Latest Trends in The Large Scale Production of MOFs in Accordance With The Principles of Green Chemistry

Green Chemistry
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Latest trends in the large-scale production of

Cite this: Green Chem., 2022, 24,
MOFs in accordance with the principles of green
9402 chemistry
a
Kacper Pobłocki, Joanna Drzeżdżon,a Barbara Gawdzikb and
Dagmara Jacewicz *a
An increasing number of research groups are focusing on patents for the production of metal–organic
frameworks (MOFs) on a large scale. MOFs, due to their porous structure, have been used in industry and
other fields for the catalysis, capture, and storage of gases such as methane and carbon dioxide. Due to
the increasing number of European Union restrictions and the implementation of the idea of sustainable
development, the basis for the evaluation of the chemical industry is the production of innovative, high-
class materials according to the principles of green chemistry. In this review, we present the latest litera-
ture trends on the large-scale production of MOFs based on MIL, ZIF, UiO, BTC, NU, and HKUST using the
principles of green chemistry. This manuscript is unique because it presents the trends on the latest
Received 31st August 2022, patents from the most famous organometallic framework manufacturers including BASF, NuMat
Accepted 10th November 2022
Technologies, novoMOF, MOF Apps, and MOF Technologies. Furthermore, it is an accessible collection of
DOI: 10.1039/d2gc03264c information for research centres. In addition, in this work, we present a critical review of the procedures
rsc.li/greenchem for obtaining MOFs, considering the principles of green chemistry.
1. Introduction globally. However, large-scale action is needed to slow down

climate change (Fig. 1).
Scientists are joining forces to design new technologies, This is important because we are still dealing with the fol-
patents, and inventions to improve the ecological situation lowing issues:
• Global warming (numerous fires and melting glaciers),
• Water and air pollution (caused by sewage, pesticides,
smog, or acid rain),
a
Faculty of Chemistry, Department of Environmental Technology, University of • Consumerism (focusing on quantity, not quality),
Gdansk, Wita Stwosza 63, 80-308 Gdansk, Poland.
• Deforestation (causes floods, droughts, and landslides,
E-mail: dagmara.jacewicz@ug.edu.pl
b
Institute of Chemistry, Jan Kochanowski University, Uniwersytecka 7, 25-406 Kielce, where the number of forests has decreased by 40% since the
Poland beginning of the 20th century),
Kacper Pobłocki is currently a Dr. Joanna Drzeżdżon is an

master’s student at the assistant professor at the
Department of Environmental Department of Environmental
Technology at the Faculty of Technology, Faculty of
Chemistry of the University of Chemistry, University of Gdańsk.
Gdańsk. His research topics Her scientific interests focus on
focus on the design of syntheses olefin polymerization catalysts,
of new organometallic com- including the application of
pounds and their use as “green” “green chemistry” principles. She
precatalysts in olefins polymeriz- has published more than 50 aca-
ation reactions. demic papers in international
journals, as well as 2 patents.
Kacper Pobłocki Joanna Drzeżdżon
9402 | Green Chem., 2022, 24, 9402–9427 This journal is © The Royal Society of Chemistry 2022
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Green Chemistry Tutorial Review

Fig. 1 Recent weather anomalies in the world caused by climate Fig. 2 Schematic presentation of the various applications of MOFs.
change. Created with BioRender.com. Created with BioRender.com.
• Desertification (loss of soil humus), and fied, while new organometallic frameworks are being created
• Loss of biodiversity. with unique absorption and catalytic properties. MOFs are
According to the Global Footprint Network, the ecological also used in gas storage, polymerization reactions, purifying
debt, i.e., the day when humanity uses all natural resources the liquid fuel from nitrogenated compounds,5 separation,6
that the Earth can regenerate in 365 days, is July 29 in 2021 including cooling applications (through reversible adsorption
(for comparison, it was August 22 in 2020).1 Therefore, of water), ion exchange,7 photodynamic anticancer therapy
raising the awareness of the largest industrial companies (PDT)8,9 biomedical imaging, biodiesel,10 luminescence,11
such as petroleum, chemical, pharmaceutical, and construc- lithium-ion batteries, anti-corrosion agents,12 non-linear
tion to issues related to green chemistry is crucial to achiev- optics (NLO), doubling the frequency of solar cells,13,14 and, in
ing satisfactory results in the environmental field. This can particular, in energy technology, e.g., in the production of fuel
enable the elimination of emissions from chemical sub- cells and supercapacitors (Fig. 2).
stances to the environment and prevent climate disasters. The companies that are pioneers in the production of
One possibility of environmental protection is to use porous MOFs on a large scale are undoubtedly BASF (which sells
materials, which are characterized by large open spaces, i.e., chemical compounds under the name Basolite) and MOF
so-called cages. Initially, these substances were zeolites and Technologies. These companies produce organometallic struc-
activated carbons.2 tures in accordance with the principles of green chemistry.15,16
Nowadays, MOFs (metal–organic frameworks) are the MOF Technologies relies on mechanochemistry to obtain
fastest-growing class of materials in chemistry. Metallic- porous structures such as Mg-MOF-74, ZIF-67, MIL-53(Al) and
organic structures were presented for the first time in the pub- HKUST-1. MOF Apps use solvothermal, mechanochemical,
lication by O. M. Yaghi in 1995.3,4 However, the MOF com- spray drying, and microwave-assisted processes to synthesize
pounds published several years ago are constantly being modi- ZIF-88, MIl-68, UiO-66, MIL-53(Al) and HKUST-1. Also, BASF
Dr Barbara Gawdzik is an an Dr Dagmara Jacewicz is an

Associate Professor in the Associate Professor in the
Institute of Chemistry, Faculty of Department of Environmental
Natural Sciences, Jan Technology, Faculty of
Kochanowski University of Chemistry, University of Gdańsk,
Kielce, Poland. Her scientific Poland. Her scientific interests
interest: organic chemistry, bio- are in inorganic chemistry,
organic chemistry, especially the coordination chemistry, bio-
synthesis of biologically active inorganic chemistry, physical
hetero- and macrocyclic com- chemistry and green chemistry.
pounds. She has published over She has published more than
60 academic papers 15 book 100 academic papers 43 book
Barbara Gawdzik chapters and 10 patents. Dagmara Jacewicz chapters, co-author of 2 books –
academic scripts.
This journal is © The Royal Society of Chemistry 2022 Green Chem., 2022, 24, 9402–9427 | 9403
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Tutorial Review Green Chemistry
representatives predicted the great technological importance

of MOFs using the electrochemical synthesis method of
MOF-177, HKUST-1, ZIF-8, and MIL-53(Al). However, the
turning point was the production of several tons of Al-fumarate
Basolite® A520 by BASF via hydrothermal synthesis (no longer
available). Chemical laboratories can purchase MOFs through
the well-known Merck, which is one of the largest manufac-
turers and suppliers of chemical (approximately 90 000),

analytical, and biochemical reagents, and accessories for all
types of chromatography. Consequently, the raw materials for
the production of MOFs are commercialized and available to
all chemists, with the number of customers exceeding
Fig. 3 Four main technical barriers in the commercialization of MOFs.18
1.3 million.16,17 MOFs are typically produced under solvo- Created with BioRender.com.
thermal conditions in the laboratory, where the solvent and
solute are heated to reflux. However, the solvothermal method
is not economically feasible and not recommended for com- project, which cannot be omitted herein. The dominant com-
mercial use because of the difficulty in scaling the production panies and research and scientific centres in terms of patent
due to the extended reaction time (about 24 h) and poor applications of organometallic crystal networks are in the USA
quality of the resulting material. Polar solvents are usually and Germany (BASF-Badische Anilin – und Soda-Fabrik). Fig. 4
employed to solubilize the large organic ligands used. The presents the largest chemical concerns in the production of
most common solvent appearing in the literature is DMF, MOFs on a large scale.
which is poisonous and adversely affects the environment. According to the literature on MOFs, they are increasingly
Therefore, the green chemistry principles introduced in 1991 being produced according to the principles of green
by Paul Anastas (and in publications related to MOFs in chemistry.3,4,16 “Green chemistry” has been clearly defined by
2007)15 advise against the use of these solvents.16,17 IUPAC and can be summarized as “The invention, design, and
In the field of science, patent reports on MOFs started to application of chemical products and processes to reduce or
dominate, making it possible to produce MOFs on a large eliminate the use and generation of hazardous substances”.
scale and implement them in the industrial market. The Fig. 5 presents the 12 principles of green chemistry.19–21
search for new MOFs is no longer a priority, where scientists Despite the fact that the term “green chemistry” was known
and production scientists are focusing on optimizing the pro- since 1991, the first articles related to the synthesis of MOFs
cedures for obtaining MOFs with already known structures. An without the use of harmful substrates and solvents appeared
important access requirement for potential MOF applications after 2000. The group of Lu and Babb reported the synthesis of
is the ability to routinely synthesize MOF materials in large single crystals of [Cu(INA)2]·solvent, where solvent = 2H2O,
quantities (kg scale or more) at an economical price. The MeOH, EtOH, and n-PrOH.22 In 2006, the synthesis of the
process must be a comprehensive, efficient synthesis capable same compound by the mechanochemical method was
of producing large amounts of MOFs to introduce these presented.23
materials in real applications. In addition, the synthesis pro- The large-scale production of MOFs in accordance with the
cedure must be transferable to large-scale production. By principles of green chemistry is an extremely interesting topic
observing research activities around the world, we can see a for chemists, material engineers, production technologists,
strong tendency to create new ideas, including interesting and ecologists who are focused on a better standard of living
preparation methods, quick synthesis, and original modifi- on Earth, which is why we discuss the latest reports and
cations of MOFs. However, the transition from laboratory to patents in this field herein. We classify metal–organic frame-
commercial scale is often tedious.18 There are four “leapfrog works into several types such as MIL, ZIF, UIO, BTC, NU, and
barriers” described in the literature (Fig. 3). The first one is the HKUST.24,25 Over the years, new methods have been developed
wide availability of MOFs, where there is a need to create an for the synthesis of organometallic frameworks, and thus we
innovative project. Secondly, there is a very low number of aim to present a timeline to better illustrate the chronological
scientific articles on the modification of MOF structures progress in this regard (Fig. 6).
without losing their most valuable physical property, i.e., poro-
sity. Next, is fine-tuning of their structures. Finally, the last
barrier is learning how to obtain MOFs together with the
appropriate efficiency under laboratory and production 2. General and green synthesis
conditions.18 techniques used for production of
The US5648508A patent explains how to prepare micro- MOFs
porous structures NALCO Chemical Company and Omar Yaghi
Crystalline metal–organic “microporous materials for the puri- Metal hydroxides, oxides, sulfates and acetates have been
fication of liquids and gases”. This was a ground-breaking selected to avoid the generation of toxic and corrosive by-pro-
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Fig. 4 Examples of the largest chemical concerns dealing with the production of MOFs on a large scale with exemplary compounds.16 Created
with BioRender.com.
Fig. 5 12 principles of green chemistry.19–21 Created with BioRender.com.
ducts such as the corrosive HCl, instead producing by-products

such as water and acetic acid. Another issue is the use of harm-
less, green solvents such as ionic liquids, deep eutectic
solvent, water, Cyrene and surfactants. The toxic and com-
monly used DMF should be avoided because it can decompose
into the harmful dimethylamine when heated.
2.1 Solvothermal
Secondary building blocks (SBUs) with organic linkers create
Fig. 6 Modified Rubio-Martinez’s timeline of the most common syn-
fascinating network architectures, where the solvothermal
thetic approaches patented for the synthesis of MOFs.16 Created with method is the most effective and common method used in the
BioRender.com. synthesis of complex compounds and crystal engineering of
View Article Online
MOFs. This method enables the creation of tailor-made

