 Recently Rubio-Martinez et al. (30–100 bars).171 However, despite the high industrial importance
presented for the first time the use of megasonics as an of shaping MOF powders, the interest of academic research
alternative strategy for the simultaneous separation and activa- groups to face this problematic is quite recent. In fact, the
tion of MOF crystals.163 Its operating principle is based on the structuration of MOFs into shaped bodies was initiated by some
application of high frequency ultrasound to the MOF solution, companies (mainly, BASF), which tend to keep these shaping
leading to the separation of the solid MOF particles from the processes as in-house know-how or are only disseminated in
solvent. Additionally, the megasonic treatment leads to an activation patents. In this context, BASF published the first patent application
by the simultaneous removal of occluded reagents from the MOF concerning ‘‘shaped bodies containing metal–organic frame-
crystals. This one-step process showed an improvement of up to works’’ in 2002. This patent was centered in the fabrication of
47% the surface area of the final product compared to conventional MOF-2 and MOF-5 pellets using an eccentric press. In this
methods. The method removes one stage from the downstream process, both MOFs were mixed with graphite that acts as a
processing and is readily scalable and thus capable of producing binder improving their mechanical strength.172
commercially usable product at a large scale. Pelletization under pressure is probably the most common
Shaping of MOF powders produced in any of the fabrication method used for densifying MOFs. In this process, a fine
methods explained above is also mandatory for using them in powder is pressed at a certain pressure to give pellets that
real industrial applications. For instance, extruded or compact can be crushed or fractionized by sieving. In some cases, before
MOFs in the form of beads, pellets and monolithic bodies are MOF powder is pressed, it can be blended with a binder to
required if MOFs want to be used for gas separation and storage improve the cohesion between crystals and their mechanical
applications. In methane storage (e.g. Adsorbed Natural Gas or strength. There are however two factors of this method that
ANG), for example, it is of utmost importance to fill the storage tend to affect the final adsorption properties of the pellet
tanks with the largest amount of adsorbent; a condition that shaped MOFs. From one side, the pressure applied can crush
can only be achieved if MOF powders are densely packed. the structure of the MOF due to its low mechanical stability.
Furthermore, powdered MOFs are usually more difficult to be From the other side, the use of binders can dilute the porous
Fig. 11 Examples of shaped MOFs. (a) Functional textiles; (b) paper sheets; (c) pellets; (d) extruded monolith; (e) fibers; (f) membrane; (g) foams; and (h)
granules. (r Nature Publishing group, American Chemical Society, Royal Society of Chemistry, Elsevier with permission from ref. 163–165, 167, 180 and 184).
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powder and/or cause pore blockage, resulting in a reduced it at 100 MPa, whereas its porous character totally disappears at
performance per unit mass (or volume) of the adsorbent. 1 GPa.176 In the case of ZIF-8, the BET surface area was well
As shown in Table 4, the influence of the pressure applied preserved until a pressure of 700 MPa. Above this pressure,
during pelletization of MOF powders was studied in some different reports revealed some discrepancies. While Bazer-
representative MOFs. However, systematic studies that correlate Bachi et al. observed a loss lower than 20% of its BET surface
the pelletization conditions with the resulting adsorption properties area,174 Chapman et al. observed a loss of 50% at pressures above
of MOFs are very limited, and some discrepancies can be found. 1 GPa.177 This difference can be attributed to non-reported para-
A general tendency when compressed pellets are processed is a meters, such as the pressure increase rate and the dwell time,
decrease of the BET surface area and porosity of MOFs. This is which can dramatically influence the integrity of the final pellet.
specially the case for HKUST-1 that is mechanically fragile. For Binders are sometimes utilized during this pelletization
HKUST-1, it has been described that a significant loss of its BET process. As state above, they basically serve to improve the
surface area occurs at moderate pressures. Ahn et al. reported a cohesion between MOF crystals and their mechanical stability.
loss of 50% of its BET surface area when the applied pressure Some tested binders include graphite,178 polyvinyl alcohol
was around 10 MPa,173 whereas Bazer-Bachi et al.174 and Peterson (PVA)179 and cellulose ester.174 To our knowledge, however,
et al.175 found a similar decrease when pressures of 80 MPa and there is no a systematic, rational study on the influence of the
70 MPa were applied, respectively. Other MOFs have shown better nature and concentration of these binders on the BET surface
mechanical resistance. For example, UiO-66 and analogues, area and general properties of MOFs during their pelletization.
which are known for their high mechanical and thermal stability The presence of binders is also necessary in other shaping
owing to their 12-fold connected clusters in the three spatial processes, including foaming, extrusion, granulation and cake
directions, were shown better stability during the compression crushing. In all these procedures, MOF powders are initially
process. Here, Peterson et al. observed a loss lower than 10% of dispersed in a solvent/binder mixture. The choice of the binder
the BET surface area of UiO-66 when it was pelletized under a gives a certain texture and property to the mixture, which is then
pressure of 70 MPa.175 Dietzel et al. also reported the total manipulated in different ways to obtain the desired MOF shapes.
conservation of the BET surface area of CPO-27 after tableting For example, in the extrusion process, the MOF solvent/binder
Table 4 Examples of shaped MOFs using pelletization, foaming and extrusion methods
MOF Pressure Binder Property Ref.

