Journal of CO2 Utilization 42 (2020) 101297

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Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

MOFs in carbon capture-past, present and future

R. Aniruddha a, I. Sreedhar a, *, Benjaram M. Reddy b
a
Department of Chemical Engineering, BITS Pilani Hyderabad Campus, Hyderabad, 500078, India
b
Catalysis and Fine Chemicals Department, CSIR-Indian Institute of Chemical Technology, Uppal Road, Tarnaka, Hyderabad, 500007, India

A R T I C L E I N F O A B S T R A C T

Keywords: Metal Organic Frame works (MOFs) are being widely used in carbon capture through adsorption and membrane
MOFs in carbon capture techniques, which are yet to be commercialized. This is due to their high affinity towards acidic gases and
Synthesis protocol exceptional characteristics such as crystallinity, structural stability, high surface area and flexible pore di­
Capture capacity comparative analysis
mensions. In this review, wide range of topics viz., synthesis protocols, modifications employed to further
Computational modelling
Contactors
improve their attributes, comprehensive comparison of different MOFs used in carbon capture, thermo-kinetics
Morphology and screening modelling studies, contactors and material screening. Every section has been discussed in detail in terms of
developmental trends, future challenges and prospects besides summarizing in the form of comprehensive tables
at a glance for the benefit of the readers. Solvo-thermal method was found to be the most effective synthesis
method besides ultra-sonication and microwave assisted methods, which also gave very good crystalline struc­
tures. The copper ligand based unmodified Cu-BTC MOF gave the maximum CO2 uptake value of 9.59 mmol/g at
273 K and 1 atm. Zn(Bmic)(AT) MOF was the only species to be tested at 353 K. Alternatively, a photo-responsive
MOF, Mg-IRMOF-74-III functionalized with azopyridine gave a CO2 uptake of 89 cc/g which is comparable to
many of the conventional MOFs. Kinetics indicate MOF adsorption mostly follows pseudo second order reactions
either along with Toth isotherms or modified Langmuir isotherms. Fixed and fluidized bed reactors perform the
best in terms of carbon capture studies. Moisture affinity, active sites and crystallinity were found to be the best
factors considered whilst screening of proper MOFs.

1. Introduction Carbon Capture and storage (CCS) involves the three steps of
capturing the emitted CO2, transporting the captured CO2 and finally
The ever-rising energy demand in the world is reported by the IEA storing it. The three significant methodologies for CC (Carbon dioxide
report concerning the year of 2018. According to that report [1], the Capture) are post-combustion method, pre-combustion method and oxy-
world energy demand is up by 2.3 % as compared to the previous year. fuel combustion method. In the post-combustion method [4], CO2 is
The percentage increase directly corresponds to the consumption of captured from the flue gases after the combustion process of fuels is
available fuels to meet this continuously growing demand. Corre­ completed. Post-combustion capture is most prevalent in research
spondingly, the total greenhouse gas emissions have also spiked because existing fossil fuel power plants can be retrofitted to include
considerably. During that year, 46 gigatonnes of total gaseous emissions CCS technology in this configuration. Pre-combustion method [5] in­
made their way into our atmosphere out of which 33.3 gigatonnes [2] volves the process of converting fuel into a mixture of H2/CO2 and then
were made up of carbon dioxide. The oceans act as the primary sink of capturing the CO2 from the mixture before the combustion process is
CO2, fixing over a quarter of the emitted CO2 into ocean beds. Terrestrial initiated. Oxyfuel combustion [6,7] is similar to the post-combustion
trees act as the next biggest fixers of CO2 into the lithosphere. During method in most aspects with the only significant difference being that
2018, 12 million hectares [3] of forest land was lost due to deforestation instead of air; pure oxygen is used in the combustion of the fuels.
and wildfires. This figure is only expected to rise in the 2019 report. All There are five popular methods employed to capture CO2. They are
of these factors combined to convey the need for both curbing the CO2 absorption/scrubbing, adsorption, membrane separation, cryogenic
emissions as well as the need to capture the emitted CO2. distillation and chemical looping combustion. Absorption [8,9] often

Abbreviations: CC, Carbon dioxide Capture; SA, Surface area; PV, Pore volume; DMF, N,N-Dimethylformamide; mmol/g, millimoles of CO2 per gram of adsorbent;
cc/g, cubic centimeters of CO2 per gram of adsorbent; CLC, Chemical Looping Combustion.
* Corresponding author.
E-mail address: [email protected] (I. Sreedhar).

https://doi.org/10.1016/j.jcou.2020.101297
Received 27 June 2020; Received in revised form 16 August 2020; Accepted 19 August 2020
Available online 28 August 2020
2212-9820/© 2020 Elsevier Ltd. All rights reserved.
R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

involves trapping CO2 in bulk liquids such as mono-ethanol amine processes and MOFs having a suitable structure and porosity find
etcetera. Adsorption [10] involves trapping CO2 on the surface of solid themselves to be suitable here as well. Drug delivery is yet another field
porous substances such as activated carbons. In Membrane separation wherein MOFs have likely use [41]. Since MOFs have the tendency to
process [11], semipermeable membranes (usually polymeric mem­ bond easily and act as catalytic supports, there is a huge well of potential
branes) are selected in such a manner that only CO2 is trapped. Cryo­ applications in medicinal fields. Lastly, MOFs seem to be an exciting
genic distillation [12] is a gas separation process which is essentially prospect in the study of electrical energy storage. Increasing research is
distillation at very low temperature and high pressure, except that it is being conducted to convert MOFs into super-capacitors, with Li [42] and
used to separate components of a gaseous mixture (due to their different K being the key metals of interest. Further research, however, is neces­
boiling points) instead of liquid. Chemical Looping Combustion [13] is a sary for this particular field.
technological process typically employing a dual reactor bed system. In In connection to this need in curbing emissions, it is important to
CLC, a particular metal oxide is chosen as the oxidising agent to convert have a detailed look at the studies that have already been reported.
the fuel to CO2. Then the reduced metal oxide is re-oxidised and is Herein we present a summary and assessment of the development of
employed to capture the CO2 produced. The above process is known as MOF-based materials for CO2 capture and conversion. We begin by
calcium looping combustion [14] when CaO is employed as the metal providing an overview of the various syntheses and functional modifi­
oxide. cations that were previously reported. Next, latest studies in the field of
Broadly, there are four classes of adsorbents. Metal oxides [15,16] MOF and MOF-based materials for CC are described. Thirdly, we try to
and their derived salts form the first class. Most common metal salt provide an overview of the connection between CC performance, ki­
based adsorbents/catalytic supports used are of alkaline earth metals netics, screening and best synthesis procedure to determine which MOFs
like Mg, Ca and Ba. Transition metals like Mn, Ni, and Fe etc. also find have the capability for serious CC performance. Fig. 1 is a rough outline
application in CC and related studies. Activated Carbons (ACs) and their of the work presented here.
derivatives form the next class of adsorbents. These adsorbents form a
robust class of adsorbents, which are well studied and reported. ACs [17, 2. Synthesis methods
18] are very versatile and have high thermal stability, next only to metal
oxide derived sorbents. Recent studies on carbonaceous adsorbents There are two classes of synthesis methods for i.e. conventional and
include a flexible activated carbon cloth with high surface areas and modern. Solvothermal (hydrothermal), electrochemical and sol-gel
pore volumes with the potential to separate CO2 from CH4 [19]. Carbon methods are considered as conventional methods. MOFs have always
nanotubes [20–22] were also reported to have high CO2 uptakes and been and in many experiments even now are being synthesized by these
selectivity. Zeolites [23,24] form the third of these classes. They are methods. Conversely, more modern methods involve synthesis through
natural molecular sieves, have high affinity towards acidic gases, and microwave, sonication, spray drying/evaporation and flow chemical
are tunable. Zeolites, along with activated carbons, are considered to be methods. Solvothermal [43] is the most common synthesis method for
the best commercial options for both CO2 capture and conversion. A few MOFs. It is carried out using the basic principle of heating reagents
of the latest studies include a Faujasite zeolite [25] reported to have high dissolved in a universal solvent in a closed autoclave reactor. The size of
CO2 accumulation, hierarchical zeolite-Y structures [26] with very high the crystals obtained is determined by the pressure built up in the
CC values, mesoporous zeolite 4A with good affinity towards carbon reactor as well as the temperature the reactor is subjected. The general
dioxide and zeolite nanocrystals [27] with high performance CO2 cap­ observation related to the crystal sizes was found to be that bigger
ture. The last of class are porous organic adsorbents. These consist of crystals were obtained with higher pressures and longer durations. The
metal organic frameworks [28], covalent organic frameworks [29] and obtained crystals are then washed with a solvent, most commonly
microporous organic polymers [30,31]. This class of sorbents are ver­ deionized water or ethanol. Solvothermal methods usually employ
satile and novel. They are highly tunable and have exceptional pore organic solvents such as N,N-Dimethylformamide, methanol etcetera.
volumes. Covalent organic frameworks (COFs), like novel zeolites, have
a lot of potential in CO2 capture. However, these materials are more
suited in membranous CO2 separation than in direct CO2 adsorption.
Kang et al. [32] have reported layered 2-D matrix structures comprising
of two COFs, NUS-2 and NUS-3, for effective pore sizes. Microporous
Organic Polymers are also novel in gas separation applications. Hong
et al. [33] have reported a Troger base derived MOP for selective carbon
dioxide. Wang et al. [34] have also reported a selective melamine sup­
ported organic polymer with the capability of both isolating CO2 and
removing Hg2+ ions.
Metal organic frameworks (MOFs) metal ions bonded to an organic
linker. MOFs find their applications in many areas of study. Their pri­
mary application is in gas storage and separation, especially in hydrogen
[35] and CO2 separation [36]. Indeed, their high surface areas, ideal
pore structures and good porous volumes help them other gases such as
hydrocarbons, SOx and NOx. With the right metal ions, preferably
transition metals, MOFs have substantial potential applications in
magnetism and metal ion separations. Magnetic MOFs can also be
explored for the environmental application in removal of arsenic from
water feed streams [37]. Another area of potential research is in photo
sensing [38]. MOFs with lanthanide metal linkers like Eu, Gd, Er and Yb
are employed as luminescent metal ions. Naphthalene, anthracene,
pyrene, perylene and stilbene are usually the types of ligands that are
most commonly used for the synthesis of luminescent frameworks. A
similar application is in molecular motion sensing. Other than gas sep­
arations, catalysis and gas fixation is another significant and exciting
application of MOFs [39]. CO2 fixation [40] is the next step in many CC Fig. 1. Overview of the present review.