designs with the desired application and physicochemical pro-
perties. In the solvothermal method, metal salts are dissolved
together with the organic linker in a solvent. The most popular
liquids used in the synthesis of metal–organic frameworks are
DMSO (dimethyl sulfoxide) and DMF (dimethylformamide)
due to their high boiling point (DMSO, 189 °C, and DMF,
153 °C).26–28 There are cases when the solvent used is water,
and in that case the synthesis is called hydrothermal. The
advantage of the solvothermal method is the possibility of its
optimization, i.e., selection of appropriate molar ratio of
reagents (stoichiometry), temperature, solvents, pH, reaction
time, concentration of precursors and counterions. The optim- Fig. 7 Schematic representation of different post-impregnation
ization of the reaction parameters undoubtedly influences the methods used in the synthesis of IL/MOF composites.31 Created with
morphology, shape, yield and production cost of the porous BioRender.com.
material. However, complete control over the creation of pre-

dictable architectural structures still remains elusive given that
the MOF crystallization process involves complex thermo- that consist of only ions. Also, the synthesis with green sol-
dynamic and kinetic aspects. The choice of solvent is vents is called ionothermal (Fig. 7).31 ILs based on pyrrolidi-
especially important because it is one of the factors determin- nium, pyridine, tetraalkylammonium, and 1,3-dialkylimidazo-
ing the structure of the chemical entity. In some cases, the lium cations and weakly coordinating inorganic anions, such
crystal lattices contain a solvent that is uncoordinated with as tetrafluoroborate ([BF4]−), hexafluorophosphate ([PF6]−), and
metal clusters. The presence of the solvent in the crystal lattice trifluoromethane (OT) triflate, appear most often in the litera-
as coordinated or uncoordinated molecules adversely affects ture (Fig. 8). To date, ILs have been used in conjunction with
the sorption properties and porosity of MOFs. Furthermore, IRMOF-1, CuBTC, ZIF-8, and MIL-101.32–34 Green solvents have
the presence of solvent molecules in the pores of MOFs many advantages, e.g., non-toxicity, resistance to combustion,
reduces their porosity.28,29 Additionally, it can be concluded ionic and thermal conductivity, high chemical and electro-
that polar protic solvents such as water, methanol and ethanol chemical stability, negligible volatility, and low (zero clearance)
have the ability to form hydrogen bonds with ligands contain- vapour pressure. Consequently, it is possible to carry out the
ing carboxylate and amide functionalities. In addition, polar process without reflux condensers, which undoubtedly reduces
protic and aprotic solvents can bind to metal ion centres. the cost of the synthesis.35 Also, due to the presence of high
Among the structure-determining factors, pH is imortant.29 As ion concentrations, it is possible to synthesize new, more
the pH value of the reaction medium increases, the organic porous materials. ILs can replace standard reagents and act as
linker is deprotonated. Consequently, higher temperatures a solvent or electrolyte, but their presence often interferes with
favour the formation of large crystals of higher quality. The the final structure of MOFs.36 Recent literature reports show
reaction temperature may also change the rate of crystal that IL/MOFs perform better in gas absorption, membrane
growth and nucleation. It is also worth mentioning that separation, catalysis, and conductivity applications than tra-
vacuum drying and purification of the final product are ditional MOFs. However, their use in industry is hampered by
necessary (usually using ethanol and methanol).30 their viscosity, low diffusion coefficients, clogging of their
Glass flasks are used for synthesis at low temperatures (up
to 120 °C). Alternatively, above 125 °C, Teflon-lined autoclaves
or bomb reactors are required, which can normally be used in
the temperature range of approximately 80–250 °C.30 However,
the disadvantage of the solvothermal method is its cost
because it requires the use of reduced pressure and high temp-
erature, which undoubtedly increases the costs. Another limit-
ation is the long production time required to obtain the
desired product.26
The biggest drawbacks of the solvothermal method are its
long duration (re-up to several days) and requirement of very
high temperatures, which increase the cost of the process on a
large scale. Additionally, the use of metal chlorides results in
the corrosion of the expensive heating furnaces and
reactors.28–30
2.1.1 Ionothermal. Ionic liquids (ILs, green solvents) are
usually defined as materials with a melting point below 100 °C Fig. 8 Cost common anions and cations forming ILs.31,32
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pores, problematic recycling, portability, and product purifi- to ILs, deep eutectic solvents differ in that they have at least
cation. The introduction of IL/MOF on a large scale is also pro- one neutral molecule (without charge); additionally, they are
blematic due to the presence of impurities, e.g., a small readily available, cheaper, and do not require additional purifi-
amount of water in the process of gas separation by Cu-BTC, cation by organic solvents. Thus, ecological solvents are con-
which causes a lack of selectivity in gas purification, as well as sidered.39 Interestingly, besides being reaction media for the
with a larger amount of H2O, resulting in the destruction of preparation of MOFs, DESs can play many other roles, e.g.,
the metal–organic frameworks.32–36 Additionally, the use of ILs structure steering factor by internally participating in the for-
as solvents is problematic due to the reduced BET specific mation of complex MOF structures. They can be synthesis car-
surface area of porous materials due to the clogging of their riers, making it possible to carry out the reaction at a lower
pores by ionic liquids. Authors dealing with IL/MOF compo- temperature without a reflux condenser, which can also be
sites propose the introduction of computational chemistry in used for post-synthetic modification for the creation of compo-
their research to optimize the adsorption and separation pro- sites or hybrids.37–41
cesses, go from the micro to macro scale, and consciously and 2.1.3. Surfactant-thermal process. In addition to ILs and
safely use ionic liquids.32–36 DESs, surfactants, which consist of polar water-soluble hydro-
2.1.2. Deep eutectic solvent usage. Another green method philic groups and oil-soluble hydrophobic groups, are also
for the synthesis of MOFs is the use of deep eutectic solvents used for the synthesis of MOFs. They are characterized by high
(DES).37 Generally, DESs are characterized by a very large thermal and chemical stability and low vapour pressure, and
depression of freezing point and are liquid at temperatures also have a wide range of properties depending on the pH, e.g.,
lower than 150 °C. DESs have been known since 2003, as acidic and basic, and charge, e.g., neutral, anionic, and cat-
reported by Abbott et al.38 In their publication, they showed ionic (with high ionic conductivity). Surfactants are amphi-
that mixtures of substituted quaternary ammonium salts such philes and have the ability to self-assemble into micelles,
as hydroxyethyl-trimethylammonium (choline) chloride with which helps to control the size and shape of MOF crystals.42 A
urea produce eutectics that are liquid at ambient temperature good example is the study by Duan et al., who designed a
(low melting point of 12 °C).37 In contrast, their individual method for the synthesis of meso-Cu-BTC. They found that the
components have a melting point of 302 °C (ChCl) and 135 °C size of the mesopore could be adjusted from 3.61 to 4.88 nm
(urea).38–41 Scientists attribute this phenomenon to the for- by increasing the long-chain in the alkyl groups of the surfac-
mation of hydrogen bonds between the hydrogen bond accep- tant (C12 to C18).43 The optimal H2O/EtOH ratio was 0.2 and
tor (HBA) and donor (HBD) (Fig. 9). DESs are characterized by the optimal amount of template (surfactant) was 1.35 mmol.
the high solubility of organic and inorganic compounds due Examples of the surfactants used for the synthesis of MOFs
to the production of a series of hydrogen bonds. For example, include polyvinylpyrrolidone (PVP), polyethene glycol
in a mixture of choline chloride and urea (molar ratio of 1 : 2), (PEG-400) and dodecyltrimethylammonium bromide (DTAB)
the high solubility of lithium chloride was observed at 50 °C as the reaction medium.27–29 PEG is particularly attractive due
(LiCl solubility > 2.5 mol dm−3). Further examples are silver to its non-toxicity and quick biodegradability, wide tempera-
chloride (AgCl solubility = 0.66 mol dm−3), aromatic acids ture range applicability and the oxygen atom in its structure,
(benzoic acid solubility = 0.82 mol dm−3) and amino acids which can bind with metal ions and influence the crystal
(D-alanine solubility = 0.38 mol dm−3).37,38 The authors also growth of porous materials. Compared to ILs, the use of surfac-
reported an increase in conductivity with an increase in temp- tants and DESs is much cheaper, making it a more cost-
erature, similar to imidazolium-based ionic liquids. Compared effective method for large-scale use.42,43 However, a serious
drawback should be mentioned, which is the problem of the
simultaneous formation of several MOF crystalline phases that
are difficult to separate in pure forms.29
2.2 Mechanochemistry
Mechanochemical synthesis (Fig. 10) is considered to be one of
the greenest methods, conforming with the idea of sustainable
development.16 Depending on the needs, neat grinding (NG),
liquid-assisted grinding (LAG) and liquid-ion-assisted grinding
(ILAG) can be distinguished as the three main strategies used in
the mechanochemical synthesis of MOFs.28,29 The other advan-
tages of this process are it is carried out at room temperature
(possibly slightly higher) and without the use of solvent (or a
very small amount), undoubtedly reducing the production
costs.44 Additional advantages include the repeatability, control
of the speed and short duration of the process (5–60 min),18
which can be accelerated by the use of various types of electric
Fig. 9 Examples of DES components.38–40 grinders, whereas solvothermal methods last from several hours
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Fig. 11 Schematic diagram depicting the syntheses of 3D MOF-based

aerogels or hydrogels via (top) direct mixing and (bottom) in situ growth
methods.45–50 Created with BioRender.com.
metal–organic frameworks, during which dust formation is

Fig. 10 Comparison of the traditional manufacture of MOFs with that possible and is dangerous for employees.45–50
for the direct mechanochemical synthesis by twin screw extrusion.18
Created with BioRender.com.
2.4 Electrochemical
The electrochemical method for the synthesis of MOFs is based
to several days. The most common metal salts used for the syn- on the mutual conversion between substrates and electricity.
thesis of MOFs are oxides and acetates, generating water or Electrochemical synthesis has specific advantages over tra-
acetic acid as by-products, which are easy to remove by heating. ditional solvothermal synthesis including the use of ambient
However, the disadvantage is that the control of the crystal mor- temperature instead of 120 °C,16 ambient pressure instead of
phology and particle size of the product is limited. Also, special high-pressure autoclaves, mild reaction conditions that recycle
electric grinders, mortars and pestles are needed, increasing the the nitrate counterions, and significantly reduced reaction time
cost. Additionally, the final product may not be pure due to con- compared to the conventional solvothermal synthesis method.
tamination from the grinding reactors, which adversely affects Additionally, it is possible to control the synthesis via the
its performance. Fig. 10 presents a comparison of the tra- applied voltage. In addition, the electrochemical method makes
ditional synthesis method with the twin screw extrusion it possible to synthesize thin films or coatings.51 According to
method.16,44 the latest work by Ren and Wei,52 the electrochemical synthesis
methods of MOF can be divided into three categories depend-
2.3 Aerogel or hydrogel synthetic method ing on the direction of electron transfer and the place where the
nucleation process occurs, as follows: (1) surface electrode
The sol–gel method is a unique method for the synthesis of
nucleation (ESN) including anodic dissolution (Fig. 12) and
MOFs (Fig. 11). The use of MOF composite aerogels and aero-
cathodic deposition, (2) indirect bipolar electrodeposition
gels is particularly attractive in biomedical applications due to
(IBED) and (3) electrophoretic deposition (EPD). The former two
their high porosity, high water content, and excellent biocom-
methods are based on the immediate MOF formation in the
patibility.45 The high porosity of MOF composite aerogels
reaction system, while the latter is based on the initial MOF syn-
leads to high potential adsorption applications, while their
thesis and subsequent deposition. HKUST-1 is synthesized on a
low density and excellent mechanical properties improve their
large scale by BASF.52 The original synthesis design was based
transport and processability, respectively.46–48 Composite aero-
on immersing a copper plate (Cu2+ source) in a solution con-
gels can also be reused after simply washing with water, which
taining an organic linker (BTC) and electrolyte. When a specific
is ideal for industrial applications. For example, ZIF-67 with
current (1.3 A) and voltage (12–19 V) are applied, the copper(II)
supporting material sodium alginate is used for water purifi-
ions are released from the electrode into the solution. After
cation, ZIF-8 and ZIF-67 together with acrylamide (AM) and
150 min, the HKUST-1 structure with a specific surface area of
2-hydroxyethyl (HEA) are applied for drug delivery and ZIF-8,
1820 m2 g−1 is formed (compared with the solvothermal
ZIF-67, and Fe-MOF together with proteins (Burkholderia
method of 1550 m2 g−1).27–29
cepacia lipase and penicillin G acylase) is an excellent
biocatalyst.49,50 However, the cost of large-scale production,
including the cost of raw materials and equipment, is a down- 2.5 Microwave-assisted synthesis
side of this method. The other limitations include the low Microwave-assisted synthesis (MAS) is based on the interaction
efficiency of the resulting MOFs and the disposal of powdered of electromagnetic waves with a material containing an electric
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thinning, that is, reducing pressure. Then, high tensile forces