Pellet
HKUST-1 — Alox C and graphite Very high adsorption capacity for CO2 178
70 and 700 MPa Without binder 50% decrease of the BET surface area (after 700 MPa) 175
Maintained ammonia removal capacity
0.24–40 MPa Cellulose ester, K15M 76% decrease of the BET surface area (after 40 MPa) 174
3–35 MPa Without binder 50% decrease of the BET surface area (after 10 MPa) 173
MIL-53(Al) 1–8 bar Polyvinyl alcohol Below 5 bar, constant selectivity 179
Above 5 bar, selectivity decreased
UiO-66 — Graphite 22% decrease of the BET surface area 212
Suitable material for o-xylene over p- and m-xylene
separation at low concentrations
70 and 700 MPa Without binder Maintained BET surface area 175
16% decrease in octane loadings (after 700 MPa)
ZIF-8 398–1432 MPa Cellulose ester, K15M 10% decrease of the BET surface area (after 1432 MPa) 174
No change in catalytic reactivity
SIM-1 40–398 MPa Cellulose ester, K15M 28% decrease of the BET surface area (after 398 MPa) 174
CPO-27-Ni 0.1–1 GPa Without binder Maintained methane storage capacity 176
MOF Binder Property Ref.
Foam
MIL-101(Cr) Ni foam Decrease in hydrogen storage 182
capacities (19%)
UiO-66 Polyurethane Maintaining more than 70% of 184
the adsorption capacity for
benzene and n-hexane
UiO-66-NH4, Carboxymethylcellulose — 185
Mg-MOF-74,
HKUST-1, ZIF-8
HKUST-1@Fe3O4 Carboxymethylcellulose High catalytic activity 185
in C–H oxidation
Extrusion
HKUST-1 Silres MSE 100 70% decrease of the 180
Culmial MHPC 20 000 P BET surface area
Zr-MOF Sucrose and water 50% decrease of the 182
BET surface area
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mixture forms a paste that can then be extruded to induce shaping