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R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

These solvents were proven to be hazardous to the environment and Usually, the reactants are placed in a tightly sealed system, and subject
their disposal is a problem. Hence, to curb these hazardous impacts the to intense microwave irradiation. These radiations provide the neces­
focus of synthesizing MOFs have shifted to aqueous methods. Hydro­ sary conditions that facilitate the formation of MOF crystals. This is also
thermal method in essence is the same as solvothermal methods, with a popular method of synthesis as it takes only a few hours for the process
the only difference being that water is used as a solvent instead of an to achieve completion. Mean process temperatures may vary from 303 K
organic compound. Post cleaning, drying is done usually in a vacuum. to 393 K. Although this method provides excellent crystal sizes and
The temperatures in this process range between 350 K–473 K for auto­ tenability, it is very hard to synthesize significant quantities of MOFs at
clave heating and the average time is between 2–6 days. Excellent once.
crystal sizes can be obtained from this method with a high degree of Fig. 2 lists the pros and cons of each of these major syntheses.
tenability. Also, pore sized and crystal structures can be well defined in Table 1 displays a few MOFs synthesized by various methods, in
hydrothermal method. Duration of synthesis is one of the major draw­ latest literature. Solvo(hydro)thermal, although not a new method in the
backs of this method in general. Along with the duration, the high timeline of various methods, was found to be the most popular method.
requirement of energy to maintain these elevated levels of pressure and This method delivers very good crystalline structures within MOFs. The
temperature for long durations is another drawback. Mechanochemical synthesis itself is not energy extensive when compared to electro-
synthesis [44] processes involve the usage of mechanical methods, most chemical method and the temperatures rarely exceed 393 K. The
frequently, centrifugation and agitation to obtain MOF crystals. The drawback however, is that these temperatures are needed to be main­
reagents are left to react in a beaker and subject to stirring for a specified tained for days to obtain crystalline MOFs.
time. Post stirring the products are centrifuged/filtered off and dried However, a new method, microwave-assisted solvothermal synthesis
under vacuum for half a day or so. Temperatures are not as high as in was found to be quite promising. Through this method, MOFs with
solvothermal method and the time is also significantly shorter being relatively high pore volumes and surface areas can be synthesized. A
only a few hours on average with more time on drying than the actual pressing issue with normal methods of synthesis is the yield of MOFs.
synthesis itself. The plusses of this type of synthesis is that a lot of time is Almost all of the aforementioned methods above give low yields. In
saved. Crystal sizes however, are predetermined mostly and specific to comparison, microwave assisted solvothermal method was found to give
each MOF being synthesized. Sonochemical [45] methods employ sound greater yields according to Schlesinger et al. [105] along with very good
frequencies to facilitate chemical reactions and crystal formations. The surface area, pore volumes and crystallinity. Also according to Schle­
reagents are taken in a beaker or a glass reagent bottle and subjected to singer et al., the solvent-assisted mechano-chemical method also proved
high frequencies of sound waves to complete the synthesis. Post to be an exciting new method that wielded potential for large-scale
completion, the products are filtered from the remaining suspension and production.
allowed to dry in an oven (preferably under vacuum conditions). As of yet, the challenges involved in MOF production are,
Ultrasonication [46] (the use of ultrasonic waves) is the most preferred
sonochemical method as it rapidly increases temperatures in an expo­ 1 Lack of economical means for mass production.
nential rate. Owing to this, the time involved in this synthesis method is 2 Lack of any type of large/industrial scale of production.
usually within one hour. The speed of completion is one of the salient 3 Most methods with excellent yield and crystal properties are very
features of this method. However, yields are often low in this synthesis energy intensive, ex microwave-assisted synthesis.
and this alone prevents this method from being scaled up. Other syn­ 4 Tedious synthesis procedures for promising synthesis methods.
thesis methods of this type include the usage of high frequencies of
audible sound. Electricity is employed in certain syntheses of MOFs. 3. CC performance
These methods are termed as electrochemical methods [47]. These are
also rapid processes taking only a few minutes for synthesizing MOF As a critical shared physical property, MOFs, in general, have
crystals and can be done in ambient temperatures, much like sono­ excellent BET surface areas. Overall, MOFs can be utilized in CC in the
chemical methods. The biggest drawback of this method is that it gives following four forms viz pure, functionalized and in combination with
less pore volumes, poor crystallinity and relatively low surface areas. adsorbents. Pure MOFs by themselves can be good excellent CO2 traps.
Spray drying/evaporation [48] methods involve no external forces to Choi et al. [106] studies on HKUST-1 displayed a great CC value of 3.3
bring about the desired products. They are very simple drying tech­ mmol/g with a BET surface area of roughly 850 m2/g. Another pure
niques to obtain the MOF powders/crystals. These processes are usually MOF, UiO-66 [107] demonstrated great CC value of 2.32 mmol/g. In
time-consuming and take long periods to yield significant amounts of that same study Cu3(BTC)2, another MOF, recorded an even higher CC
MOF crystals. Another class of synthesis methods that involve no value 4.4 mmol/g and both these had excellent BET surface areas above
external energies are chemical flow methods. In these methods [49,50], 1400 m2/g. The highest CC value recorded in Table 2 was that of Cu-BTC
the reagents are left to react completely on their own. As such, the time mentioned by Szczęśniak et al. [108]. This pure MOF recorded an
of synthesis depends on the time of completion of each reaction. Re­ outstanding amount of 9.59 mmol/g at 273 K, 1 atm and 5.33 mmol/g at
agents are taken in a sealed Roughly, the time average time observed is 298 K. These values were attributed to the high inherent affinity towards
variant between ten minutes to three days and the temperature of re­ CO2. In that very study, Cu-BTC and its derivatives were compared to
actions vary between 303 K–573 K. Microwave synthesis [51,52] sub­ another series of adsorbents termed as aPPy(/GO) (polypyrrole derived
jects the reagent mixtures/solutions to constant microwave radiation. carbons and graphene oxide adsorbents). For the same temperatures and

Fig. 2. Comparison of the major synthesis methods.

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R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Table 1
Various synthesis procedures.
S MOF Synthesis method and Process Process Properties Merits Demerits Ref
No reagents employed Conditions

1 Nanocellulose leaf- Sol-Gel method. Celloluse, Zinc nitrate, Stirring the BET SA: 14 m2/g Extremely eco- Low BET SA and [53]
like zeolitic Cellulose, zinc nitrate, Triethylamine, 2,2,6,6 mixture for 2 BJT PV: 0.03 cc/g friendly process. BJT PV. Long
imidazolate triethylamine, 2,2,6,6-tet­ tetramethylpiperidine- min. Cooling XRD: Highly Process gives synthesis time.
framework (ZIF-L) ramethylpiperidine-1-oxyl 1-oxyl radical and 2- overnight at 276 Crystalline high
radical and 2- methylimidazole were K. FTIR: Strong crystallinity.
methylimidazole all added and amide moiety Excellent
gelatinized. Post peaks. mechanical
gelatinization, freeze- Particle size: stability.
drying was done to 100− 200 nm
obtain the MOF block.
2 UTSA-16 Co Hydrothermal method. All reagents were added Stirring, BET SA: 500 m2/g Extremely eco- Long synthesis [54]
UTSA-16 Ni Cobalt acetate, nickel in ethanol and heated in constant heating BJT PV: 0.21 cc/g friendly process. time.
acetate, citric acid, an autoclave. Post at 120 ◦ C for two XRD: Crystallite Process gives
potassium hydroxide and heating, the crystals days and sizes range from high
ethanol. were dried. Nickel subsequent 40− 71 nm crystallinity.
acetate was then used to cooling for six Favourable pore
replace Co as per hours. sizes.
requirement.
3 Cu-ABDC Solvothermal method. All reagents were added Stirring the BET SA: 217 m2/g Gives good Slightly energy [43]
Copper nitrate, 2-amino­ in methanol and heated mixture well for BJT PV: 0.028 cc/ crystallinity. intensive.
terephthalic acid, N, N- in an autoclave. Post 10 min and then g Decent BET SA.
dimethylformamide and heating, the crystals constant heating TGA: Thermal
methanol. were dried. at 110 ◦ C for one limit at 360 ◦ C
day and
subsequent
vaccum drying
at 60 ◦ C.
4 Ca-MOF/Al2O3 Solvothermal and All reagents were added Stirring the XRD: Highly A novel template Energy [55]
template methods. in methanol and heated mixture well Crystalline type process. intensive. Ca/Al
Calcium nitrate, L-calcium in an autoclave. Post along with FTIR: Strong Ease of synthesis ratio can affect
lactate, aluminum nitrate, heating, the crystals constant heating amide moiety is high. Highly the morphology
2-aminoterephthalic acid, were dried. After drying, at 80 ◦ C for two peaks. stable
terephthalic acid, N,N- the crystals were hours and adsorbents can
dimethylformamide, calcined using the MOF subsequent be synthesized.
ethanol and water. template. calcination for
four hours at
800 ◦ C.
5 AlFu Solution method and wet All reagents were added Stirring the BET SA: 828 m2/g Novel synthesis Time [56]
impregnation. in methanol and heated mixture well at BJT PV: 0.436 cc/ route. Ease of consuming.
Aluminum nitrate, in an autoclave. Post 25 ◦ C for twelve g synthesis is high.
disodium fumarate, heating, the crystals hours and XRD: Indicates
polyethyleneimine, were dried. subsequent strong binding
tetraethylenepentamine vacuum drying between AlFu and
and methanol. for a day at 60 TEPA.
◦
C. Post drying, FTIR: Strong
addition of hydroxyl moiety
TEPA is done. peaks.
6 Zn-TMU Ultrasonication method. All reagents were added BET SA: 5− 1500 Low CO2 [57]
Zinc acetate, 4,4′ - in ethanol and treated m2/g uptakes.
oxybisbenzoic acid, 1,4- with ultrasound. Post BJT PD: 0.436 cc/ Functionalizing
bis(4-pyridyl)-2,3-diaza- heating, the crystals g compound
1,3-butadiene, 2,5-bis(4- were dried under TGA: Thermal contributes to a
pyridyl)-3,4-diaza-2,4- vacuum. limit at 400 ◦ C pore blockage,
hexadiene, N1,N4-bis-
((pyridin-4-yl) methylene)
benzene-1,4-diamine, N,
N-dimethylformamide,
ethanol and water.
7 MIL-53(Al) Hydrothermal method. All reagents were added Stirring the FTIR: Strong Good CC uptake Long duration of [58]
Aluminum nitrate, in methanol and heated mixture well for hydroxyl, amide potential. synthesis.
hydrochloric acid, nitric in an autoclave. Post three days at and alkene peaks.
acid, ethylene glycol, PET heating, the crystals 220 ◦ C and
flakes, water and benzene were dried. subsequent
1, 4-dicarboxylic acid. drying.
8 AC-Cu-BTC Hydrothermal method. All reagents were added Stirring the BET SA: 1202 m2/ Presence of fine Process is time [59]
Copper nitrate, 1,3,5-tri­ in methanol and heated mixture well at g mesoporous. taking.
carboxybenzene, in an autoclave. Post 25 ◦ C for twenty BJT PV: 0.53 cc/g Very high BET
resorcinol, poly heating, the crystals minutes and XRD: Bond SA. The process
(ethyleneoxide)-poly were dried. subsequent between metal has potential for
(propylene oxide)-poly heating in an ion and organic future hybrid
(ethylene oxide) triblock autoclave for a linker unaffected sorbents.
copolymer, formaldehyde, 12 h at 120 ◦ C. even after the
(continued on next page)