act, causing local rupture of the continuous medium (liquid).
The excess energy carried by the acoustic waves causes the
bubbles to grow and eventually implode, which is the source of
local shock waves. The disadvantages of the sonochemical
method are that ultrasonic waves can break up the crystals that
are formed or hinder the formation of large single crystals,
which will make it impossible to characterize them by X-ray

diffraction.53
2.7 Continuous flow

According to the latest patent reports, Marta Rubio-Martinez
16
et al. developed a synthetic method based on continuous flow
Fig. 12 Electrosynthesis of MOFs by anodic dissolution. Created with
BioRender.com.
chemistry (Fig. 14). The continuous flow method enables the
continuous production of MOFs over a longer period.
Moreover, the continuous flow approach can provide an
increased reaction rate and enables the production of organo-
metallic structures with greater efficiency, without wasting the
material surface, while controlling the particle size, making it
possible to easily optimize the synthesis and its reproducibil-
ity. Additionally, the surface area to volume ratio for the reac-
tion mixture in the flow reactor is much higher than that in
Fig. 13 Microwave reactor. Created with BioRender.com. the batch reactor, contributing to improved heat and mass
transfer. Another advantage is the use of less solvent and
energy than with conventional synthesis methods. By using
charge, e.g., polar solvent molecules that conduct ions in a this process, it is possible to produce porous materials in
solid (Fig. 13). The MW rays interact directly with the sub- amounts close to that required for wide application. This is a
strates, causing the reaction medium to heat faster, thereby technique that combines many processes, including heating,
increasing the synthesis efficiency. Additionally, the MW thermal treatment and processing, which enables the large-
heating is volumetric, which allows for an even reaction in the scale synthesis of HKUST-1.54,55 Also, continuous synthesis
entire volume of the reactor.16,27 The other advantages include can be combined with the electrochemical technique.
morphological control, easy change of reaction parameters Consequently, scientists obtained much larger BET areas
and short synthesis time due to the fast nucleation and crystal ranging from 1550 m2 g−1 to 1716 m2 g−1 and used a higher
growth. Unlike the surfactant-thermal process, MOF crystals BTC concentration ranging from 481 to 1531 m2 g−1.120,121 It is
can be easily separated from the undesirable by-products due worth mentioning that systems with continuous flow can be
to the phase selectivity.28 Similar to the previous methods for broadly divided into three categories including continuous
the synthesis of MOFs, MW has disadvantages, including the flow (hydro) solvothermal synthesis (CFHS/CFSS), continuously
requirement of specialized equipment to generate optimal stirred tank reactors (CSTR), and micro or multi-fluid
irradiation power, resulting in poor reproducibility of the systems.56 A good example of the use of the ultrafast and low-
product and preventing industrial implementation. Another cost continuous flow method was presented by Bagi et al.57
issue that hinders the synthesis of MOFs on an industrial scale Highly crystalline monodisperse MOF-808 nanoparticles were
is the difficulty in isolating large single crystals.29
2.6 Sonochemical method

The sonochemical method uses ultrasonic waves of very high
frequencies (20 kHz–10 MHz).16 It is a cost-effective, selective,
environmentally friendly method that contributes to high-yield
end products with a homogeneous structure and morphology.
Compared to electrosynthesis or MW, it has been proven that
the sonochemical method is better in terms of simplicity, ease
of isolation of porous materials, reduced crystallization time
and energy efficiency due to the use of the cavitation
phenomenon.27–29 Cavitation is the process of dynamic for-
mation, growth and disappearance of vapoured gas bubbles in Fig. 14 Diagram of continuous flow method for the synthesis of
a liquid.53 The formation of bubbles occurs in the cycle of MOFs.55 Created with BioRender.com.
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synthesized in a residence time of 5 min under flow compared by reducing the pressure of the liquid CO2 above its critical
to 48 h in batch, resulting in a productivity of 95 155 kg m−3 temperature, which significantly reduces the surface tension.
day−1, which represents a two-orders of magnitude increase to Therefore, it can be concluded that it is a cost-effective green
that in batch mode (335.5 kg m−3 day−1).57 However, there are and mild MOF activation alternative, but with low chemical
several reports on the disadvantages of flow chemistry such as and thermal stability.58,59
uneven flow of the solvent under pressure and problems with
continuous flow reactors. Additionally, these reactors are very
expensive. In summary, continuous flow chemistry is a cost- 4. Production of MOFs based on MIL
effective method for production on an industrial scale, which
is consistent with the idea of sustainable development and the In 2002, the world of science learned about a new type of
principles of green chemistry (if the solvent used is, for metal–organic framework, i.e., MIL (Matériaux de l’Institut
example, water and the metal source is metal oxides or Lavoisier). The original compound presented by the Ferey
acetates). group was MIL-47 (containing vanadium in the +3 and +4 oxi-
dation states, a terephthalate anion, which acts as a ligand,
and DMF was used as the solvent). MOFs based on MIL are
3. Activation of MOFs characterized by the use of metal cations from group-d with
different degrees of oxidation, e.g., MIL-53 contains V(III,IV),60
3.1 Thermal activation
Cr(III),61 Fe(II,III),62,63 Al(III)64 and terephthalic acid derivatives,
To determine the porosity and surface area of MOFs, trapped e.g., 2-aminobenzene-1,4-dicarboxylate.65 The second popular
solvent particles should be removed from the pores by an acti- compound from the Lavoisier Institute is MIL-100 and
vation process. The most common method for the activation MIL-88A. In 2009, Patricia Horcajad’s research group proved
of stable MOFs is by heating them under vacuum,58 where the that MIL materials are non-toxic nanocarriers for anti-cancer
remaining less stable porous structures may decompose. Thus, and retroviral drugs such as busulfan, cidofovir, and azidothy-
to avoid this problem, the solvent is replaced with another sub- midine triphosphate. It has been shown that 40% of the mass
stance with a low boiling point and lower surface tension of doxorubicin is stored in MIL-101-NH2, and then after
before heating, e.g., ethanol and acetone.58 30 min, it is activated in liver cells. The presence of the drug
was confirmed in animal cells for another two weeks. Due to
3.2 Supercritical CO2 drying the porous nature of the surface of metallic organic com-
An interesting compound used in the synthesis of MOFs is pounds, they act as molecular sponges, and thus the active
supercritical carbon dioxide (scCO2). Carbon dioxide (CO2) is a substances of drugs were better absorbed and easier to visual-
special chemical with a low critical temperature (304.21 K) and ize. Mössbauer spectroscopy proved that MOF compounds can
modest critical pressure (73.83 bar). The use of scCO2 is gener- act as contrast agents. Scientists applied MIL-88A nano-
ally difficult due to the limitation of the ultra-low solubility of particles in female rats by controlling the sequence of the gra-
the MOF precursors. CO2 is a poor solvent due to its apolar dient and the spin echo, and it was possible to observe that
nature and low dielectric constant; however, it is non-flam- the treated organs were darker than usual.24,65
mable, has low toxicity, and is abundant.58 Overall, scCO2 has Human senses cannot fully determine the presence of pol-
been used to activate MOFs to generate new properties. By lutants, for example, with the naked eye. In cultural insti-
using scCO2, the solvent molecules in the pores can be elimi- tutions such as museums or art exhibitions, organic pollutants
nated without creating surface tension and capillary forces.59 such as aldehydes, acids and sulphides are present (Table 1).
This is attributed to the transition from phase scCO2 to For example, acetic acid is produced by the hydrolysis of cell-
gaseous CO2, which is released into the atmosphere or ulose acetate in wood, plywood, furniture and flooring. To
recycled. Hupp et al. found that zirconium-based metal– detect the concentration of harmful chemicals, a composite
organic frameworks activated by scCO2 showed significantly material based on MIL-101(Cr) has been patented. This inven-
higher surface area Brunauer–Emmett–Teller (BET) values tion acts as an optical indicator for detecting the saturation of
than that activated by other conventional processes such as an absorbent. The data is extremely satisfactory, where its
solvent exchange. The advantage of this method is its speed large-scale synthesis takes place with an efficiency of approx.
and porosity control based on the CO2 pressure. This trans-
lates into the use of MOFs in water adsorption, hydrogen, and
methane storage.59 Similar to the conventional activation Table 1 Average pollution measurement in 17 cultural heritage
process, scCO2 drying involves three general steps, as follows: institutions66
(1) pre-exchanging the as-synthesized solvents with liquid CO2-
Average measurement score of
compatible organic solvents (miscible with liquid CO2 and not Pollutant 17 cultural heritage institutions
causing any damage to the components, e.g., methanol and
ethanol), (2) exchanging the organic solvents with liquid CO2 Formaldehyde 42 ppb
Formic acid 14 ppb
(the CO2 exchange process is usually carried out at 0–10 °C) Acetaldehyde 23 ppb
and (3) evaporating CO2 in its supercritical state. This is done Acetic acid 32 ppb
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solution such as Cu2+, Al3+, and Mn2+ and heat treatment

caused the crystallization of mainly MIL-96(Al) compounds.
However, after removing the aluminium ions and re-adding
BTC to the solution, MIL-96 based on Cu/Ni/Mn was co-
precipitated.67–70
Most synthetic methods use nitrate salt as the metal source.
However, it should not be used in the solvothermal method
because the toxic HNO3 is released. An exception to the rule is