of the MOF into different morphologies (Table 4). Following this
latter method, Kaskel et al. mixed HKUST-1 crystals with a silicone
resin and a plasticizer to form a paste that was subsequently
extruded into monolithic HKUST-1 strings in a ram extruder. In
this case, the decrease of the BET surface area was significant (70%
of its initial BET surface area) due to the presence of binders and Fig. 12 Commercially available MOF-based products released in 2016. (a)
heating conditions, but the performance of the extruded monolith NT-7815 micro-adsorbent for extending the storage life and quality of
was higher than the monolith obtained by in situ synthesis of many fruits and vegetables by Decco Post-Harvest and MOF Technologies
HKUST-1 in cordierite honeycombs.180 The extrusion method was and (b) ION-X gas storage tank for storing speciality gases used in the
electronics manufacturing industry by Numat Technologies. (r The
also used by Ren et al. to prepare UiO-66 spherical pellets (with a
Springer Nature reprinted with permission from ref. 191).
BET surface area of 674 m2 g1 that corresponds to 50% of its
initial value) from a paste made of UiO-66 and 10 wt% sucrose/
H2O mixture using a granulator.181 gradually until the first MOF-based products released in 2016
Starting from the binder-solvent–MOF mixture, monolithic by MOF Technologies and Numat Technologies (see Fig. 12).189,190
MOF foams can also be formed (Table 4). In this case, the nature of MOF production at scale is now underway which will help secure
the binder tends to form macroporous foam-type solids in which customer confidence and open the door for other MOF-based
the MOF can be entrapped. Similar MOF foams can also be products. However, the growing market will push the MOF
produced by synthesizing the MOF in the presence of pre-formed suppliers for further cost-efficiency, reproducibility and environ-
foam. Using both approaches, foams with MIL-101,182 HKUST-1183 mental sustainability to remain competitive. Here is a brief
and UiO-66184 were prepared. For example, Wang et al. synthesized summary of companies working with MOFs in production,
a foam monolith composed of HKUST-1@Fe3O4-MF (MF means technology development and retail to date.
magnetic fluid) by dispersing HKUST-1@Fe3O4-MF particles in an MOF Technologies was founded in 2012 based on patented
aqueous carboxymethylcellulose solution. The treatment with mechanochemical manufacturing technology invented at the
acetonitrile and finally drying led to the formation of monolithic Queen’s University of Belfast.47 This innovative process allows
foams with high catalytic activity for C–H oxidation.185 the production of MOFs using little or no solvents. Solvent-free
Other shaping processes require the formation of a dried synthesis has advantages in both waste and energy management.
MOF cake that is crushed. Here, the MOF powder is mixed with Solvent waste is a major issue in the chemical industry. The
a certain amount of a binder (typically, polyvinyl alcohol (PVA)) energy required to initiate reaction can sometimes be reduced
and the resulting mixture is dissolved in a solvent forming a paste. using mechanical energy rather than thermal energy. Recently
This paste is then dried, crushed and sieved into the wanted this method has been configured for continuous production
particle size fraction. Denayer et al. used this method to prepare through extrusion which is scalable.
MIL-53(Al) pellets using PVA as the binder. As revealed by N2 It is unknown how many MOFs can be manufactured using
adsorption isotherms, the MIL-53(Al) pellets showed a loss of BET mechanochemical synthesis, however MOF Technologies offer
surface area of 32% but maintained good CH4/CO2 selectivity a wide catalogue for direct purchase. At the end of 2016 they
capacities.179 Finally, other methodologies have also started to be sold around 100 kg of MOFs from their catalogue: magnesium
explored to incorporate MOFs into fibers186 and papers, and shape formate, Cu-BTC (HKUST-1), ZIF-8, Al(OH) fumarate, ZIF-67,
them into alginate-based spherical beads187 or ceramic beads.188 Mg-MOF-74 and Zn-SIFSIX-pyrazine. See Table 5 for a summary
These few examples, indicate that the shaping of MOFs for of MOFs for sale from each manufacturer.
specific applications is still in an embryonic stage and strong MOF Technologies were the first to announce a MOF-based
efforts have still to be dedicated to the rational study of this process commercial product available through fruit and vegetable
if we want to be able to access to the real commercial applications. It supplier Decco Worldwide Post-Harvest Holdings. The product
is also clear that, in adsorption-related applications, this shaping has been registered with the U.S. Environmental Protection
process must respect the relatively low thermal, chemical and Agency under the proprietary name NT-7815 (EPA reference:
mechanical stability of MOFs so that their adsorption capacities 2792-79). NT-7815 is described as a micro-adsorbent delivering
are mostly preserved. For other applications, however, this latter 0.7 wt% of 1-MCP, which is a gas that blocks postharvest
condition is not so important. In catalysis, for example, Bazer-Bachi ethylene responses, extending the storage life and quality of
et al. observed that, even though pelletization of ZIF-8 decreased its many fruits and vegetables. MOF Technologies has not released