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Table 1 (continued )
S MOF Synthesis method and Process Process Properties Merits Demerits Ref
No reagents employed Conditions

HCl, ethylenediamine, After that addition of

ethanol and water. vaccum drying porous carbon.
was done at 120 FTIR: Presence of
◦
C for twenty carboxyl group.
hours. TGA: Thermal
limit at 600 ◦ C
9 Zn(BPZNH2)⋅DMF Solvent method. Dissolution of all Temperature of BET SA: 350 m2/g Relatively Slightly [60]
3-Nitro-4,4′ -bipyrazole, 2- reagents at 333 K for 14 333 K. BJT PV: 0.57 cc/g shorter time of expensive.
propanol, hydrazine h (continuous dropwise XRD: Bond synthesis.
Hydrate, RANEY© 2800 addition of propanol) between metal Process develops
nickel (Ni-Re) slurry, and subsequent addition ion and organic a high surface
water and ethanol. of Raney Ni slurry every linker unaffected area and pore
two hours for the next even after the volume.
eight hours. After that, addition of
zinc acetate is added to porous carbon.
obtain a final solution. FTIR: Presence of
Finally, centrifugation is carboxyl group.
used to separate the TGA: Thermal
crystals. limit at 703 K.
10 DETA–MIL-100(Fe) Solvothermal method. Dissolution of all BET SA: 719 m2/g [61]
Iron powder, 1,3,5-ben­ reagents at 423 K for 24 BJT PV: 0.27 cc/g
zene tricarboxylic acid, h and subsequent XRD: DETA
water, removal of unreacted affected the
diethylenetriamine, trimesic acid. Finally, crystal peak
hydrofluoric acid, nitric the crystals were intensity as
acid and ethanol. impregnated with compared to MIL-
DETA. 100(Fe).
FTIR: Presence of
carboxylate,
hydroxyl and
amine groups.
TGA: Thermal
limit at 703 K.
11 UiO-66 [F4_UiO-66 Solution reflux method. The reagents were Mentioned in BET SA: 1282 m2/ Good surface [62]
(Ce)] Tetrafluoroterephtalic dissolved in deionized synthesis g area was
acid, cerium ammonium (DI) water in a round procedure. BJT PV: 0.5 cc/g obtained.
nitrate, acetic acid and bottom flask. The FTIR: Presence of
water. solution was heated to carboxylate,
110 ◦ C under stirring hydroxyl and
and refluxed for 24 h. amine groups.
The obtained solid was
collected and washed
thrice with DI water and
once with acetone. The
solid was then dried in
oven at 80 ◦ C for 24 h.
12 MIL-140 [F4_MIL- Solution reflux method. The reagents were Mentioned in BET SA: 739 m2/g Synthesis gives
140A(Ce)] Tetrafluoroterephtalic dissolved in deionized synthesis BJT PV: 0.27 cc/g the adsorbent
acid, cerium ammonium (DI) water in a round procedure. FTIR: Presence of water resistance.
nitrate, acetic acid and bottom flask. The carboxylate and
water. solution was heated to amine groups.
110 ◦ C under stirring
and refluxed for 24 h.
The obtained solid was
collected and washed
thrice with DI water and
once with acetone. The
solid was then dried in
oven at 80 ◦ C for 24 h.
13 een-Mn2(dobpdc) Microwave synthesis Reagents were first Microwave FTIR: Presence of Inherent [63]
followed by ultra dissolved and subject to conditions were carboxylate and hydrophobicity
sonication and wet microwave heating. 140 ◦ C, 150 psi carbamate achieved.
impregnation. Then water was and 20 min. groups.
H4dobpdc (4,4′ - exchanged with Sonication
dihydroxy-(1,1′ - methanol and subject to conditions were
biphenyl)-3,3′ - ultra sound treatment. 40 ◦ C for 12 h.
dicarboxylic acid), Finally, the powder
Manganese chloride, obtained was cleaned
DMF, methanol, water, under vacuum.
toluene and N-
ethylethylenediamine.
14 TEPA-MIL-101 Acetic solvothermal All reagents were added BET SA: 1400 m2/ 3D printing gives Long synthesis [64]
method followed by 3D in methanol and heated g high tenability. time.
printing. in an autoclave. Post BJT PV: 0.76 cc/g
Chromium nitrate, heating, the crystals FTIR: Presence of
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R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Table 1 (continued )
S MOF Synthesis method and Process Process Properties Merits Demerits Ref
No reagents employed Conditions

terephthalic acid, PVA, were dried. carboxylate,

TEPA, bentonite clay, Subsequently TEPA was hydroxyl and
glacial acetic, methanol added through wet amine groups.
and ethanol. impregnation.
15 Cu3(pmtz)6·DMF Solvothermal method. Same as all solvothermal Stirring the XRD: Cu–N bonds [65]
4,4′ ,4′ ’-((1,3,5-triazine- autoclave processes as mixture well and in the equatorial
2,4,6-triyl)tris described above. subsequent plane are much
(azanediyl))- heating in an shorter than those
tribenzonitrile, NaN3, autoclave for 72 in the axial
NH4Cl, anhydrous DMF, h at 90 ◦ C. After direction.
Cu(NO3)2·3H2O, that vaccum TGA: Thermal
acetonitrile, hydrochloric drying was done limit at 573 K.
acid at 120 ◦ C for
twenty hours.
16 Zn2(BDC)2(DABCO) Solvothermal method. Same as all solvothermal Stirring the BET SA: 1700 m2/ Tunable pore [66]
Zinc nitrate, H2BDC, DMF, autoclave processes as mixture well and g size and
NaH2PO4, DABCO, K3[Fe described above. subsequent BJT PV: 0.39 cc/g chemistry.
(CN)6], ethanol and water. heating in an XRD: A well-
autoclave for 48 defined
h at 120 ◦ C. crystallinity was
After that shown.
vaccum drying TGA: Thermal
was done. limit at 703 K.
17 [Zn(BPDI)(Py)2] Sonication followed by Zinc acetate is dissolved Sonication for BET SA: 14 m2/g Tunable coating [67]
solvothermal method. in pyridine by sonication one hour. BJT PV: 0.12 cc/g thickness.
Pyromellitic dianhydride, for 1 h. Subsequently, Stirring the
glacial acetic acid, both solutions are mixture well and
glycine, deionized water combined on an subsequent
and polyethylenimine. autoclave reactor. The heating in an
obtained powder is autoclave for 24
dried. The dried powder h at 100 ◦ C.
is then impregnated After that
with PEI. vaccum drying
was done.
18 {[Pb2(L)2(H2O)]- Solvothermal method. Not mentioned Not mentioned [68]
H2O}n
19 IISERP-MOF26 Solvothermal method. All reagents were added Stirring the FTIR: Presence of Not mentioned Not mentioned [69]
([NH2(CH3)2] Copper acetate, 1,4-ben­ in water and heated in mixture well and Cu-O, hydroxyl
zene di-carboxylic acid an autoclave. Post subsequent and Cu-N bonds.
(H2BDC), N,N’- dimethyl heating, the crystals heating in an TGA: Thermal
acetamide, N,N’-dimethyl were dried. autoclave for 72 limit at 473 K.
formamide, water and h at 120 ◦ C.
methanol. After that drying
was done.
20 MgFe2O4@UiO-66- Magnetic induction Subjecting the MFCs to 31 m T of BET SA: 470 m2/g Shorter synthesis Energy [50]
NH2 method. an external magnetic magnetic XRD: Good time. intensive.
Zirconium amino field with a field induction. crystallinity
terephthalate, magnesium strength of 31 m T using Heating upto SEM: Particle size
ferrite, benzoic acid, 2- a magnetic induction 120 ◦ C. of 200 nm.
aminoterephthalic acid heater, resulted in
and ethanol. heating the MFCs to 120
◦
C.
21 UiO-66-NH2 Solvothermal method. All reagents were added Stirring the XRD: Increased Much shorter [52]
Zirconium chloride, 2- in water and heated mixture well and peak size synthesis time
aminoterephthalic acid, (both conventional and subsequent indicating high when magnetic
N, N’- microwave) in an heating CC uptake. modulators were
Dimethylformamide, autoclave. Post heating, (magnetic Crystal sizes were employed.
acetic acid, hydrochloric the crystals were dried. modulators) in 500 nm. Higher
acid, acetone and water. an autoclave for FTIR: Presence of crystallinity
30 min at 150 N-H, C-N groups. obtained.
◦
C. TGA: Thermal
limit at 673 K.
22 [Ni(btzip) Solvothermal method. All reagents were added Nickel wire was XRD: Octahedral Good [70]
(H2btzip)]⋅ Nickel wire, 4,6-bis(tria­ in water and heated in employed coordination. crystallinity,
2DMF⋅2H2O zol-1-yl)isophthalic acid, an autoclave. Post instead of nickel FTIR: Presence of water stability.
acetonitrile, DMF, acetone heating, the crystals salts. carboxyl groups.
and water. were dried. TGA: Thermal
limit at 603 K.
23 IISERP-MOF24 Solvothermal method. All reagents were added 90 ◦ C heating for BET SA: 771 m2/g Permanent Limited CC [71]
Cerium nitrate, in ethanol and heated in 5 days in an XRD: 3-D layered porosity. uptake.
iminodiacetic acid, 4,4′ - an autoclave. Post autoclave. pillared MOF.
biphenyldicarboxylic heating, the crystals Subsequent FTIR: Presence of
acid, DMF, ethanol and were dried. drying. carboxylate,
water. hydroxyl and
amine groups.
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6
R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Table 1 (continued )
S MOF Synthesis method and Process Process Properties Merits Demerits Ref
No reagents employed Conditions