presented in the publication by Sánchez-Sánchez et al.,71
where they proposed the synthesis of MIL-53(Al) at room temp-
erature using disodium terephthalate (Na2BTC). Consequently,
nanocrystalline MIL-53(Al) with pores free of H2BDC was
Fig. 15 Block diagram of obtaining a film based on an MOF obtained (Fig. 17).71,72 The surface areas estimated using the
(MIL-100).66
BET method were 1048 and 1144 m2 g−1 depending on the
reaction time (4 h–7 days), which improve the size of the
crystal MIL-53. Moreover, it is one of the most stable MOFs
70%, with a BET surface area of approx. 4000 m2 g−1. The only given that it is thermally stable at temperatures higher than
drawback of the experiments is the reduction of the process 500 °C in the presence of oxygen, which is related to high
temperature from about 220 °C to 160 °C due to the addition chemical stability under ambient conditions.
of acetic acid.66 The course of the reaction was examined by
means of environmental porosimetry (PEE) ellipsometry,
which showed slow regeneration due to the interactions of the
free spaces of the porous material and CH3COOH (Fig. 15).66
Another example of the application of MIL-based organic
metal compounds is in lithium-ion (LiB) batteries, a rapidly
growing sector of mobile energy sources used in electric cars,
laptops, power banks, solar panels, electric bikes, and
cameras. However, little information is available about the
downside of introducing LiBs on a large scale. Namely, by
2030, 2 million tons of lithium-ion battery waste due to the
popularization of electric cars may appear. However, despite
EU regulations, only about 5% of waste is recycled due to tech-
nical reasons and the high cost of LiB recovery.67 As an
example, MIL-96(Al) was obtained from the large-scale re-
cycling of lithium-ion batteries (Fig. 16). It was formed in the
process of solvothermal synthesis, during which the batteries Fig. 17 General reaction for the preparation of MIL-53(Al) by conven-
were dissolved in an acidic environment ( pH 1–3). Then the tional (top) and the room temperature (green synthesis method).71,72
addition of the organic BTC ligand to the metal cations in the Created with BioRender.com.
Fig. 16 Flow chart of the recycling method of Li-ion batteries.67 Created with BioRender.com.
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Subsequently, Martinez Joaristi et al.73 developed a green, We would like to emphasize that we believe that mechano-
electrochemical method for the synthesis of a homogeneous chemical synthesis is the most suitable for the large-scale pro-
MIL-100(Al) porous material. A solution of BTC in 100 mL duction of MOFs in accordance with the principles of green
ethanol/waterer was used. The mixture was heated to 60 °C in chemistry. For example, Pilloni et al.78 reported the synthesis
an electrochemical cell with 2 aluminium electrodes spaced at of MIL-100(Fe). These researchers mixed H3BTC and Fe
least 3 cm apart and a current density of 10 mA cm−2. The (NO3)3·9H2O in a Teflon-coated stainless steel grinding jar,
resulting material was filtered and cleaned with ethanol at and then added 5 mL of tetramethyl ammonium hydroxide
room temperature overnight, and then filtered again and dried (TMAOH) aqueous solution. Subsequently, the mixture was
at 100 °C.73 The given reaction conditions were from the milled on a vibrating ball mill. The thick paste was collected
optimization of the process, which led to the formation of a after 1 h of grinding. Then, the sample was dispersed in water
porous material with a specific surface area of 969 m2 g−1 and and centrifuged three times at 2500 rpm.78 After washing, the
pore volume of 0.54 cm3 g−1.73 sample was air-dried at room temperature. The synthesized
In 2017, Permyakova et al.74 synthesized MIL-160(Al) using material had a pore volume of 0.386 cm3 g−1 and surface area
the non-corrosive and slightly hygroscopic Al(OH)(CH3COO)2 of 1033 m2 g−1. Its specific surface area was much lower than
as the metal source and 2,5-furandicarboxylic acid as the that reported using the solvothermal method, but more envir-
linker (1 : 1 molar ratio), while the solvent was water. The onmentally friendly because it does not use toxic solvents and
mixture was stirred and heated under reflux for about the material was synthesized at room temperature, which
24 h.75,76 The resulting white material was filtered, washed reduces the energy costs.78 The commercially available
with ethanol and dried in an oven, yielding 13.9 g of dry MIL-100 has a specific surface area greater than 1300–1600 m2
MIL-160(Al) (STY = 185 kg m−3 day−1).74 Scientists successfully g−1. The authors additionally investigated the thermal stability
synthesized MIL-160(Al) on a larger scale, yielding 400 g of of MIL-100 using the TGA method, finding that the mechano-
powder with an efficiency of 93%, specific surface area of chemically synthesized MIL-100(Fe) is more thermally stable
1150 m2 g−1 and Vpore = 0.479 cm3 g−1. The optimization of the than the commercially available material. The weight loss of
synthesis to obtain the largest possible BET surface area was the porous material sample by approximately 33 wt% occurred
based on different reaction times (12–72 h) and temperature in the range of 298–393 K, which is the result of dehydration.
(100–150 °C). Material shaping was performed using the con- The weight loss of about 39 wt% was observed in the range of
ventional wet granulation method by mixing MIL-160(Al) 547–673 K, which is associated with the collapse of the
powder with 10 wt% silica salt. The physicochemical stability MIL-100 structure.78 Additionally, the synthesized material
of MIL-160(Al) was characterized by seasonal nitrogen storage. showed a higher adsorption capacity towards 4,6-dimethyl-
The monitoring of 6 adsorption–desorption cycles in the dibenzothiophene (4,6-DMDBT) from diesel fuel at ambient
reactor using a combination of PXRD, TGA, IR spectroscopy temperature than the commercially available MIL-100.
and nitrogen-sorption porosimetry demonstrated that MIL-160 Moreover, the ball-milled sample exhibited higher crystallinity
(Al) exhibits excellent physicochemical stability given that no than the commercial MIL material.78
changes were observed compared to the starting material.74–76 In our opinion, the modern production of MIL-based MOFs
Another example is the synthesis of Al-MIL-68-Mes ([Al(OH) should move from solvothermal (hydrothermal) methods to
(O2C-C3H4-CO2)]·nH2O).77 This porous material was prepared the modern mechanochemical method (Fig. 10). This solution
by dissolving mesaconic acid (Mes) in water and mixing it after is part of the ecological basis of “green chemistry” due to the
adding NaOH. Then, Al2(SO4)3·18H2O was added as the source fact that solvents are not required, especially organic solvents.
of aluminium(III) ions (3 mmol). This suspension was placed Here, we present a comparison of the preparation of MILs
in a microwave oven and heated for 45 min at 95 °C with stir- using different synthetic techniques in Table 2.
ring. The solid was then filtered and redispersed, while stirring
in water at 25 °C for 30 min. Then, the product was filtered,
rinsed with acetone and dried under ambient conditions.77 5. Production of MOFs based on ZIF
The MOF was heated for 30 min at 90 °C in an oven to activate
it. The specific surface area of MIL-68-Mes was determined to Another class of metal–organic frameworks is ZIFs (zeolite
be 1040 m2 g−1 and VMIC = 0.42 cm3 g−1. Its sorption behaviour imidazole frameworks). Their topology resembles naturally
towards water and methanol vapour was also investigated. The occurring porous materials, i.e., zeolites. The metals used in
water vapour isotherm exhibited a sigmoidal shape without the synthesis of ZIFs are mainly the following cations, i.e., iron
pronounced hysteresis and with a steep increase in uptake at (II and III), cobalt(II), zinc(II), and copper(II). However, the
around p/p0 of ≈0.5 (from 60 mg g−1 at p/p0 = 0.45 to 340 mg element that distinguishes these structures from others is the
g−1 at p/p0 = 0.55) and a maximum capacity of 374 mg g−1 at p/ presence of imidazole organic moieties and their modified
p0 = 0.9, which indicate a similar capacity to that of other derivatives.88 Alternatively, the physicochemical aspect of poro-
water-stable MOFs such as Al-MIL-53-Fum (450 mg g−1) 12 and sity that distinguishes this group of compounds is their higher
CAU-10-H (340 mg g−1).77 Additionally, the nitrogen isotherms thermal and chemical stability, and accordingly these com-
measured prior to and after water sorption were virtually iden- pounds have better use in capturing pollutants. Another
tical, which indicates that the material is chemically stable.77 advantage is their higher stability in both water and oxygen
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Table 2 Comparison of methods for the synthesis of MOFs based on MILs
Temperature Surface area

MOF Method Substrates/solvent [°C] [m2 g−1] Ref.
Large-scale production of MOFs based on MIL