adsorption properties, it did not change its catalytic activity.174 any details regarding the MOF incorporated within the product.
With the announcement of the new product, MOF Technologies
have expanded their production facility capable of producing
4. Perspectives and commercial 15 kg h1 in preparation for full scale between 5 and
developments 10 tonnes per year from 2018 depending on which MOF.191
NuMat Technologies established in 2013, have also released
Since the first patent filed in 1995 and assigned to the Nalco a MOF-based product called ION-X based on a proprietary set of
Chemical Company, commercialisation of MOFs progressed MOFs for storing gases such as arsine, phosphine and boron
View Article Online
Table 5 Sales catalogue of MOFs available by each manufacturer commercialization of the MOF-material. ProfMOF prefer water-
based and continuous flow production of MOFs. Prof Norbert
MOF Manufacturer
Stock, inventor of CAU series and advisor for ProfMOF, has
Al(OH) fumarate MOF Apps developed the water-based synthesis method for some of the
MOF Technologies
CAU-10 ProfMOF zirconium MOFs and CAUs series.43,195,196 The ProfMOF catalogue
Cu-BTC BASF includes: CAU-10, UiO-66, UiO-66-ADC, UiO-66-FA, UiO-66-BDC,
MOF Apps UiO-66-BDC-NH2, UiO-66-BDC-COOH and UiO-66-BPDC/UiO-67.197
MOF Technologies
Fe-BTC BASF STREM Chemicals Inc. has become a distributor of MOFs
Magnesium formate BASF manufactured in agreement with various MOF companies
MOF Technologies
including KRICT, Inven2 and Framergy. Their catalogue includes:
Mg-MOF-74 MOF Technologies
MIL-100 KRICT (CuI)4(DABCO)2, (CuI)4(C6H14N2)2, C6H12N4(CuCN)5, PCN-250(Fe)
MOF Apps CONEKTICt F250 by Framergy, MIL-100(Fe) KRICT F100 by
MIL-101-NH2 MOF Apps KRICT, ZIF-8 and UiO-66 by Inven2.198
MIL-53 BASF
MIL-68 MOF Apps Sigma-Aldrich is a distributor of MOFs supplied by BASF
MOF-177 BASF under the product names Basolites and Basosivt. Fig. 13 shows
PCN-250(Fe) Framergy
the total number of academic publications that reference these
UiO-66 series Inven2
MOF Apps products. The actual number of sales or quantities is unavailable
ProfMOF and therefore these numbers represent the minimum. According to
ZIF-67 MOF Apps this data, Sigma-Aldrich has made at least a total of 1198 sales for
MOF Technologies
ZIF-8 BASF research purposes. Their catalogue includes: Cu-BTC Basolites
MOF Apps C300 by BASF, MIL-53 Basolites A100 by BASF, Fe-BTC Basolites
MOF Technologies F300 by BASF, ZIF-8 Basolites Z1200 by BASF, MOF-177 Basolites
STREM Chemicals Inc.
Zn-SIFSIX-pyrazine MOF Technologies Z377 by BASF, Mg-Formate Basosivt M050 by BASF and Al-fumarate
Basolites A520 by BASF (no longer available).199
Pseudo-startup MOFWORX from CSIRO Australia is commer-
trifluoride for the electronics industry.192 The company is cializing MOFs based on patented flowchem manufacturing
setting up a facility in Asia that will receive MOF-filled tanks technology together with a diverse material and application-
from the United States. NuMat has a partnership with one of based portfolio. The group have built a reactor called Mindi (the
the top gas companies in Asia who will fill the tanks with gas aboriginal name for a mythological serpent that spits out white
which will then be distributed to customers. Asia which contains powder) that is capable of 10 kg h1 production. The company
most of the major manufacturers of electronics in the world and aims to become a product development house for MOF-based
therefore this position will likely offer direct access to this market technologies supported by their own manufacturing capability.200
which is 70% of the total demand. NuMat will lead the initial Other companies are working towards the commercialization
production of the proprietary set of MOFs for ION-X and have of MOFs such as the MOF company, MOFGen, Framergy, ACSY-
explored multiple manufacturing methods including flow, NAM and Promethean particles.201–204 MOFGen are developing
mechanochemical, solvothermal and others. nanoporous materials for materials for a number of applications
MOF Apps, founded in 2013, are the exclusive licensee for including medical devices, wound-healing and consumer health-
UiO-66 and the zirconium-based family of MOFs. With a focus care. Framergy own the license for PCN-250 which can be used
on MOF Application Services, the company aims to bring research
and industry together to identity and develop commercially viable
application opportunities in the areas of gas storage, industrial
cooling, toxic gas protection and healthcare. MOF Apps develops
and offers integrated solutions using MOFs which are cost-
competitive and which outperform state-of-the art systems.
MOF Apps have sold the most amount of MOF to a leading
vehicle manufacturer in August 2015 to test as adsorbed natural
gas fuel platform.193
ProDia is a Horizon 2020 project funded through the European
commission. It is a consortium of over 15 parties focused on the
development of reliable production methods of nanoporous
materials and their applications. Pilot-scale production of up
to 100 kg will be led by Johnson Matthey for water-based
synthesis, MOF Technologies for mechanosynthesis and Axel
One for spray-drying synthesis.194
ProfMOF founded in 2015 by a group of scientists at the Fig. 13 Number of publications referring to the Basolites and Basosivt
University of Olso, Inven2 and Kongsberg, focused on the products supplied by Sigma-Aldrich.
View Article Online
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Chem Soc Rev