24 MIL-96(Al) Solvothermal method. All reagents were added The mixture was TGA: Thermal Hydrophobic Low-pressure [72]
Aluminium nitrate, in ethanol and heated in stirred for 10 limit at 703 K. nature and process.
trimesic acid, deionized an autoclave. Post min and heated tunability.
water, ethanol. heating, the crystals to 180 ◦ C for 24
were dried. h.
25 Mg-CUK-1 Hydrothermal method. All reagents were added Heating at 573 K BET SA: 586 m2/g High stability Low [73]
2,4-Pyridinedicarboxlic in water and heated in for 35 min. XRD: Soft towards H2O and temperature CC.
acid, magnesium nitrate, an autoclave. Post crystallinity. H2S.
potassium hydroxide and heating, the crystals FTIR: Presence of
deionized water. were dried. carboxylate,
hydroxyl and
amine groups.
26 MOF-76-Ce Solvothermal method All reagents were added Stirring for 15 BET SA: 754 m2/g Fast synthesis. [74]
Trimesic acid, DMF, in water and heated in min and heating XRD: Good
Cerium nitrate and an DrySyn heating block at 140 ◦ C for 30 crystallinity.
distilled water. set. Post heating, the min. FTIR: Presence of
crystals were dried. carboxylate,
hydroxyl and
amine groups.
TGA: Thermal
limit at 703 K.
27 Double-Walled Zn Solvothermal method. All reagents were added Heating at 90 ◦ C BET SA: 215 m2/g Open Lewis acid [75]
(II)-Carboxylato 5-(1H-imidazol-1-yl) in water and heated in for 72 h. FTIR: Presence of sites for CO2
Phosphate MOF isophthalic acid, Zinc an autoclave. Post carboxyl group. capture.
nitrate, DMF, ethanol and heating, the crystals
water. were dried.
28 MWCNT/MIL-101 Solvothermal method. All reagents were added Reflux for 48 h BET SA: 3745 m2/ Excellent [76]
(Cr) composite Chromium nitrate, 1,3 in water and heated in at 120 ◦ C and g morphology and
benzene dicarboxylic acid, an autoclave. Post autoclave for 8 h BJT PV: 1.95 cc/g crystallinity.
ammonium fluoride, heating, the crystals at 220 ◦ C. XRD: Presence of
water were dried. MWCNT didn’t
affect
crystallinity.
FTIR: Presence of
C = C, C-N, O-C-O
and –COO groups.
TGA: Thermal
limit at 623 K.
29 PPIA-MOF-5 Propane-1,3-diol, Refluxing and drying. Refluxing at a XRD: Crystallinity Crystallinity [77]
hydroquinone, DMF, temperature of affected with affected with
chloroform, Itaconic acid, 130 ◦ C for 4 h exposure to air/ exposure to air/
terephthalic acid, water, and drying at moisture. moisture.
zinc acetate and zinc room FTIR: Presence of
nitrate. temperature for C = C, C-N, C = O
24 h and and –COO groups.
activated at 200 TGA: Thermal
◦
C for 2 h. limit at 623 K.
30 NOTT-202 Biphenyl-3,3′ ,5,5′ -tetra- Heated to 90 ◦ C for 1 Good Exceptionally [78]
(phenyl-4-carboxylic day, separated by crystallinity. high CC uptake
acid), biphenyl-3,3′ ,5,5′ - filtration, washed with value of 20
tetrabromide, 4-boronic DMF and dried in air. mmol/g.
acid phthalic acid,
potassium phosphate, 1,4-
dioxane, DMF and indium
nitrate
31 FJI-H14 Solvothermal method. Heated at 120 ◦ C for 3 BET SA: 904 m2/g Good CO2 CC only at room [79]
2,5-di(1H-1,2,4-triazol-1- days, cooled to room BJT PV: 0.45 cc/g selectivity. temperatures.
yl)terephthalic acid, temperature and dried. TGA: Thermal
copper nitrate, acetone limit at 573 K.
and water.
32 polyILs@MIL-101 Reflux method. Reacted at 200 ◦ C for 8 BET SA: 2462 m2/ Superb [80]
1-vinyl-3- h, refluxed in water for g morphology.
ethylimidazolium 24 h, refluxed in ethanol BJT PV: 1.26 cc/g
bromide, terephthalic for 24 h twice, in NH4F FTIR: Presence of
acid, chromium nitrate, aqueous solution at 85 imidazole ring.
HF, water, ethanol, AIBN ◦
C for 12 h and washed TGA: Thermal
and o-DVB. with hot ethanol, dried limit at 663 K.
overnight at 160 ◦ C in
vacuum.
33 TbL Solvothermal method. Kept in a 130 ◦ C oven for XRD: Indicate Good water Applications in [81]
Lanthanide salts, 1-(4- 72 h. Cooled to room water stability. stability. catalysis.
carboxybenzyl)-1H- temperature, washed
pyrazole-3,5-dicarboxylic with CH3CN and
acid, CH3CN and ethanol. ethanol, and dried in air.
34 Ba-MOF [82]
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R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Table 1 (continued )
S MOF Synthesis method and Process Process Properties Merits Demerits Ref
No reagents employed Conditions

N,N′ -bis(isophthalic acid)- Reagents were mixed in XRD: Good Good CO2
oxalamide, tetra-n-tert- DMA and distilled crystallinity. selectivity.
butylammonium bromide, water. The mixture was TGA: Thermal
barium salts, water and sealed in a glass vial and limit at 703 K.
ethanol. heated at 95 ◦ C for 48 h.
35 MOF1 Solvothermal method. Stirred for 30 min and BET SA: 946.74 High CC value. Low [83]
1,3,5-tris (4- then transferred to an m2/g temperature CC
carboxyphenyl) benzene, autoclave and heated at XRD: Trigonal
DMF, water, ethanol, Sm 100 ◦ C for 72 h and system
(NO3)3.6H2O, Gd cooled naturally.
(NO3)3.6H2O and Ce
(NO3)3.6H2O.
36 HNUST-6 Solvothermal method. Mixture was stirred for BET SA: 1093 m2/ High CO2 [84]
Copper nitrate, MOPBD, 10 min in air and sealed g selectivity, good
ethanol, HBF4, DMF and in a 20 ml autoclave, BJT PV: 0.455 cc/ moisture
water. which was heated at 85 g stability.
◦
C for 72 h. XRD: Exhibits 2-
fold
interpenetration.
TGA: Thermal
limit at 673 K.
37 Graphene-MOF ZIF-8 and Graphene oxide. Carbonization. 900 ◦ C. Very high CC [85]
uptake and
selectivity.
38 [Zn2(L)(2,6- Solvothermal method. Mixture was stirred, was TGA: Thermal Good CC [86]
NDC)2(H2O)]⋅ 2,6-H2NDC, DMF, ethanol transferred and heated limit at 573 K. selectivity.
1.5DMF⋅2H2O and water. at 120 ◦ C for 3 days.
Cooled and dried next.
39 TMOF-3 Hydrothermal method. Hydrothermal reaction. XRD: Distorted High porosity. Untested in CC [87]
1,2,4,5-BTMS, 4,4′ - octahedral
bipyridine, water, acetone geometry.
and copper nitrate. FTIR: Missing
organic linkers.
40 CFA-1 Hydrothermal method. Hydrothermal reaction. Loss of [88]
Zinc trifluorome- crystallinity
thanesulfonate, 5-chloro­ after cycles.
benzimidazole, 3,3-
diaminobenzidine, zinc
acetate, gadolinium
nitrate
41 ILs@ZIF-8 Incipient wetness Wet impregnation. BET SA: 1196.1 Crstalline Low [89]
technique. m2/g stability and CO2 temperature CC.
Methanol, 1-Butyl-3- BJT PV: 0.65 cc/g selectivity.
methylimidazolium XRD: Good
Acetate, Basolite Z1200, crystallinity.
water and ethanol. TGA: Thermal
limit at 573 K.
42 MAX-MIL Hydrothermal method. Mixture was BET SA: 2670 m2/ Hydrophobic [90]
Chromium nitrate, transferred into g nature.
terephthalic acid, an autoclave BJT PV: 1.27 cc/g
hydrochloric acid, reactor and was FTIR: Presence of
Maxsorb-III, N,N placed in an C = C, C-N, O-C-O
dimethylformamide and oven. and –COO groups.
water. Temperature of
200 ◦ C for 12 h
and was cooled
down slowly.
43 PU/UiO-66 (Zr) Priming method. Additions of polymer to SA: 1125 m2/g Good as Limited use in [91]
Anhydrous zirconium the MOF suspension. XRD: Well- membrane. adsorption.
chloride, chromium Afterwards, the defined
nitrate, Terephthalic acid, dispersion was sonicated tetrahedral
fluoridric acid, and casted/dried at structure.
dimethylformamide, room temperature FTIR: Presence of
Acetone, ethanol, C = C, C-N, O-C-O
Elastollan® BASF, and –COO groups.
tetrahydrofuran and
water.
44 Co-pydc-TPB 5,5′ ,5′ ’-(pyridine-2,4,6- Solvothermal method. XRD: Stable upto Good moisture [92]
triyl) tri-isophthalic acid, 573 K. stability.
tris (3-pyridyl)-1,3,5- FTIR: Presence of
benzene, water and cobalt C = C, C-N, O-C-O
nitrate. and –COO groups.
TGA: Thermal
limit at 673 K.
45 Z11CBF-1000− 2 ZIF-11 [93]
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R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Table 1 (continued )
S MOF Synthesis method and Process Process Properties Merits Demerits Ref
No reagents employed Conditions