MIL-53 Electrochemical Aluminium electrode, BDC (terephthalic acid), H2O, DMF, KCl 90 1200 73
(Al.)
MIL-53 Electrophoretic Fluorine-doped tin oxide FTO, BDC (1,4-benzenedicarboxylic — — 79
deposition acid)
MIL-100 Spray-drying Fe(NO3)3·9H2O, BTC, DMF 180 1039 80
continuous flow
MIL-53 Flow chemistry Al(NO3)3, terephthalic acid, water 250 919 81
(Al.)
MIL-88A Spray-dryer with three- FeCl3·6H2O, fumaric acid, DMF, MeOH, H2O 180 — 82
fluid nozzle
MIL-53 Flow chemistry Metallic aluminium, BDC, DMF — 1376 83
(Al.)
MIL-100 Wet impregnation FeCl3·6H2O, benzene-1,3,5-tricarboxylic acid, water, [SO3H- 130 — 84
(Fe) (CH2)3-IM]2C4[HSO4]2/Acidic chloroaluminate IL/[BMIM][Cys]/
dual amino-functionalized ionic liquid (DAIL)
MIL-101 Wet impregnation Cr(NO3)3·9H2O, terephthalic acid, water, DAIL, or 220 1587–2049 85
(Cr) [NMP][CH3SO3]/EIMS-HTFSA
Methods for the synthesis of MIL in accordance with the principles of green chemistry
MIL-100 Electrochemical Aluminum electrode, BTC (benzene-1,3,5-tricarbocylate), EtOH, Above 60 969 76
(Al.) H2O
MIL-100 Electrochemical Iron electrode, BTC, EtOH, H2O, MTBS 110 — 84
(Fe)
MIL-100 Mechanochemical H3BTC and Fe(NO3)3·9H2O and tetramethyl ammonium Room 1033 78
(Fe) hydroxide temperature
MIL-91 Solvothermal N,N′-Piperazinebis(methylenephosphonic acid), NaOH, water, Under reflux 360 85
(Ti) titanium oxyacetylacetonate
MIL-160 Hydrothermal Al(OH)(CH3COO)2, 2,5-furandicarboxylic acid, distilled water Under reflux 1150 86
(Al.)
MIL-68- Microwave heating Mesaconic acid (H2Mes), Al2(SO4)3·18H2O, NaOH, water 95 1040 77
mes
MIL-160 Solvothermal Aluminium hydroxide acetate, 2,5-furandicarboxylic acid (FDCA), Under reflux 1150 87
(Al.) deionized water
MIL-53 Stirring at room Aluminium nitrate aqueous solution, Na2BDC, water Room 1048 71
(Al.) temperature temperature
environments (the metal–oxygen bond is hydrolysed in chemical inertia of the sulphur electrode. For the project to be
MOFs).88,89 This class of compounds also plays a significant role commercialized on a large scale, complex nanostructures
in large-scale production, having a significant impact on ecologi- should be developed, due to which the electrode plates will
cal, environmental, and economic aspects. The large-scale pro- possess a high specific energy density.91,92
duction of ZIFs is based on the patents of MOF Technologies Another invention with ZIF as the main material was
and BASF, which use the mechanochemistry and electrochemical related to a catalyst for the synthesis of methyl glycolate (MG)
techniques to synthesise ZIF-67 and ZIF-8. Significantly, these by the hydrogenation of dimethyl oxalate (DM).93 MG was used
patents use negligible amounts of solvents or none at all, which as the substrate for the synthesis of dimethyl acid, polyethyl-
is consistent with the principles of green chemistry.90 ene, glycine, and methyl glyoxylate. Many industrial plants
The first example of the application of an MOF based on produce ethylene glycol (EG) through the DMO hydrogenation
ZIF was zeolite imidazole frameworks in lithium–sulphur bat- reaction (Fig. 18).93 Production on a larger scale has lower pro-
teries.91 A combination of ZIF-8 containing zinc ions, ZIF-67
containing cobalt ions, and carbon tubing was used. The
metal–organic frameworks were located in the part of the
membrane to improve absorption and increase the chemical
energy storage capacity.91 For the synthesis of the membrane,
zinc nitrate hexahydrate and cobalt nitrate hexahydrate salts
with 2-methylimidazole were used. The membrane constructed
in this way possessed electronic adsorption channels for poly-
sulfides. It had a large surface area and showed conductive
properties, enabling it to fulfil this function. The modification
of ZIF improved the synthesis reaction kinetics and inhibited Fig. 18 Hydrogenation reaction of dimethyl oxalate, methyl glycolate,
the so-called pendulum effect of polysulfides and electro- and ethylene glycol.93
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duction costs and is respected by other companies around the authors optimized the activation of the porous material, which
world. However, to achieve satisfactory results including high had a significant impact on its specific surface area. The syn-
efficiency and low cost, it was necessary to use an appropriate thesized ZIF-8 suspension was diluted with ethanol in a ratio
catalyst, i.e., ZIF based on cobalt(II).93 The hydrogenation reac- of 1 : 1, 1 : 2 or 1 : 3. Then, it was pumped through the coil at
tion of dimethyl oxalate, methyl glycolate, and ethylene glycol ambient pressure, where the coil was (1) kept at room tempera-
is as follows: ture, (2) heated to 50 °C in a water bath, (3) sonicated in a
An important addition was the use of cobalt(II) phosphide water bath at room temperature and (4) sonicated in a water
together with silicon(IV) oxide. The introduction of phosphorus bath at 50 °C. Finally, the collected samples were collected,
molecules as an electron promoter resulted in improved elec- centrifuged and dried at 70 °C in the air and at ambient
tron efficiency. The zeolite catalyst was characterized by high pressure.96 The highest surface area was obtained by washing
stability at room temperature and in air (about 1000 h) and the ZIF-8 suspension with ethanol in a ratio of 1 : 2 with soni-
effective selectivity (reaching almost 100%); in addition, it was cation at room temperature (BET = 1772 m2 g−1). A comparable
synthesized according to the principles of green chemistry.93 value was obtained by washing the porous material with
Another example of the use of ZIF in large-scale glass pro- ethanol in a 1 : 1 ratio at room temperature (BET = 1700 m2
duction is ZIF-62-[Zn(Im)1.75(bIm)0.25] (Im = C3H3N2-imidazo- g−1). Alternatively, the least effective activation method was
late), (bIm = C7H5N2-benzimidazolate).57 The organometallic washing ZIF-8 with ethanol in a ratio of 1 : 3, using sonication
zeolite compound is a promising research product due to its at 50 °C (BET = 1276 m2 g−1).96
unique properties such as thermal stability and high melting In 2018 Marrett et al.97 presented the synthesis of ZIF-8
point viscosity. Scientists have shown that as the melting time using ZnO and HmeIm (ratio of 1 : 2.2) to ensure that
of ZIF-62 increases, the resulting toughened glass changes sufficient ligand was present to obtain complete ZnO conver-
from a transparent form (up to 5 min) to glass foam sion. The reactants were placed on filter paper in an scCO2
(30 min).94 In the intermediate stage (more than 10 min), the extraction vessel at 130 bar and 65 °C for 5 min.97 Larger-scale
density of the glass material decreases. However, the structural reactions (150 g, 200 g) were carried out in a paddle mixer
composition does not change with an increase in the melting using scCO2 for 2 h at 130 bar and 65 °C. The reaction product
time.94 was washed by stirring in MeOH overnight and pumped at
A new heterogeneous biocatalyst, ZIF-67, together with the 100 °C to remove the unreacted ligand. To illustrate its scal-
enzyme lipase have attracted attention from one of the largest ability, the 100 g synthesis of ZIF-8 was achieved in 2.5 h using
biofuel producers.95 This is a remarkable example, where the a 50% stoichiometric excess of HmeIm. These larger-scale
use of the biocatalyst produces biodiesel by esterifying reactions gave a shaped product in the form of a cylindrical
soybean oil. Scientists have proven that after 6 transesterifica- block. The BET area ranged from 1687 to 1894 m2 g−1.
tion cycles, the enzyme efficiency does not decrease.95 Optimization of the research showed that the change in temp-
Consequently, it is an extremely efficient catalyst that can be erature (45–90 °C) and pressure (90–130 bar) did not signifi-
used several times. Moreover, the organometallic scaffold of cantly affect the reaction.97
the complex compound protects the lipase against inactivation Schejn et al. reported 98 the synthesis of a ZIF-8 crystal pre-
under harsh reaction conditions, e.g., high temperature. pared by mixing 2-methylimidazole with various zinc salts (Zn
Therefore, the above-mentioned biocatalyst is an ideal example (acac)2, Zn(NO3)2, ZnSO4 or Zn(ClO4)2) in methanol using the
for industrial use on a large scale.95 molar ratio of Hmim/Zn2+ salt of 8/1. The synthesis was con-
An interesting article was presented by the Munn group96 ducted under nitrogen flow at room temperature with stirring
who synthesized ZIF-8 on a large scale using 2-methyl- for 1 h.98 Both the particle size and morphology were found to
imidazole, ammonium hydroxide and an aqueous solution of be dependent on the reactivity of the Zn(II) salt. By using
zinc acetate dihydrate using a continuous flow method. ZnCl2, Zn(acac)2 or ZnI2, crystals with sizes ranging from ca.
Activated ZIF-8 was produced on the lab-scale and pilot-scale 350 and 650 nm were obtained. Finally, the ZnBr2 low reactive
at a rate of 27 g h−1 and 810 g h−1, respectively, with the acti- salt was found to generate microcrystals. By analysing the ther-
vated material showing a surface area of 1800 m2 g−1. This mogravimetry and BET measurements of the ZIF-8 crystals
setup consisted of a concentric pipe-in-pipe arrangement, made from Zn(NO3)2, Zn(acac)2 and ZnBr2, it was found that
which allowed rapid mixing of the preheated downstream, the changes in particle size induced changes in stability and
delivered through the inner pipe, with the room temperature adsorption properties. It was found that small ZIF-8
upstream.96 This arrangement allows for instant mixing of the crystals made from Zn(NO3)2 showed the largest surface area
reactants and short residence times given that the resultant (1700 m2 g−1 and pore volume 0.66 cm3 g−1) and the best cata-
particle suspension exits at the top of the reactor where it is lytic activity in the Knoevenagel and Friedländer reactions.
rapidly cooled by a cooling jacket. The pilot-scale sample was In turn, crystals were prepared from ZnBr2 (SBET = 1713 ±
synthesized at 100 °C, and XRD analysis confirmed that there 45 m2 g−1 and pore volume = 0.63 cm3 g−1) and Zn(acac)2 (SBET
was no trace of crystalline impurities. Additionally, the compli- = 1477 ± 36 m2 g−1 and pore volume = 0, 55 cm3 g−1).98 The
ance of the BET surface with an equivalent sample on a labora- most significant feature observed in the TGA results is the
tory scale was confirmed. However, the morphology of ZIF-8 size-dependent thermal stability up to 300 °C in the case of
differed from that synthesized on the laboratory scale. The the smaller 141 nm-sized nanocrystals prepared from Zn
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Table 3 Comparison of methods for the synthesis of MOFs based on ZIFs
Surface area
MOF Method Substrates Solvent [m2 g−1] Ref.
Large-scale production of MOFs based on ZIF

ZIF- 8 Solvothermal Zinc nitrate hexahydrate, DMF, H2O 1300–1800 99
2-methylimididazole (Hmim) and
100
ZIF-8 Electrochemical Zinc electrode, 2-methyl imidazolate AcN, H2O, DMF, EtOH, 1400–1700 101
MTBS
ZIF-8 Electrochemical Zinc electrode, 2-methyl imidazolate DMF, H2O, MTBS 1730 102
ZIF-4 Electrochemical Zinc electrode, imidazole DMF, H2O, MTBAMS (tri- 750 102
butylmethyl-ammonium
methyl sulphate)
ZIF-14 Electrochemical Zinc electrode, 2-ethylimidazole DMF, H2O, MTBAMS 598 102
ZIF-7 Electrochemical Zinc electrode, benzimidazole DMF, H2O, MTBAMS 358 102
ZIF-67 Electrochemical Cobalt electrode, 2- methylimidazole DMF, H2O, MTBAMS 1521 102
Synthesis methods of ZIF in accordance with principles of green chemistry
ZIF-8 Bipolar electrochemistry Zinc wire, 2-methylimidazole Water — 103
ZIF-8 Flow chemistry Zinc nitrate hexahydrate, Ammonia, water 1770 104
2-methylimidazole
ZIF-8 Flow chemistry Zinc acetate,2-methylimidazole, Water, ethanol 1800 96
ammonium hydroxide
ZIF-8 Ionothermal 2-methylimidazolate, zinc cations with [BMIM][Tf2N]/C5H15NO2 374 31
sodalite topology
ZIF-8 Extraction with supercritical Zinc oxide, imidazole/2-ethylimidazole, Supercritical carbon dioxide 1687–1894 105
CO2
ZIF-8 Extraction with supercritical 2-Methylimidazole, ZnO Water, supercritical carbon 1229–1315 98
CO2 dioxide
ZIF-8 Hydrothermal 2-Methylimidazole, ZnO nanorods layer Water, methanol, ethanol — 98
(hexamethylenetetramine, Zn(NO3)2·6H2O
in water)
ZIF-8 Synthesis was conducted Zn(Oac)2, Hmim Methanol 1477 ± 36 98
under nitrogen flow at room
temperature
ZIF-8 Extraction with supercritical Zn(acac)2 ·H2O, Hmim Supercritical carbon dioxide 1319–1702 106
CO2
ZIF-8 Extraction with supercritical Zn(acac)2, Hmim Supercritical carbon 1156 106
CO2/Ionothermal dioxide, [emim][BF4] and
107
ZIF-8/beech Stirring at room temperature Zn(NO3)2·6H2O, 2-methylimidazole Methanol, deionized water 26 107
composite
(NO3)2, and up to 390 °C in the case of the larger 1050 nm- structures discussed herein is UiO (University of Oslo), which
sized crystals prepared from ZnBr2. A sharp weight loss step of was discovered by Lillerud.108 An example worth noting is
ca. 63–64% was observed for all the nanocrystals upon further UiO-66, which is made of zinc(IV) cations and SBU secondary
increasing the temperature from 400 °C to 500 °C, indicating building blocks (acting as Lewis acids due to free electron
the thermal decomposition of the ZIF-8 nanocrystals in this pairs). This organic metal network is described in the litera-
temperature range.98 ture as an ideal absorbent for heavy metal ions, organic pollu-
In summary, the production of ZIFs on an industrial scale tants, and biomacromolecules. UiO-66 is the most popular
has many advantages because it is possible with several compound of the UiO subclass due to its remarkable chemical
methods, not only the traditional methods of hydrothermal and mechanical stability.108,109 It is resistant to acids and
and solvothermal synthesis. Sonochemical, mechanochemical, bases, and avoids the use of toxic organic compounds such as
and method-accelerating agent methods are used to obtain DMF, acetone, and methanol, and therefore it is perfect for
ZIFs. We present a comparison of the preparation of ZIFs wastewater treatment.109,110 An additional aspect of improving
using different synthetic techniques in Table 3. the issue of contamination monitoring is the modification of
the obtained UiO by adding a luminescent group next to the
linker. The luminescent groups in MOFs based on UiO are
6. Production of MOFs based on UiO lanthanide groups. For example, Govindaraju et al. created a
new photoluminescent compound (AuNCs@UiO-66)111 for the
Removal of chemical pollutants in the ecosystem is extremely determination of Hg2+ at very low concentrations, Dong et al.
important because they endanger the lives of humans and prepared an Eu3+@UiO-66 nanocomposite (organic linkers
animals. Ecologists control the parameters of pollution and were 1,3-benzenedicarboxylic acid, dipicolinic acid, and zirco-
the use of absorbents, and therefore another subclass of MOF nium chloride),112 and Zhu and Yan synthesized
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MPO, diisopropyl fluorophosphate = DFP, and Soman = GD.84