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New synthetic routes towards MOF production

1. Introduction the tenets of organometallic cluster chemistry with established

Marta Rubio-Martinez was born Ceren Avci-Camur was born in

Review Article Chem Soc Rev

Aaron Thornton completed a Inhar Imaz was born in Hendaia

Wollongong Australia in 2005. Science from the Université

Daniel Maspoch was born in Matthew Hill graduated from a

Chem Soc Rev Review Article

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Chem Soc Rev Review Article

nucleation theory.57 In the same line, Gascón et al. observed

tricarboxylate)-copper(II) compound.60 More recently, Deyaner et al.

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Table 1 Electrochemical synthesis of MOFs with diﬀerent routes and conditions

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Three fluid nozzle

SIFSIX-3-Zn ZnSiF6xH2O/pyrazine/MeOH 2.4 85 57 136

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modify MOFs;135,136 the synthesis of multivariate or multi-

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PFR HKUST-1149 1.2 min 85 4533 1805

20 min 250 1300 1010

CSTR UiO-66154 8–40 h 100–120 — 810

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In 2013 Chang et al. reported the proof-of-concept mesoscale

successful up-scaling of this process was demonstrated in a

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MOF Pressure Binder Property Ref.

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mixture forms a paste that can then be extruded to induce shaping

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J. Am. Chem. Soc., 1995, 117, 10401–10402.

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frameworks, Microporous Mesoporous Mater., 2016, 224, 1358–1374.

Chem Soc Rev Review Article

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Chem Soc Rev Review Article

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201 The MOF company, http://themofcompany.com. Organic Frameworks, 2014.

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