Solvothermal followed Stirring at STP BET SA: 1020 m2/ Usage in Xe

by carbonization. for 3 h and g capture.
carbonation at BJT PV: 0.481 cc/
1273 K for eight g
hours. FTIR: Presence of
graphite peaks.
46 Zn4O-based MOF 2,2′ -(pyridine-2,5 diyl) Solvothermal method. Reaction in a BET SA: 511 m2/g Good as catalyst [94]
diterephthalic acid, Zn4O DMF/C2H5OH BJT PV: 0.21 cc/g support.
cluster, zinc nitrate, mixed solvent at XRD: Strong
105 ◦ C for three peaks.
days.
47 [IL@MOF] 1,1,3,3-Tetramethyl Wet impregnation onto XRD: Low Membrane [95]
@Matrimid®5218 guanidiniumazide, 1-ethyl Mg-MOF-74 and MOF-5. intensity peaks. material.
3-methylimidazolium TGA: Thermal
tricyanomethane, Mg- limit at 623 K.
MOF-74 and MOF-5.
48 ZIF-300-PEBA ZIF-300, 2-mImH, bbImH, Solvothermal followed Heated at 393 K XRD: Good Membrane [96]
MMMs zinc nitrate, DMF and by fabrication. for nearly 3− 6 crystallinity. material.
water. days, TGA: Thermal
centrifugation at limit at 573 K.
10,000 rpm for
10 min and
washed by DMF.
49 UTSA-16(Co) Water, ethanol, clay, PVA Mixing followed by 3D Reagents were BET SA: 727 m2/g Need of more CC [97]
and MOF. printing. combined and BJT PV: 0.29 cc/g experiments.
mixed at 250 XRD: Strong
rpm for 2 − 3 h. peaks.
50 PPI600 PPI Pyrolysis. Pyrolysis was BET SA: 951 m2/g Good CC at low Low [98]
carried out at BJT PV: 0.51 cc/g pressure. temperature CC
600 ◦ C for 1 h. XRD: Strong
peaks.
51 PCN-222(Fe) Zirconium(IV) chloride, Synthesis of BET SA: 3745 m2/ Potential in CC [99]
methyl 4-formylbenzoate, PCN-222: ZrCl4, g undiscovered.
pyrrole, benzoic acid, iron FeTCPPCl and BJT PV: 1.95 cc/g
(II) chloride, propionic benzoic acid in XRD: Presence of
acid, chloroform, ethanol, DMF were MWCNT didn’t
methanol, glucose, ultrasonically affect
sucrose, fructose, sodium dissolved. The crystallinity.
ascorbate, cyclamate, mixture was FTIR: Presence of
hydrochloric acid, N,Nʹ- heated at 393 K C = C, C-N, –COO
dimethyl formamide, for 48 h. groups.
NaOH and TGA: Thermal
tetrahydrofuran. limit at 623 K.
52 [BMIM][BF4]/MOF [BMIM][BF4], CuBTC, and Evaporation method Solution was XRD: Good Good CO2 [100]
ZIF-8. mixed at 35 ◦ C crystallinity. affinity.
solvent was FTIR: Presence of
completely C = C, C-N, –COO
evaporated. groups.
Dried at 105 ◦ C.
53 CNFs/Cu/BTC-3 Chitosan, poly(vinyl Evaporation method. Mixture was BET SA: 104.6 Good More suited for [101]
alcohol), copper nitrate, stirred and m2/g crystallinity. membranes.
1,3,5-benzenetricarbox­ precipitate was BJT PV: 0.0689
ylic acid, and 1,2,3,4 dried in a cc/g
butanetetracarboxylic hot air oven at XRD: Good
acid. 120 _C for 12 h. crystallinity.
54 MOF-74 (Ni) Nickel nitrate, 2,5-dihy­ Microwave method Solution was BET SA: 1243 m2/ Good CO2 [102]
droxyterephthalic acid, N, heated at 140 ◦ C g affinity.
N-dimethylformamide, for 60 min under BJT PV: 0.72 cc/g
methanol and ethanol. stirring. XRD: Good peak
Products were intensity.
filtered and
dried at 250 ◦ C.
55 ZIF-8/PESf Solvothermal method. ZIF-8 XRD: Good peak Membrane [103]
composite membranes intensity. material.
were obtained
after
crystallization
for 6 h at
353− 373 K.
Washed with
methanol and
dried at 363 K
under vacuum
for 4− 6 h.
56 g-CD-MOF [104]
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9
 R. Aniruddha et al.
Table 2
MOF CC performance table.
S MOF Metal Linker Synthesis Method Functionalizing compound CC BET CO2 Merits Demerits Ref
No Conditions Surface uptake
Area (m2/ capacity
g) (mmol/g)

1 pip-γCD-MOF K γ-Cyclodextrin Wet impregnation Piperazine 333 K, 1.1 0.0273 Quick CO2 Loss of crystalline [112]
atm adsorption, High nature. Stable
CO2 affinity. only up to 333 K.
Degradation of
–NH group over
time.
2 PVAm(0.4)@MIL-101 Cr Terephthalic acid Ship in a bottle Polyvinylamine 298 K, 1 2253 3.0 High initial CO2 Stable only at low [113]
technique atm affinity, high BET temperatures.
SA.
3 PVAm(0.7)@MIL-101 Cr Terephthalic acid Ship in a bottle Polyvinylamine 298 K, 1 1919 3.3 High initial CO2 Stable only at low
technique atm affinity, high BET temperatures.
SA.
4 PVAm(1.0)@MIL-101 Cr Terephthalic acid Ship in a bottle Polyvinylamine 298 K, 1 1359 2.8 High initial CO2 Stable only at low
technique atm affinity, high BET temperatures.
SA. Unavailability of
pores.
5 Cu-BTC Cu Benzene-1,3,5-tricarboxylic acid Sonochemical 273 K, 1 1760 9.59 High initial CO2 Low temperature [108]
method atm affinity, high CO2 CC
selectivity.
6 Cu-BTC/GO2 Cu Benzene-1,3,5-tricarboxylic acid Sonochemical 273 K, 1 1820 9.05
method atm
10

7 Cu-BTC/GO5 Cu Benzene-1,3,5-tricarboxylic acid Sonochemical 273 K, 1 1520 8.46

method atm
8 Cu-BTC/GO10 Cu Benzene-1,3,5-tricarboxylic acid Sonochemical 273 K, 1 1380 9.59
method atm
9 HKUST-1 Cu Benzene-1,3,5-tricarboxylic acid 298 K, 1 855.61 3.3 High initial CO2 Mostly [106]
atm affinity, high CO2 microporous
selectivity.
10 PAN/HKUST-1(40 %) Cu Benzene-1,3,5-tricarboxylic acid Electrospinning Polyacrylonitrile 298 K, 1 248.13 1.4 High pore
fibers atm blockage.
11 PAN/HKUST-1(60 %) Cu Benzene-1,3,5-tricarboxylic acid Electrospinning Polyacrylonitrile 298 K, 1 420.40 2.5 High pore
fibers atm blockage.
12 NH2-β-CD-MOF K Mono-6-deoxy-6-amino- Vapour diffusion 273 K, 1 0.549 Good CO2 affinity. Untested beyond [114]
β-cyclodextrin (6-NH2-β-CD) method atm High 273 K.
hydrophobicity.
13 MIL-101(Cr, Mg) Cr, Terephthalic acid Hydrothermal 301 K, 1 2747.4 1.9 Good CO2 affinity. Unstable in moist [109]
Mg method atm Very high BET conditions.
surface area.

Journal of CO2 Utilization 42 (2020) 101297

14 5% PEI-MIL-101(Cr, Mg) Cr, Terephthalic acid Wet impregnation Polyethylenimine 301 K, 1 1258.330 2.5 Good CO2 uptake. Amine
Mg atm Decent surface degradation.
area. Unstable in moist
conditions.
15 10 % PEI-MIL-101(Cr, Mg) Cr, Terephthalic acid Wet impregnation Polyethylenimine 301 K, 1 3.1 High CO2 affinity. Amine
Mg atm High CC uptake. degradation.
Unstable in moist
conditions.
Untested at
higher
temperatures.
16 20% PEI-MIL-101(Cr, Mg) Terephthalic acid Wet impregnation Polyethylenimine 323.249 3
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 R. Aniruddha et al.
Table 2 (continued )
S MOF Metal Linker Synthesis Method Functionalizing compound CC BET CO2 Merits Demerits Ref
No Conditions Surface uptake
Area (m2/ capacity
g) (mmol/g)

Cr, 301 K, 1 High CO2 affinity.

Mg atm High CC uptake.
17 30% PEI-MIL-101(Cr, Mg) Cr, Terephthalic acid Wet impregnation Polyethylenimine 301 K, 1 2.6 High CO2 affinity.
Mg atm
18 40 % PEI-MIL-101(Cr, Mg) Cr, Terephthalic acid Wet impregnation Polyethylenimine 301 K, 1 128.412 2.4 High CO2 affinity.
Mg atm
19 MIL-101 Cr Cr Terephthalic acid Solvothermal 298 K, 1 2400 1.5 Good CO2 affinity. Unstable in moist [64]
method atm High BET surface conditions.
area. Untested at
higher
temperatures.
20 TEPA-MIL-101 Cr Terephthalic acid Wet impregnation Tetraethylenepentamine 298 K, 1 520 3.5 High CO2 affinity. Pore blockage.
atm High CC uptake.
21 PEI-MIL-101 Cr Terephthalic acid Wet impregnation Polyethylenimine 298 K, 1 480 2.0 Good CO2 affinity. High pore
atm Good CC uptake. blockage.
22 UiO-66/FA_mod Zr 1,4-benzene dicarboxylic Modulated 298 K, 1 1520 1.5 CC uptake is low. [115]
acid synthesis atm Untested at high
temperatures.
23 Qc-5-Cu Cu Quinoline-5- carboxylic acid Sonochemical 298 K, 1 2.48 Low cost Low porosity [116]
method atm synthesis. Good relative BET SA.
CO2 selectivity.
24 SIFSIX-3-Cu Cu Pyrazine Solution method Polyvinyl alcohol 298 K, 1 300 1.02 Good porosity. Relatively low [117]
atm CO2 affinity.
25 Zn(im-P-im) Zn Azolate Hydrothermal 298 K, 1 3.54 Excellent thermal [118]
11

method atm stability. Low

hydrophilicity.
26 Ni-4PyC Ni Pyridine-4-carboxylic acid Hydrothermal 298 K, 1 3.11 High CO2 affinity. [57]
method atm
27 30% PEI-Zn/Co ZIF@450 Zn, Imidazolate Wet impregnation Polyethylenimine 298 K, 1 35 1.4 Pore blockage [110]
◦
C Co atm
28 40 % PEI-Zn/Co ZIF@450 Zn, Imidazolate Wet impregnation Polyethylenimine 298 K, 1 11 1.8 Optimum value
◦
C Co atm
29 f-MWCNTs@Zn/Co-ZIF Zn Imidazolate Ultrasonication, Carboxylate 298 K, 1 1187 High CO2 affinity. Pore blockage [119]
Wet impregnation atm
30 N-MWCNTs@ZIF-8 Zn Imidazolate Ultrasonication, Amine 298 K, 1 1141 Optimum value Pore blockage
Wet impregnation atm
31 N-MWCNTs@ZIF-67 Zn Imidazolate Ultrasonication, Amine 298 K, 1 1127 High CO2 affinity. Pore blockage
Wet impregnation atm
32 N-MWCNTs@Zn/Co-ZIF Zn Imidazolate Ultrasonication, Amine 298 K, 1 1189 High CO2 affinity. Pore blockage
Wet impregnation atm