UiO-66-NH2 is a heterogeneous catalyst synthesized according
to the principles of green chemistry because scientists mini-
mize the production of hazardous substances during the
reaction and limit the use of solvents, minimizing their
harmfulness.114
In 2018 Karadeniz et al. reported115 the mechanochemistry
synthesis of UiO-66-NH2 in a mill, where the precursors

[Zr6O4(OH)4(CH3COO)12]2 and 2-aminoterephthalic acid (in a
molar ratio of 1 : 12) were milled with 50 µL of H2O. This
process took 90 min and the yield of the product was 95% and
its specific surface area was 815 m2 g−1. Alternatively, changing
Fig. 19 Scheme of a catalyst-fiber composite for adsorbing and
the water to methanol increased the surface area to 945 m2
decomposing a chemical agent, which involves the steps of electro- g−1. The synthesis of UiO-66-NH2 was readily applicable on a
spinning a nanofiber-forming polymer solution and dispersing a metal– 10-gram scale by using a planetary mill (BET = 610 m2 g−1) and
organic framework between a nanofiber surface and a nanospace was also performed by solid-state flow synthesis using twin-
formed by the nanofibers by electro-spraying a UiO-66-based MOF-
screw extrusion (TSE) (BET = 885 m2 g−1), affording more than
containing solution.114 Created with BioRender.com.
100 g of catalytically active UiO-66-NH2 material in a continu-
ous process at a rate of 1.4 kg h−1. In turn, UiO-66 was syn-
thesized in two reaction steps. Terephthalic acid, triethylamine
Eu3+@UiO-66-NH2-IM (IM = imidazole-2-carboxaldehyde) for and 50 µL of H2O were placed in a Teflon apparatus, and then
the determination of aniline up to about 0.1%.113 milled for 30 min at 25 Hz using two stainless steel beads.
UiO-66-NH2 (containing zircon cations and terephthalic Then, the Zr12 precursor was ground and added to this
acid as the ligand) is also described as an excellent catalyst mixture.115 The materials were stirred for an additional
for the hydrolysis reactions of highly toxic substances such as 90 min. The resulting final product was washed with methanol
poison warfare agents, e.g., organophosphonates (Fig. 19). and dried in air (SBET = 1145 m2 g−1). Alternatively,
Due to its numerous hydroxyl groups, it can decompose sub- changing water to methanol reduced the specific surface area
stances that threaten human life, such as paraoxon-methyl = to 1020 m2 g−1.115
Table 4 Comparison of the methods for the synthesis of MOFs based on UiO
Reaction BET [m2

MOF Methods Substrates time g−1] Ref.
Large-scale production of MOFs based on UiO

UiO-66 Continuous flow chemistry ZrCl4, 1,4-tricarboxylic acid (BDC), DMF 10 min 1186 118
UiO-66 Solvothermal BDC, ZrCl4, water, DMF, benzene, and acetone 24 h 1187 119
UiO-66 Anodic and cathodic- Zirconium oxide foil, ZnO2, BDC, DMF, H2O, acetic acid, — — 120
electrophoretic deposition HNO3
UiO-66 Electrophoretic deposition FTO (fluorine-doped tin oxide), BDC, Zr-containing nodes — — 121
UiO-66- Continuous flow ZrCl4, 2-nitro-BDC, acetic acid, H2O 63 s 679 121
NO2
UiO-66- Continuous flow ZrCl4, 2-NH2-BDC, DMF, H2O 63 s 752 121
NH2
UiO-66 Continuous flow ZrCl4, BDC, DMF, H2O 63 s 1106 121
Hf-UiO-66 Microwave [Hf6O4(OH)4], BDC, DMF, CH3COOH 3 min 950 122
Zr-UiO-66 Microwave [Zr6O4(OH)4], BDC, DMF, CH3COOH 3 min 1400 122
UiO-66 Wet impregnation Zirconium tetrachloride, terephthalic acid, hydrochloric 16 h 523–996 31
acid DMF, [PSMIM][HSO4]
Synthesis methods of UiO in accordance with principles of green chemistry
UiO-66 Synthesis with green bioderived Zirconium(IV) oxychloride octahydrate, terephthalic acid, 24 h 500–1300 116
solvent – Cyrene Cyrene
UiO-66 Solvothermal Zr(SO4)2·4H2O, H2BDC-NH2(2-aminoterephthalic acid), — — 123
water
UiO-66 Mechano-synthesis [Zr6O4(OH)4(C6H5CO2)12], terephthalic acid, a small amount 75 min 1020 124
of methanol
UiO-66 Mechano-synthesis [Zr6O4(OH)4(C2H3CO2)12], terephthalic acid, a small amount 75 min 1020 124
of methanol
UiO-66 Mechano-synthesis [Zr12O8(OH)8(CH3COO)24], terephthalic acid, 90 min 1145 124
UiO-66 Mechano-chemistry [Zr6O4(OH)4(CH3COO)12]2, triethylamine, terephthalic acid, 90 min 1145 124
50 µL H2O
UiO-66- Mechano-chemistry [Zr6O4(OH)4(CH3COO)12]2, 2-aminoterephthalic acid, 50 µL 90 min 815 124
NH2 H2O
View Article Online
An interesting article on the green synthesis of UiO-66 was

presented by Zhang et al.116 Zirconium(IV) oxychloride octahy-
drate was dissolved in Cyrene, acetic acid and water. After ter-
ephthalic acid was dissolved in Cyrene, it was added to the
mixture with Zr(IV). The mixture was heated at 80 °C for 12 h.
The specific surface area was 500 m2 g−1. This is a much lower
value than the synthesis with DMF, where SBET = 1300 m2 g−1.116
In summary, UiO-66 is supplied in large numbers on an

industrial scale by Strem Chemicals.117 This compound is charac-
terized by high chemical and mechanical stability and a large
specific surface.117 Due to the variety of methods for obtaining
MOFs based on UiO, namely, the mechanochemical method,
microwave-assisted procedure, continuous flow method, and
electrochemical method, the materials can be obtained based on Fig. 21 Continuous and large-scale production process developed by
environmentally safe procedures. Table 4 shows the preparation Norafin in the context of the NanoMOF project.17 Continuously MOF-
particle-loaded PET nonwovens (HKUST-1 < 63 mm from Johnson
of UiO using different synthetic techniques.
Matthey Company; loading capacity: 25 g m−2.17 Created with
BioRender.com.
7. Production of MOFs based on BTC

Currently, there are several MOFs based on BTC (1,3,5-benze- Textile technology is one of the fastest-growing industries.
netricarboxylic acid) on the market.125,126 MOFs based on BTC Unexpectedly, metal–organic frameworks have found appli-
are commercially available through Merck.127 They are also cation in this field. The resistance to moisture and the
produced by BASF (Fe-BTC) and MOF Apps MOF Technologies mechanical and temperature stability of porous structures
(Cu-BTC and MOF-199).83 BASF also boasts a patented electro- make them attractive to many companies that provide protec-
chemical synthesis method that uses sacrificial anodes as a tive clothing to healthcare professionals, chemists, biologists,
metal source. In this way, harmful acid residues such as chlor- and soldiers.17 Companies such as Norafin and Blucher are
ides and nitrates are avoided.97 The validity of this method great examples of introducing metalorganic frameworks in the
was confirmed by Campagnol et al. They reported the electro- textile industry.17 The combination of MOFs with textiles
chemical synthesis and investigation of the luminescent pro- based on PET, linen, and aramid, which have been coated with
perties of Gd-BTC and Tb-BTC (electrolyte: MTBS, solvent: a polymer binder (latex and acrylate), is carried out by electro-
methanol/water).128 prenaturation or chemical fixation. The penetration of
Problems with water contamination with drugs or poiso- HKUST-1 and Fe-BTC in the voids of the fibers turned out to
nous chemicals are still the main topic of scientists dealing be a brilliant idea because their adsorption performance
with environmental analysis. Interesting physicochemical pro- against ammonia, hydrogen sulfide acid, and cyclohexane is
perties are demonstrated by the organometallic skeleton of Fe- promising17 (Fig. 21).
BTC.129 This MOF based on BTC is combined with magnetite It is also worth paying attention to a few examples of the
Fe3O4 in a solvothermal synthesis. This synthesis procedure synthesis of MOFs using deep eutectic solvents. Zhao et al.
increased the MOF absorption capacity. It was used in the reported131 that they synthesized [NH4][Zn(BTC)(NH3)2]·H2O
adsorption of drugs such as diclofenac sodium (DCF), ibupro- using Zn(CH3COO)2 as the zinc salt, BTC as the ligand, and
fen (IB), and naproxen sodium (NS) (Fig. 20). This represents a choline chloride, urea, and deionized water as the solvent.131
new functional and stable composite material.130,131 The yield was 37.9%. The porous material showed a weight
loss of 20.73% in the temperature range of 30–300 °C, corres-
ponding to the loss of one water molecule, one NH4+ cation
(5.26%), and two NH3 molecules (9.94%) per formula unit.
The weight loss of [NH4][Zn(BTC)(NH3)2]·H2O between 300 °C
and 550 °C may be related to the decomposition of BTC
ligands and the collapse of the framework.131
Siew et al. presented an article in 2018132 about the green syn-
thesis of an MOF based on BTC. Both Cu3(BTC)2(H2O)3·10H2O
and Cu2(OH)(BTC)(H2O)·2H2O were successfully synthesized by
changing the synthesis conditions. The slower rate of addition
of the Cu(Oac)2 precursor solution to H3BTC prevented the for-
mation of bidentate inter-cluster bridges during the in situ
Fig. 20 Chemical structure of diclofenac sodium (DCF), ibuprofen (IB), installation of Cu3(BTC)2(H2O)3·10H2O. In turn, Cu2(OH)(BTC)
and naproxen sodium (NS). (H2O)·2H2O showed a lower BET surface area and a smaller pore
View Article Online
volume compared to Cu3(BTC)2(H2O)3·10H2O. The specific

surface area of Cu2(OH)(BTC)(H2O)·2H2O when mixing the reac-
tants for 1 h was 36 m2 g−1, while that upon mixing for 24 h was
SBET = 61 m2 g−1. Also, large differences were noted when the
copper salt and H3BTC were mixed before adding water (SBET =
253 m2 g−1).132 In turn, the Cu3(BTC)2(H2O)3·10H2O synthesized
by the dropwise addition of Cu(Oac)2 solution into the H3BTC
mixture and mixing for 24 h contributed to the formation of a

porous material with a specific surface area of 471 m2 g−1. The
10-fold higher concentration of Cu and H3BTC contributed to
the material with SBET = 708 m2 g−1. Additionally,
Cu3(BTC)2(H2O)3·10H2O had a higher adsorption capacity
(16 mg g−1) compared to Cu2(OH)(BTC)(H2O)·2H2O (3.79 mg
g−1). Therefore, it can be concluded that CuBTC with
Cu3(BTC)2(H2O)3·10H2O is a potentially better adsorbent.132
Many reviews and articles demonstrate the synthesis of
MOFs based on BTC; however, works with chloride salts,
nitrates, and small amounts of DMF cannot be included
herein. This creates an opportunity for the development and
introduction of the principles of green chemistry in synthetic
methods based on the BTC ligand.131
Fig. 22 Two-step synthesis of the tetra acid ligand for NU-1000. No
Summarizing the recent achievements in the synthesis of need for chromatographic purification.133 Created with BioRender.com.
MOFs based on BTC, it is worth noting that with an increase
in the amount of water as the solvent in the synthesis, the pro-
ducts are obtained in the form of larger crystals. Depending
on how we intend to obtain the final morphological effect, the
amount of water should be appropriately adjusted the syn-
thesis protocol.
8. Production of MOFs based on NU

NU-1000 (NU = Northwestern University) is a well-known meso-
porous photocatalyst with pore sized of above 2 nm, with the
general formula of [Zr6(μ3-OH)4(μ3-O)4(H2O)4(OH)4(TBAPy)2] Fig. 23 Synthesis of NU-1000 from H4TBAPy and ZrOCl2 with benzoic
[H4TBAPy = 1,3,6,8-tetrakis( p-benzoic-acid)pyrene].133 MOFs acid as a modulator. NU-1000 can be prepared via a one-step reac-
tion.133 Created with BioRender.com.
based on NU have been reported as an organometallic skeleton
capable of gas separation and heterogeneous catalysis.133–135
Their synthesis on a large scale is possible thanks to the use of
inexpensive substrates such as tetrabromopyrene and 4-(ethox- chemical properties.109 BiOI@NU-1000 exhibits high porosity,
ycarbonylphenyl)boronic acid.112 The procedure for the prepa- crystallinity, and the best photocatalytic performance com-
ration of NU-1000 can be performed in 10 days without the pared to other MOF compounds applied to date for PHE
need for the purification of the final products, yielding ( photocatalytic hydrogen evolution), with the hydrogen pro-
200 mg–2.5 g of NU-1000.136 One of the most popular methods duction efficiency of 610 μmol h−1 g−1. It has also been
for the synthesis of NU-1000 is presented in Fig. 22 and 23. reported that the photocatalyst separates photoinduced charge
This method was published in Nature and is most often used carriers, improves the photocurrent intensity, and reduces the
by scientists. However, due to the use of DMF in the final stage photoelectric impedance.133,134 The high photocatalytic
of the synthesis, it cannot be called a “green” method for the activity of BiOI@NU-1000 under visible light (400–800 nm)
synthesis of MOFs. This research area remains a field for the should also be emphasized due to its large specific surface
development of new synthetic techniques because thus far it area, the construction of the photocatalyst according to the “Z”
has not been possible to propose a method for the synthesis of scheme, and its highly dispersed heterojunction.132
NU-1000 consistent with the principles of green An interesting example is the synthesis of NU-901 presented
chemistry.133–136 by the Fidelli group in 2018.135 These scientists used
Several products have been produced based on the modifi- mechano-synthesis, in which the metal source was
cation of NU-1000 as the parent compound, which is a useful Zr12O8(OH)8(CH3COO)24 and the organic ligand was the widely
compound for several applications due to its rich physico- used H4TBAPY. The surface area of NU-901 was 1250 m2 g−1.
View Article Online
Table 5 Comparison of MOF synthesis methods based on NU-1000
MOF Method Substrates BET surface area [m2 g−1] Ref.
NU-1000 Electrophoretic FTO — 79

deposition
NU-1000 Phase-pure Zirconyl chloride hydrate, benzoic acid in DMF, — 137 and 138
TBAPy (1,3,6,8-tetrakis(p-benzoic acid)pyrene)
NU-1000-BzTz Phase-pure Benzothiazolium salt, BzTz, acetonitrile, zirconyl — 139 and 140
chloride hydrate, TBAPy

NU-1000 Phase-pure Zirconyl chloride hydrate, TBAPy trifluoroacetic acid (TFA) 2220 141
NU-1000-TFA Phase-pure Zirconyl chloride hydrate, TBAPy trifluoroacetic acid (TFA) 2180 141
However, there are only a few examples in the literature on the

synthesis of NU according to the principles of green chemistry.
Chlorides or nitrates are still widely used metal salts. Most of
the methods also use the environmentally harmful DMF in the
final stage.135
More than 10 years ago, the production of NU-based MOFs
Fig. 24 Reaction scheme for the synthesis of Cu3(BTC)2 metal organic
was carried out with the use of environmentally toxic organic
framework (HKUST-1). Created with BioRender.com.
solvents such as DMF using the solvothermal method.
However, currently, the synthesis of this type of MOF is par-
tially carried out by the sonochemical method and mechano-
Copper(II) nitrate hydrate was mixed with benzenetricarboxylic
synthesis. Here, we present a comparison of the preparation of
acid dissolved in a mixture of choline chloride and 1,3-di-
NU-1000 using different synthetic techniques in Table 5.
methylurea (1 : 2 molar ratio). The mixture was heated to about
70 °C and ultrasonically treated for 30 to 120 min at different
power levels.144 The product was washed with deionized water
9. Production of MOFs based on and ethanol before being left to cool to room temperature and
HKUST dried at 80 °C for 5 h and activated at 180 °C for 12 h under
vacuum. Depending on the washing method, different BET
The last subclass of MOFs discussed herein is HKUST (Hong specific surface areas were obtained.144 Washing with de-
Kong University of Science and Technology). HKUST-1 is the ionized water once gave SBET = 31 m2 g−1, while washing twice
most popular and widely known MOF, which is produced by gave SBET = 1449 m2 g−1, and Vpore = 0.60 cm3 g−1. However,
BASF and distributed by Merck.83 Together with ZIF-8, it is syn- the highest specific surface was obtained by washing 2 times
thesized via the electrochemical method using protector with water and twice with ethanol, giving SBET = 1822 m2 g−1
anodes with microwave heating (MW). The combination of and Vpore = 0.76 cm3 g−1.144
these techniques has a positive effect on the yield (96%), STY Xu et al. also presented an interesting method for the syn-
(64 800 kg d−1 m−3), BET number (1550 m2 g−1), pore volume thesis of HKUST-1.145 NaOH was added to an aqueous Cu
(0.63 cm3 g−1), and quality of the obtained product, avoiding (NO3)2·3H2O solution, and then the ethanolic H3BTC solution
the use of metal salts such as chlorides and nitrates.44 The was added and sonicated for 5, 10, 30, 60, 120 min at room
space–time efficiency (STY) is a parameter that determines temperature.145 The sample was washed thoroughly with
whether a process is profitable. According to the calculations ethanol and dried at 100 °C overnight. The BET surface area
of scientists, the profitability of processes without the use of was 1721 m2 g−1. HKUST-1 was used as the adsorbent to
solvents (or a negligible amount) is 1 to 3 orders more finan- remove sulfur compounds from a model liquid fuel. The
cially advantageous.142,143 results showed that the adsorbing capacity of Cu-BTC for DBT
Also a method called synthesis by extrusion is notable.18 It at room temperature is 8 mg S g−1.145
is based on synthesis without solvents or their use in negli- One of the first reports on the electrochemical synthesis of
gible amounts (mechanochemistry), which is consistent with HKUST-1 was presented by Mueller et al.56 Specifically, 5 mm
the principles of green chemistry. Scientists using twin and thick copper plates were placed as anodes in the electro-
single screw extruders made it possible to synthesize HKUST-1 chemical cell, while H3BTC was dissolved in methanol.56
on a macro scale. Cu(OH)2 together with BTC serve as sub- HKUST-1 was synthesised within 150 min at a voltage of 12–19
strates, with the addition of a small amount of industrial V and current of 1.3 A. The specific surface area was 1649 m2
alcohol (32% by weight) (Fig. 24). The maximum throughput g−1, and finally 1820 m2 g−1 after activation at 250 °C. The size
reached 1 kg per hour and the BET surface area was of the HKUST-1 crystals ranged from 0.5 nm to 5 nm.56
1600–1850 m2 g−1.18,142 Currently, MOFs based on HKUST are produced with the
Notably, an innovative method for the sonochemical syn- use of solvents such as ethanol, isopropanol, and hydrochloric
thesis of HKUST-1 using DESs was proposed by Kim et al.144 acid via the sonochemical method. This approach is halfway in
View Article Online
Table 6 Comparison of the methods for the synthesis of MOFs based on HKUST-1
BET surface
Method of synthesis Substrates Solvent and electrolyte area [m2 g−1] Ref.
Large-scale production of MOFs based on HKUST-1

Electrochemical Copper electrode, benzene EtOH, H2O, methanol acetonitrile, DMF, DMSO, 1153–1624 143
1,3,5-tricarboxylate MTBS
Electrochemical Copper electrode, Cu EtOH, H2O, MTBS 1309 146
(NO3)2·3H2O, BTC (trimesic

acid),
Spray-dryer (two-fluid Cu(NO3)2·2.5H2O, BTC DMF, EtOH, H2O 1260 147
nozzles)
Mechanochemical Copper(II) hydroxide trimesic MeOH 1738 148
acid
Solvothermal Cu(NO3)2·2.5H2O, BTC DMF : H2O 1500–2100 149
and
150
Continuous flow scCO2 Cu(NO3)2·2.5H2O, BTC Dry DMSO, methanol, supercritical carbon dioxide 1616–1220 149
extraction
Synthesis methods of HKUST-1 in accordance with principles of green chemistry
Electrochemical Copper electrode, 1,3,5- MeOH 1820 56
benzenetri-carboxylic acid
Electrochemical Copper mesh, benzene 1,3,5- EtOH : H2O, MTBS — 143
tricarboxylic acid
Electrochemical Copper electrode, benzene EtOH : H2O, MTBS — 130
1,3,5-tricarboxylic acid
Sonochemical with heating Cu(NO3)2·3H2O, BTC, Choline chloride/urea (molar ratio 1 : 2) 1506 151
and under pressure and
152
Sonochemical Cu(NO3)2·3H2O, BTC, Choline chloride, 1,3-dimethylurea (molar ratio 31–1822 144
1 : 2), the product was washed twice with de-ionized
water and ethanol
Ultrasonic at room (Cu(NO3)2·3H2O, H3BTC, NaOH, deionized water 1721 145
temperature ethanol
Stirring at room temperature Copper acetate monohydrate Methanol, distilled water 708 153
([Cu(Oac)2·H2O]), BTC
line with the principles of “green chemistry” because, in our method can be used on a large scale for the activation and
opinion, attempts should be made to develop protocols for the continuous synthesis of MOF materials. In addition, it
synthesis of these compounds using ionic liquids as solvents, enables the recovery of wastewater and unreacted material,
given that they can be recovered during production and con- which is a challenge in water-based hydrothermal and super-
tinuously reused. Here, we present a comparison of the prepa- critical systems. However, the authors used DMF, and there-
ration of HKUST using different synthetic techniques in fore it is worth trying to use green solvents and other sub-
Table 6. strates to test whether it is possible to obtain MOFs other
than UiO.154
Also, several pre- and post-synthetic modification methods
10. Conclusions and future usually alter the characteristics of the pores, which poses a
perspectives challenge for subsequent applications. Therefore, in our
opinion, experimental research should be combined with
Organometallic frameworks are widely used in catalysis, sep- computational design to obtain materials with high physico-
aration, absorption, and storage. The increasing number of chemical stability and high porosity. The precise location of
patents have enabled the production of MOFs on a large the functional groups and a thorough understanding of the
scale. However, it is necessary to consider the economic limit- application mechanisms in stable metal–organic frameworks
ations, excessive use of solvents, and attention to the possi- will ensure optimal reaction efficiencies and the possibility of
bility of using organometallic structures in several cycles. large-scale application. Moreover, it seems attractive to
Future research should focus on combining synthetic tech- conduct systematic studies on mechanical stability with the
niques such as MW or electrosynthesis with flow-reactor post- use of XRD diffraction, radial crushing strength, and theore-
processing. An interesting proposal is a novel method for the tical calculations. Undoubtedly, the development of the stabi-
continuous synthesis of UiO-66 using supercritical carbon lity of the MOF and its interaction with other fields of
dioxide (scCO2) introduced by a custom counter-current research will lead to more promising and innovative
mixer to provide enhanced heat and mass transfer to MOF applications.
precursor materials. The production rate was 104 g h−1 and We sincerely hope that this review will inspire other
the reaction time was <3 s. The authors showed that this scientists and research groups to create new, innovative
View Article Online
DES). However, there are many disadvantages in the prepa-

ration of bioMOF, e.g., poor chemical and thermal stability as
well as lack of control over porosity. In addition, more
advanced technology will be needed for potential industrializ-
ation. In contrast, in biomass@MOF, higher porosity and
surface area are preferred, the formation of toxic by-products
is avoided, improved mechanical properties and biocompat-
ibility are noticeable and re-use is possible. The degradation of