Journal of CO2 Utilization 42 (2020) 101297

33 PM24@ MIL-101 Cr Terephthalic acid Double solvent Polymethacrylamide 298 K, 1 2550 2.9 Very high BET SA [120]
method atm
34 PM36@ MIL-101 Cr Terephthalic acid Double solvent Polymethacrylamide 298 K, 1 2480 2.7 Very high BET SA
Method atm
35 R-PM24@ MIL-101 Cr Terephthalic acid Double solvent Polymethacrylamide, 298 K, 1 2410 3.6 Good CC uptake.
method Protonated atm Very high BET SA.
36 NH2-ZIF-8 Zn Imidazolate Solvothermal 298 K, 1 635.2 49.1 [121]
method. atm
37 18% NH2-ZIF-8 Zn Imidazolate Pre-modification Polyaniline 298 K, 1 789.7 53.57 Increase in SA
atm after loading. High
tunability.
38 ZIF-90 Zn Imidazolate 717.96 2.20 Good CC value. [122]
(continued on next page)
 R. Aniruddha et al.
Table 2 (continued )
S MOF Metal Linker Synthesis Method Functionalizing compound CC BET CO2 Merits Demerits Ref
No Conditions Surface uptake
Area (m2/ capacity
g) (mmol/g)

323 K, 1
bar
39 UiO-66 Zr 1,4-benzene dicarboxylic Solvothermal 298 K, 1 1401 2.32 [107]
acid atm
40 Cu3(BTC)2 Cu Benzene-1,3,5-tricarboxylic acid Electrochemical 298 K, 1 1627 4.40
atm
41 NH2-UiO-66 Zr 1,4-benzene dicarboxylic Solvothermal 2-amino terephthalic acid 298 K, 1 1254 3.32 Absence of crystal Structural
acid method atm defects. instability at
higher
temperatures.
42 NH2-Cu3(BTC)2 Cu Benzene-1,3,5-tricarboxylic acid Electrochemical 2-amino terephthalic acid 298 K, 1 1242 3.86 Absence of crystal Structural
method atm defects. instability at
higher
temperatures.
43 UiO-66 Zr 1,4-benzene dicarboxylic Solvothermal 298 K, 1 838 2.27 [123]
acid method atm
44 UiO-66/GO Zr 1,4-benzene dicarboxylic Solvothermal Graphene oxide 298 K, 1 1184 3.37 Higher CC value
acid method atm due to graphene
oxide. Very high
BET SA.
45 UiO-66-NH2 Zr 1,4-benzene dicarboxylic Solvothermal N,N-dimethylformamide 298 K, 1 822 2.59
acid method atm
46 UiO-66-NH2/GO Zr 1,4-benzene dicarboxylic Solvothermal N,N-dimethylformamide, 298 K, 1 1052 3.80 Higher CC value
acid method Graphene oxide atm due to graphene
12

oxide. Very high

BET SA.
47 30TEPA/UiO-66 Zr 1,4-benzene dicarboxylic Solvothermal and Tetraethylenepentamine 348 K, 1 199 3.70 Good CC value at [124]
acid wet impregnation atm high temperature.
methods.
48 NH2-UiO-66 Zr 1,4-benzene dicarboxylic Solvothermal N,N-dimethylformamide 298 K, 1 1258 3.15 High CC value. [125]
acid method atm High BET SA.
49 GMA-UiO-66 Zr 1,4-benzene dicarboxylic Solvothermal and Glycidyl methacrylate 298 K, 1 965 4.28 Very high CC Untested at
acid sonication methods atm value. High BET higher
SA and temperatures.
crystallinity.
Superb affinity
towards CO2.
50 MOF-200 Zn 1,3,5-tris(4-carboxy[1,2-biphenyl]-4- Solvothermal 298 K, 1 1265 1.17 [126]
yl)-benzene) method atm
323 K, 1 1.05

Journal of CO2 Utilization 42 (2020) 101297

atm
348 K, 1 0.95 Poor performance
atm
51 MOF-200/GO Zn 1,3,5-tris(4-carboxy[1,2-biphenyl]-4- Solvothermal and Graphene oxide 298 K, 1 167 1.34 Graphene oxide
yl)-benzene) sonication methods atm enhances CC
value.
323 K, 1 1.21
atm
348 K, 1 1.09 Poor performance
atm
52 GO@ZIF-8 Zn Imidazolate Solvothermal and Graphene oxide 298 K, 1 1200 0.8 Poor CC values. [127]
sonication methods atm
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 R. Aniruddha et al.
Table 2 (continued )
S MOF Metal Linker Synthesis Method Functionalizing compound CC BET CO2 Merits Demerits Ref
No Conditions Surface uptake
Area (m2/ capacity
g) (mmol/g)

53 MH-0 Cu, Benzene-1,3,5-tricarboxylic acid Sonication Molybdenum sulphide 298 K, 1 1272 4.12 Excellent CC [128]
Mo atm values.
54 MH-1 Cu, Benzene-1,3,5-tricarboxylic acid Sonication Molybdenum sulphide 298 K, 1 1208 3.70 Excellent CC
Mo atm values
55 MH-2 Cu, Benzene-1,3,5-tricarboxylic acid Sonication Molybdenum sulphide 298 K, 1 1639 4.64 Excellent CC Untested at
Mo atm values. Very high higher
BET SA. Strong temperatures.
affinity towards
CO2.
56 MH-3 Cu, Benzene-1,3,5-tricarboxylic acid Sonication Molybdenum sulphide 298 K, 1 1521 4.38 Excellent CC Untested at
Mo atm values. Very high higher
BET SA. Strong temperatures.
affinity towards
CO2.
57 Fe(pz)[Pt(CN)4] Fe, Pt Pyrazine Pyrazine 298 K, 1 431 4.7 A good tenability Hydrophilic [129]
atm and high CC nature.
values.
58 MIL-101(Cr)-NH2 Cr Terephthalic acid Hydrothermal 2-aminoterephthalic acid 308 K, 1 2000 3.4 Low particle [130]
method atm agglomerations
and high BET SA.
59 UiO-66(Hf) Zr, Hf 1,4-benzene dicarboxylic Solvothermal 298 K, 1 940 1.50 High CC value Works at low [131]
acid method atm temperatures
only
273 K, 1 2.38
13

atm
60 UiO-66(Hf)-NH2 Zr, Hf 2- Modulated 298 K, 1 1067 2.80 High CC value Low temperature
aminoterephthalic acid hydrothermal atm CC
273 K, 1 3.99
atm
61 UiO-66(Hf)-(OH)2 Zr, Hf 2,5-dihydroxyterephthalic acid Modulated 298 K, 1 922 4.06 High CC value Low temperature
hydrothermal atm CC
273 K, 1 4.93
atm
62 UiO-66(Hf)-(COOH)2 Zr, Hf 1,2,4,5-benzenetetracarboxylic acid Modulated 298 K, 1 378 1.20 High CC value Low temperature
hydrothermal atm CC
273 K, 1 1.67
atm
63 UiO-66(Hf)-(F)4 Zr, Hf 2,3,5,6-tetrafluoro-1,4- Modulated 298 K, 1 329 0.82 Low temperature
benzenedicarboxylic acid hydrothermal atm CC
273 K, 1 1.23

Journal of CO2 Utilization 42 (2020) 101297

atm
64 GO-TAc/MOF-60 Cu 1,3,5- Reflux method 1-Butyl-3- 298 K, 1 1763 5.62 Excellent sorption [132]
benzenetricarboxylic acid methylimidazolium atm performance
tetrafluoroborate and
graphene oxide
65 Meso-Tetraphenyl Cu Tetraphenylporphinato ligand He–Ag Laser N,N-dimethylformamide 298 K, 40 3418 1.74 Ultra high BET SA [133]
Porphinato–Cu(II) Assisted Synthesis atm
66 PPIA-MOF-5(40 %) Zn Terephthalic acid Polypropylene itaconate 298 K, 1 12.35 3.5 High CC value Low BET SA [77]
atm
67 Ni(II)-MOF Ni 1,3,5- tribenzyl-1,3,5-triazine-2,4,6- Microwave 298 K, 27 3181 2.69 High BET SA Effective at high [134]
(1H,3H, 5 H)-trione synthesis atm pressure
68 PAN/HK@HK3-A NFM Cu 1,3,5-benzenetricarboxylate Polyacrylonitrile 912 3.9 [135]
(continued on next page)
 R. Aniruddha et al.
Table 2 (continued )
S MOF Metal Linker Synthesis Method Functionalizing compound CC BET CO2 Merits Demerits Ref
No Conditions Surface uptake
Area (m2/ capacity
g) (mmol/g)

Solvothermal, 273 K, 1
Electrospinning atm
69 Bz@InOF-1 In Biphenyl-3,3 , 5,5 -tetracarboxylate
′ ′
Solvothermal Benzene 298 K, 1 2 [136]
method atm
70 MIL-96(Al)–Ca1 Al, Benzene1,3,5-tricarboxylic acid Solvothermal Calcium carbonate 273 K, 9.3 754.57 10.22 Works at high [137]
Ca method atm pressure
71 MIL-96(Al)–Ca2 Al, Benzene1,3,5-tricarboxylic acid Solvothermal Calcium carbonate 273 K, 9.3 594.15 9.38 Works at high
Ca method atm pressure
72 50PEI@meso-UiO- Zr, Lauric acid Solvothermal Polyethyleneimine 298 K, 1 92 1.39 Pore blockage [138]
66− 0.2Cu Cu method atm
73 Zn(Bmic)(AT) Zn 1H-benzimidazole-5-carboxylic acid Solvothermal 5-aminotetrazole 353 K, 5 3.53 Works in mild [139]
method bar conditions
74 Zn(BPZ) Zn 3-nitro-4,4′ - bipyrazole Solvothermal 298 K, 1 930 5.1 High CC value [140]
method atm
75 PEI(50)@NU-1000 Zr 1,3,6,8-tetrakis(p-benzoic acid) Ultrasonication Polyethylenimine 298 K, 1 604 1.75 Low cyclic [111]
pyrene atm stability
76 Ca3L2(H2O)2(DMA)2 Ca (4,8)-connected flu(fluorite) 298 K, 1 4.32 Largely untested [141]
atm
77 PCN-250(Fe2Co) Fe, 3,3′ ,5,5′ -azobenzenetetracarboxylic Solvothermal 298 K, 1 1653 2.23 High BET SA [142]
Co acid method atm
78 ACN1/3@Cu-BTC Cu Terephthalic acid 298 K, 1 1504 4.32 Moisture stability [143]
atm
79 mmen-Mg2(dobpdc) Mg Dimethyl ethylene diamine Seeded synthesis Polyethylenimine 298 K, 1 894 3.33 Good CC CC decreases in [144]
atm performance moisture
14

80 sod-ZMOF-chitosan In 4,5-Imidazoledicarboxylic acid Reflux method Sodalite and chitosan 298 K, 1 22.23 [145]
atm
313 K, 1 14.55
atm
343 K, 1 12.41 Decent
atm performance
81 {[(CH3)2NH2][Zn2(L) Zn 5-(1H-imidazol-1-yl)isophthalic acid Solvothermal 298 K, 1 4.99 Uses mostly in [75]
(H2O)PO4]⋅2DMF}n method atm catalysis
82 MOF-505@5GO Cu 3,3, 5,5 -biphenyltetracarboxylic acid Hummer’s method Graphene oxide 298 K, 1 1279 3.94 High CO2 [146]
atm selectivity
83 UTSA-16 Co Citric acid Vacuum heating 333 K, 4.5 Good CC value in [147]
0.85 atm moisture
84 Imi1/3@Cu-BTC Cu 1,3,5-benzenetricarboxylic acid Temperature Imidazole 298 K, 1 1694 4.4 Fast synthesis, Untested at [148]
synthesis method atm Moisture stability higher
temperatures
85 NbOFFIVE-1-Ni Ni, Pyrazine Solvothermal Niobium Pentoxide 298 K, 1 1.3 [149]

Journal of CO2 Utilization 42 (2020) 101297

Nb method atm
86 Tb-L Ln 10,10′ -bis(4-carboxyphenyl)-9,9′ - Reflux method 298 K, 1 1.84 Poor CC [150]
bianthryl atm performance
87 Cu-BTC-PEI-2.5 Cu 1,3,5-benzenetricarboxylic acid Polyethylenimine 298 K, 1 885.73 4.15 Good CC [151]
bar
313 K, 1 2.61
bar
328 K, 1 1.60
bar
88 [Ni-4PyC, Ni9(m- Ni Pyridine-4-carboxylic acid Solvothermal 298 K, 10 945 8.2 Potential in humid [152]
H2O)4(H2O)2(C6NH4O2) method bar CC
18.solvent]
(continued on next page)
 R. Aniruddha et al.
Table 2 (continued )
S MOF Metal Linker Synthesis Method Functionalizing compound CC BET CO2 Merits Demerits Ref
No Conditions Surface uptake
Area (m2/ capacity
g) (mmol/g)

89 LDH@ZIF-67 Zn Imidazolate Hydrothermal 303 K, 1 0.52 Good potential in [153]

method atm CC
90 ZIF-8− 90 100 % Zn Imidazolate Hydrothermal 273 K, 1 949 5.22 [154]
method atm
91 MOF-505 Cu 5,5′ -(pyridine-2,5- diyl)diisophthalic Solvothermal 273 K, 1 5.51 Decent CO2 [155]
acid method bar affinity
92 HNUST-7 Cu 4′ -(3,5-dicarboxybenzamido)-[1,1′ - Solution method 273 K, 30 2804 26.1 High pressure CC [156]
biphenyl]-3,5-dicarboxylic acid bar
93 opt-UiO-66(Zr)-(OH)2 Zr 2,5-dihydroxyterephthalic acid Modulated 298 K, 1 1230 5.63 Excellent CC value [157]
hydrothermal atm
94 [Zn2(NH2BDC)2(dpNDI)]n Zn 2-aminoterephthalic acid, N,N -di(4- ′
Solvothermal 298 K, 1 1.26 Thermally [158]
pyridyl)-1,4,5,8-naphthalenediimide method atm susceptible
95 [Zn5(btz)6(bdc)2(H2O)2]⋅ Zn Benzotriazolate, 1,4- 298 K, 1 895.7 2.16 Higher N2 [159]
7DMA benzenedicarboxylate atm selectivity
96 MIL-53 Al Benzene-1, 4-dicarboxylic acid Ultrasonic method 298 K, 1 137.9457 0.05 Low CC value [160]
atm
97 MWCNT@MIL-53 Al Benzene-1, 4-dicarboxylic acid Multi-wall carbon 298 K, 1 143.5005 0.3 Low CC value
nanotubes atm
98 CNF@MIL-53 Al Benzene-1, 4-dicarboxylic acid Carbon nano fibers 298 K, 1 139.803 0.1 Low CC value
atm
99 MWCNT@MIL-101 Cr Terephthalic acid Hydrothermal Multi-wall carbon 298 K, 1 0.003 Low CC value [161]
method and wet nanotubes atm
impregnation
100 1⋅MeCN Cu 4-(4-pyridyl)-2,5-dipyrazyl-pyridine Solvothermal MeCN 298 K, 1 0.82 Low CC value [162]
15

method atm
313 K, 1 0.66 Low CC value
atm
101 1-mmen Mg 1,5-Dioxido-2,6- Microwave method N,N’- 298 K, 1 99 4.13 High CC uptake [163]
naphthalenedicarboxylic acid dimethylethylenediamine atm
1-en Mg 1,5-Dioxido-2,6- Solvothermal 298 K, 1 40 2.63 Pore blockage
naphthalenedicarboxylic acid method atm
1-ppz Mg 1,5-Dioxido-2,6- Microwave method Piperazine 298 K, 1 47 3.15 High CC uptake
naphthalenedicarboxylic acid atm
102 1000-as Zn 2-methylimidazole Mechanochemical 298 K, 1 1292 3.31 High CC uptake, [164]
and carbonization atm BET SA
methods
1000- clean Zn 2-methylimidazole Mechanochemical 298 K, 1 1222 3.22 High CC uptake,
and carbonization atm BET SA
methods
103 MOF-888 Ni 1′ ,2′ ,3′ ,4′ ,5′ ,6′ -hexakis(4- Sonication 800 Torr 38 1.07 Low CC uptake [165]

Journal of CO2 Utilization 42 (2020) 101297

carboxyphenyl)- and 298 K
benzene
MOF-889 Mg 1′ ,2′ ,3′ ,4′ ,5′ ,6′ -hexakis(4- Sonication 800 Torr 144 2.46 Low CC uptake
carboxyphenyl)- and 298 K
benzene
MOF-890 Cu 1′ ,2′ ,3′ ,4′ ,5′ ,6′ -hexakis(4- Sonication 800 Torr 295 2.59 Low CC uptake
carboxyphenyl)- and 298 K
benzene
MOF-891 Cu 1′ ,2′ ,3′ ,4′ ,5′ ,6′ -hexakis(4- Sonication 800 Torr 200 2.59 Low CC uptake
carboxyphenyl)- and 298 K
benzene
104 476-MOF Dy Benzene-1,3,5-tribenzoate 898 1.68 [166]
(continued on next page)
 R. Aniruddha et al.
Table 2 (continued )
S MOF Metal Linker Synthesis Method Functionalizing compound CC BET CO2 Merits Demerits Ref
No Conditions Surface uptake
Area (m2/ capacity
g) (mmol/g)

Solvothermal 293 K, 1 CC could be

method atm enhanced
477-MOF Dy 4,4′ ,4′′ -s-triazine-2,4,6- Solvothermal 293 K, 1 902 1.92 CC could be
triyltribenzoate method atm enhanced
105 ɤ-CD-MOF K ɤ-CD Flow chemical 303 K, 1 970.3 0.55 Low CC uptake [167]
atm
106 NPC-6 Cu 5,5′ -(piperazine-1,4-diyl)- Solvothermal 293 K, 1 1579 4.83 Very high CC Low temperature [168]
diisophthalate acid method atm
107 TMOF-1 Cu 4,4′ -bipyridine and disodium 1,2- Hydrothermal 298 K, 1 238 1.45 Poor performance [169]
ethanedisulfonate method atm
108 [Cu2L(H2O)2]• Cu 5,5′ -(dimethylsilanediyl) 273 K, 1 1145.9 6.65 Good CC [170]
4H2O•2DMF diisophthalic acid atm
16

298 K, 1 1145.9 5.2 Good CC

atm
109 Cr-MIL-101-SO3H Cr Monosodium 2-sulfoterephthalic acid Flow chemical Tris(2-aminoethyl)amine- 313 K, 150 2.28 Inexpensive Mediocre CC [171]
method functionalized mbar synthesis uptake
110 MIL-91(Al) Al N,N′ - Hydrothermal 303 K, 1 Good at high [172]
piperazinebismethylenephosphonic method bar pressures
acid
111 Co2L2(AzoD)2⋅2DMF (1) Co Azobenzene-3,3′ -dicarboxylic acid, Solvothermal 298 K, 1 0.56 Poor performance [173]
N1,N4-di(pyridin-4-yl) method atm
terephthalamide
112 Al-soc-MOF-1 Al 3,3′′ ,5,5′′ -tetrakis(4-carboxyphenyl)- Solvothermal 298 K, 1 5585 High BET SA High pressure [174]
pterphenyl method bar
113 PN@MOF-5 Zn 1,4-benzenedicarboxylic acid Solvothermal 1,2-diethynylbenzene 3.48 Good CC uptake [175]
method

Journal of CO2 Utilization 42 (2020) 101297

R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Table 1 (continued )
S MOF Synthesis method and Process Process Properties Merits Demerits Ref
No reagents employed Conditions

Vapour diffusion Heating the FTIR: Presence of Permanent CO2

method. mixture slowly -OCCO- moiety. capture.
over diffusing
methanol over
seven days.