MOFs is particularly important due to the release of metal
ions and organic linkers into the environment and their
accumulation in organs where short-term oxidative stress may
occur, causing severe toxicity. We suspect that the develop-
ment of bioMOF may take a similar form to the topic related
to nanoparticles, where new plant extracts are increasingly
used for their production. In summary, in striving for sustain-
able development, the rational and effective use of biomass
Fig. 25 Examples of solvents, metal ions, and ligands that fit with the and biomolecules complies with the requirements of green
principles of green chemistry and those that are harmful and poiso-
development and undoubtedly contributes to environmental
nous.155 Created with BioRender.com.
remediation.157–159
Due to their extremely high level of porosity and large
specific surface area, MOFs are considered important
porous materials to improve the environmental aspects. The materials for a variety of applications. By selecting the appro-
unlimited possibilities of the application, modification, and priate metal fasteners and knots, the average pore size and
creation of composite MOFs allow for their wide application MOF area can be easily adjusted. Analyzing the results pre-
following the principles of green chemistry. This should be a sented herein, we can say that green solvothermal synthesis
common topic these days, and thus we encourage the use of methods using Ils as solvents are troublesome due to the clog-
ionic liquids instead of harmful, poisonous solvents such as ging of the MOF pores and reduction of their specific surface
DMF.136 The new challenges for scientists represent a bright area. Therefore, we think that a good solution would be the
future for the development of MOFs around the world. design of carriers, e.g., carbon nanotubes, or to use cheaper
We prepared a graphic presenting the solvents, metal ions, DES equivalents. To date, the MOFs synthesized via mechano-
and organic linkers that comply with the principles of chemical and electrochemical methods and the continuous
green chemistry, as well as those that should be avoided due flow method have the highest porosity. However, each case
to their harmfulness to people and the environment should be analyzed individually because, depending on the
(Fig. 25). optimization, where the range of SBET values varies between
Green solvents are non-toxic, recyclable, biodegradable, and 1000–2000 m2 g−1. This shows how important it is to finally
may not involve a high energy cost of synthesis. Several activate and remove the solvent from the MOF pores to make it
alternative solvents that fulfill, to a greater or lesser extent, this as porous as possible.
definition are included in Fig. 26.137 Analyzing the articles on The thermal decomposition of MOF materials is related to
MOFs, we think that future perspectives will focus on the the breaking of their coordination bonds. The thermal stability
increasing use of biomass for the synthesis of new high-per- of MOFs is usually determined by the strength of their coordi-
formance, biodegradable, porous green materials containing nation bonds, which can be increased by replacing low-value
biocompatible transition metal ions, bioligands (amino acids, metal ions with that with a higher oxidation state. The second
polypeptides, and saccharides) and green solvents (Ils and way to improve their thermodynamic stability is the frame
interaction, through the interpenetration of the network,
which can be modified by matching the organic linkers.27–29
Chemical stability refers to the preservation of the struc-
tural integrity of the framework under the influence of a
specific chemical (external and internal factors). A way to
improve the chemical stability of MOFs in water and prevent
their degradation is to increase the resistance of coordination
bonds by introducing hydrophobic functional groups (e.g., CF3
fluorine network or some long alkyl groups). This action pre-
vents the replacement of organic linkers by OH− or H+ groups.
Our observations show that MOFs composed of high-value
Fig. 26 Division and examples of green solvents.156 Created with metal ions and carboxylates show good stability in acid solu-
BioRender.com. tions. Alternatively, MOFs made of metal ions with a low oxi-
View Article Online
Table 7 Comparative collection of the methods for the synthesis of MOFs
Synthetic method Advantages Disadvantages Ref.
Slow diffusion Formation of single crystals (X-ray examination) Slow process, taking several months 17, 160–163
No special conditions. Synthesis performed at Obtaining small amounts of MOFs
ambient pressure and room temperature
Solvothermal Easy industrial transposition The reactions take a long time, up to several days 17, 164–167
Possibility of alternating heating and cooling to High energy consumption due to the fact that the
support crystal growth synthesis is conducted at high temperatures (up to

250 °C)
It requires the purchase of airtight heating furnaces
and small reactors into which one can introduce
salts derived from one type of metal
Mechanochemical Solvent-free, cheap, and easy method Restricted control over crystal morphology and 17, 168–173
product particle size
Using mechanical force instead of high temperature Secondary phases are usually obtained
and reduced pressure
Room temperature or slightly elevated Special grinders/mills or mortar and pestle
One pot synthesis (timesaving) Possible impurities from milling reactors
Microwave A simple and ergonomically attractive method No easy and quick industrial implementation 17, 174–179
Reduction of crystallization time and improvement Difficult to isolate large single-crystals
of yield
Ability to control the morphology of MOFs
Easy change and strict control of reaction parameters
MW heating is volumetric, which enables uniform
reaction throughout the entire reactor volume and
results in enhanced reaction rate
Ultrasound Efficient in the isolation of phase-pure materials Ultrasound waves can break crystallites, hindering 17, 179–181
Homogeneous particle size and morphology in short the formation of large single-crystals for X-ray
periods diffraction studies
Continuous Flow Tailor MOF crystal sizes Some continuous flow reactors are expensive and 182–187
cannot handle pressure
Short reaction time Uneven flow at pressure
Highly controlled mass and heat transport
conditions
Remarkable reproducibility
The perfect method for large-scale production
Aerogels or Owing to their large porosity, high water content, High cost for large-scale production, including the 176,
hydrogels and excellent biocompatibility, MOF composite cost of raw materials and equipment 188–200
hydrogels have a strong potential for biomedical
applications
The high porosity of MOF composite aerogels leads Low performance of MOFs
to strong potential applications in adsorption, while
their low densities and excellent mechanical
properties enhance their transportation and
processability, respectively
Composite aerogels can also be reused after simple The problem associated with the utilization of
cleaning with water, which is ideal for industrial use powdered MOFs is the possibility of dust formation
Ionothermal Possibility of replacing harmful organic solvents High viscosity, low diffusion coefficients, and 31, 130–135
such as DMF with ionic liquids problematic recycling and 190
There is no need for reflux condensers or a sealed
system that may contain autogenous pressure due to
low or zero vapor pressure of IL
High concentration of ions results in obtaining new, Reduced surface area compared to MOFs based on
more porous materials unmodified Ils due to pore clogging
dation state and linkers based on azolates are characterized by Finally, we would like to compare the advantages and disad-
greater stability in basic solutions.27–29 vantages of the most important methods for the synthesis of
In summary, designing the synthesis of new, stable MOFs MOFs, making this review very attractive (Table 7).
should be guided by the Pearson hard/soft acid/base (HSAB)
theory. The stability of porous materials and complex com-
pounds is greater when a soft acid (low-value transition metal Abbreviations
ions) is combined with a soft base (azolates) to form stronger
bonds and the rate at which the substrates react with each MOFs Metal–organic frameworks
other increases. In contrast, hard acids (high-value metal ions) (HMTA)(CuCN)5 (Hexamethylenetetramine)penta[copper
form stronger acids with hard bases (carboxylates). The inter- (I) cyanide]
actions between hard and soft pairs tend to be less stable.27–29 ZIF Zeolitic imidazolate framework
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MIL Materials of Institut Lavoisier Conflicts of interest

HKUST Materials from The Hong Kong
University of Science and Technology There are no conflicts to declare.
UiO University of Oslo
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Latest Trends in The Large Scale Production of MOFs in Accordance With The Principles of Green Chemistry

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Latest Trends in The Large Scale Production of MOFs in Accordance With The Principles of Green Chemistry

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Green Chemistry

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Latest trends in the large-scale production of

1. Introduction globally. However, large-scale action is needed to slow down

Kacper Pobłocki is currently a Dr. Joanna Drzeżdżon is an

Green Chemistry Tutorial Review

Dr Barbara Gawdzik is an an Dr Dagmara Jacewicz is an

Tutorial Review Green Chemistry

representatives predicted the great technological importance

turers and suppliers of chemical (approximately 90 000),

Green Chemistry Tutorial Review

Fig. 5 12 principles of green chemistry.19–21 Created with BioRender.com.

ducts such as the corrosive HCl, instead producing by-products

Tutorial Review Green Chemistry

MOFs. This method enables the creation of tailor-made

material. However, complete control over the creation of pre-

Green Chemistry Tutorial Review

Tutorial Review Green Chemistry

Fig. 11 Schematic diagram depicting the syntheses of 3D MOF-based

metal–organic frameworks, during which dust formation is

Green Chemistry Tutorial Review

thinning, that is, reducing pressure. Then, high tensile forces

which will make it impossible to characterize them by X-ray

2.7 Continuous flow

2.6 Sonochemical method

Tutorial Review Green Chemistry

Green Chemistry Tutorial Review

solution such as Cu2+, Al3+, and Mn2+ and heat treatment

because the toxic HNO3 is released. An exception to the rule is

Tutorial Review Green Chemistry

Green Chemistry Tutorial Review

Table 2 Comparison of methods for the synthesis of MOFs based on MILs

Temperature Surface area

Large-scale production of MOFs based on MIL

Tutorial Review Green Chemistry

Green Chemistry Tutorial Review

Table 3 Comparison of methods for the synthesis of MOFs based on ZIFs

Large-scale production of MOFs based on ZIF

Tutorial Review Green Chemistry

MPO, diisopropyl fluorophosphate = DFP, and Soman = GD.84

synthesis of UiO-66-NH2 in a mill, where the precursors

Reaction BET [m2

Large-scale production of MOFs based on UiO

Green Chemistry Tutorial Review

An interesting article on the green synthesis of UiO-66 was

In summary, UiO-66 is supplied in large numbers on an

7. Production of MOFs based on BTC

Tutorial Review Green Chemistry

volume compared to Cu3(BTC)2(H2O)3·10H2O. The specific

mixture and mixing for 24 h contributed to the formation of a

8. Production of MOFs based on NU

Green Chemistry Tutorial Review

Table 5 Comparison of MOF synthesis methods based on NU-1000

MOF Method Substrates BET surface area [m2 g−1] Ref.

NU-1000 Electrophoretic FTO — 79

chloride hydrate, TBAPy

However, there are only a few examples in the literature on the