pressure as with Cu-BTC, aPPy displayed CC values of 7 mmol/g and The most important observation from Table 2 is that most MOFs have
4.03 mmol/g respectively. Impressive still is the fact that in this high CC uptake values only at low temperatures i.e. from 273 K to 303 K.
particular study, pure aPPy had a BET surface area of 2420 m2/g in As temperature of the capture process increases, a steep decrease in CC
comparison to pure Cu-BTC’s 1760 m2/g. Both aPPy and Cu-BTC nearly values could be observed. Wang et al. [176] explained that with the
had the same isosteric heats of adsorption at 24.9 kJ/mol and 25.45 increase in process temperature stability of MOF crystal structures are
kJ/mol respectively. The higher value of isosteric heat of adsorption for compromised. Singo et al. [145] also recorded the CC performance of
Cu-BTC is reportedly due to the higher porosity. This porosity in turn sod-ZMOF-chitosan (chitosan loaded ZMOF) at three different temper­
results in van der Waals forces that keep CO2 strongly adsorbed through atures 298 K, 313 K and 343 K. The CC values at these temperatures are
dispersive interactions. 978 mg/g, 640 mg/g and 546 mg/g respectively, which gives a marked
The second form in which MOFs are commonly tested in gas sepa­ decrease in CC capacity. The same trend is also reported in the findings
ration is with an additional functional group. A good deal of research is of Aarti et al.’s [151] CC studies on Cu-BTC-PEI-2.5. The studies were
under works in regards to which functionalizing compound performs the conducted at 298 K, 313 K and 328 K, for which the CC values were
best at CO2 capture and at what percentage of loading. Poly­ found to be 4.15 mmol/g, 2.61 mmol/g and 1.6 mmol/g. The structural
ethyleneimine is a popular functionalizing compound that works well stability of MOFs faded even with low increase in temperatures, which in
with MOFs. Lawson et al. [64] reported a MOF known as PEI-MIL-101 to turn caused a degradation in the values of CO2 adsorbed.
have a decent CC value of 2 mmol/g for a BET surface area of 480 m2/g. Another critical issue associated MOFs is their affinity towards
In comparison to the pure MIL-101′ s 1.5 mmol/g (for a surface area of moisture. This greatly hampers their ability to trap other gases.
2400 m2/g), this is only a slight improvement. Gaikwad et al. [109] also Furthermore, the crystalline structures of MOFs collapse entirely when
worked with a similar MOF MIL-101(Cr, Mg) which reported a CC value they come into contact with moisture. There are three possible ways to
of 1.9 mmol/g for a surface area of 2747 m2/g. In this study, MIL-101 increase the CC capacity as well decrease the influence the effects of
(Cr, Mg) was loaded with the percentages of 5, 10, 15, 20, 30 and 40. moisture. Increasing open metal sites is one way of increasing in­
All of them gave decent CC values but the 10 % PEI-MIL-101(Cr, Mg) teractions between acidic gases and MOF structures as is given by
gave the highest CC value of 3.1 mmol/g. In the findings reported by Mohamedali et al. [177]. Metal ions with multiple positive valences
Cheng et al. [110] and Kang et al. [111] the respective MOFs showed tended to give some of the best adsorption values. Pre-synthetic modi­
decent CC values. The former reported on a functionalized MOF desig­ fications also present an interesting option to influence CC values.
nated as 40 % PEI-Zn/Co ZIF@450 ◦ C. This MOF showed a CC value of Pre-synthetic modifications [178] include altering the solvent compo­
1.8 mmol/g despite having a surface area of only 11 m2/g. PEI(50) sition, temperature, etcetera to influence the morphology of the MOF
@NU-1000 [111] also recorded in a modest 1.75 mmol/g for a decent and hence the CC capacity. The final technique is post-synthesis [179]
surface area of 600 m2/g. Other popular functionalizing compounds are functionalization involves modifying the obtained MOF after synthesis
polyaniline, polyacrylonitrile and other amines. Amines are known to be to suit a particular need. This type of change enhances important factors
greatly attracted towards acidic oxides such as CO2 due their highly like hydrophobicity and specific selectivity towards CO2.
basic nature.
The third form in which MOFs are employed is in combination with 4. Adsorption based on stimulus response
sorbents. Szczęśniak et al. [108] applied the combination of Cu-BTC
with graphene oxide (GO) at three different variants designated as Conventional, and commercial, adsorption processes include two
Cu-BTC/GO2, Cu-BTC/GO5 and Cu-BTC/GO10. They showed CC values types viz pressure-swing adsorption [180] and temperature-swing
of 9.05 mmol/g, 8.46 mmol/g and 9.59 mmol/g for surface areas of adsorption [181]. These two technologies account for most of the CC
1820 m2/g, 1520 m2/g and 1380 m2/g. Despite a decrease in BET sur­ studies both in research and at operational levels. But these are only two
face area, the CC value of Cu-BTC/GO10 was found to be identical to the amongst a vast types of adsorption processes that respond to various
pure version of the MOF. Graphene oxide enhanced the CC uptake stimuli [182]. Broadly classified as follows
ability despite a reduction in available sites to an apparently optimum
value. Sami Ullah et al. [126] compared the CC uptake of both MOF-200 • Pressure responsive
and the graphene oxide loaded MOF designated as MOF-200/GO to be • Temperature responsive
1.17 mmol/g and 1.34 mmol/g. Interesting to note that despite having • Photo-responsive
extraordinarily high BET surface areas of 3624 m2/g and 3359 m2/g for • Magnetic field responsive
MOF-200 and MOF-200/GO respectively, the CC uptake value is • Electric field responsive
underwhelming. These low values were attributed to the low CO2 per­ • Guest molecule responsive
centage in the feed itself. Hence, both the studies indicated that GO had
high affinity towards carbon dioxide. Multi walled carbon nanotubes With the common methods, pressure and temperature swing
(MWCNT) are another class of sorbents that are being used in tandem adsorption, proving to be slightly expensive, the need for potentially
with MOFs. MWCNT@MIL-53 [160] displayed a CC value of 0.3 mmol/g more inexpensive is always important from an engineering point of
at 298 K at 1 atm. In comparison, the pure MIL-53 reported a value of view. Magnetic field responsive [183], as the name suggests, are mate­
just 0.05 mmol/g. This was attributed to pore blockage and interference. rials/adsorbents that utilize a magnetic field to induce CO2 capture.
MWCNT@MIL-101 [161] also recorded a low CC value 0.03 mmol/g Electric field responsive adsorbents [184] utilize an electric to induce a
and for the same reasons as above. Overall, much work is yet to be done charged CO2 capture. Guest molecule responsive adsorption [185] in­
on this field of multiple adsorbents. dicates the deployment an additional compound/material to implement

17
R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

a temporary CO2 capture. being faced by these adsorbents.

Amongst these, photo-responsive adsorbents, have been/are being Major challenges that are involved in these setups are issues of in­
studied with great interest. Photo-responsive adsorbents [186], the dustrial scale ups. Secondly, the compounds employed as light sensitive
materials which use the shift in photo waves to induce a temporary CO2 facilitators are hazardous to the environment and large scale usage
capture. Usually a combination of UV–vis lights to induce the adsorption could lead to major contamination incidents [196]. The organic pre­
and desorption processes as illustrated by Fig. 3. An organic isomer or cursors to these light sensitive compounds are often carcinogenic in
enantiomer is usually coated/doped on an adsorbent framework to nature, so prolonged periods of exposure could lead to fatal outcomes.
facilitate the capture. Azobenzene functionalized photo-responsive Future studies in this field should be more focused on finding
adsorption [187] has become well known in the recent past. MOFs eco-friendlier light sensitive CC facilitators.
themselves being good organic receptors, readily accept the assistance of
photo-responsive organic molecules. Junkil Park et al. [188] have re­ 5. Kinetics and simulation modelling
ported a Mg-IRMOF-74-III functionalized with azopyridine to be
employed in CC studies. This material was reported to have a CC uptake 5.1. Adsorption isotherms
value of 89 cc/g, which also happens to be the highest photo-responsive
CC value for a MOF ever recorded. This value is also comparable to the The four primary adsorption isotherms are employed to study
ones obtained through conventionally followed pressure/temperature adsorption processes in general are the Langmuir [197], Freundlich
adsorption. Prasetya et al. [189] have reported another novel [198], Toth [199] and Sips [200] adsorption isotherms. The Langmuir
Azo-DMOF-1 MOF based membrane networks with potential in isotherm [201–204] is often the most commonly used to explain
photo-responsive separation. Amines and nitrogen containing aromatic adsorption phenomenon. This model considers the following
organic compounds were found to be highly light sensitive as explained assumptions:
by Lei Cheng et al. [190]. The critical parameters involved in such an
adsorption are the surface areas of the basic adsorbent frameworks, • the molecules are adsorbed onto a fixed number of active sites
nature of the light sensitive compound employed and the intensity of the • monolayer adsorption takes place
light employed as explained by Haldar et al. [191]. Dinesh et al. [192] • each active site can hold only one molecule at a time
has reported the synthesis of various light sensitive molecules to aid in • each site is at the same energy level
photo-receptive CO2 capture. Most of these compounds were aromatic • surface of the adsorbent is homogeneous
compounds like 4-iodo-2,5-dimethylthiophene, 2-chlor­ • there is no interaction between the adsorbed molecules
o-4-iodo-5-methylthiophene, para-toluene sulfonic acid etcetera. Li • the adsorption system is in equilibrium
et al. [193] reported a combination of photo-magnetic responsive ad­
sorbents. In one of their other studies [194], they report of a The Freundlich isotherm is the simplest isotherm that considers
photo-magnetic CO2 release of a dual photo-magnetic responsive multilayer adsorption and high level of heterogeneity. In this model, it is
framework named PCN-250 (mPCN). Without additional heat or pres­ assumed that multilayer formation occurs and adsorption takes place at
sure, a 96.8 % CO2 release was observed at atmospheric pressure. random sites. This model also takes into account of the possibility that as
Similarly, Lyndon et al. [195] coated methyl red dye on Mg-MOF-74 to adsorption progresses there is a decrease in adsorption of subsequent
obtain an 84 % uptake changes only with variations in irradiation molecules. In the Toth adsorption model, it is assumed that most sites
intensities. have a lower adsorption energy than the energy peak of maximum
The major advantage of this type of adsorption is that it relies on adsorption. The Toth isotherm [181,205–207] modifies the Langmuir
visible light, one of the most abundant sources of stimuli. This could be equation to reduce the error between the experimental and predicted
considered as an immediate cut in adsorption costs. As no heat is values of adsorption. This model is best suited for heterogeneous sys­
involved in the process, the stability MOFs in such experimental setups tems in which multiple adsorption layers occur. The Sips model
can improve greatly. Since stability is directly linked to cyclic or [208–211] includes both the Freundlich and Langmuir models, has three
repeated usage, it can be predicted that the cyclic performance MOFs in parameters taken from the theory of these models. Hence, like the Toth
these kinds of setups can be improved upon. This is a major cost saver as model, it has a greater capacity to describe adsorption equilibrium than
lack of cyclic stability in conventional setups is one of the challenges both Langmuir and Freundlich.

Fig. 3. Photo-responsive CO2 adsorption.

18
R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

5.2. Kinetic models CO2 being more preferred by the MOF over CH4. Chang et al. [217] have
also identified the exact adsorption sites of CO2 on the MOF Znbpetpa
Two types of models are commonly employed to explain adsorption using DFT and canonical Monte Carlo simulations.
processes in general, adsorption kinetic and diffusion kinetic models. In Coordinatively Unsaturated Metal sites (CUMs) are also amongst the
adsorption kinetic models, adsorption is assumed to be the rate deter­ key factors simulation studies consider to determine CO2 capture limits.
mining step. This is usually assumed in cases of chemisorption, wherein Open or unsaturated metal often act like basic sites and attract the acidic
the adsorption is of a chemical nature. Three primary adsorption kinetic CO2 molecule. Hou et al. [218] elucidate on this factor using a combi­
models exist. They are: nation of DFT and GCMC. Their findings conclude that the high CO2
adsorption ability of M-MOF-74 is due to the strong acid-base in­
• Pseudo first order model teractions between the metal ions and CO2. The research also stated that
• Pseudo second order model there were strong interactions between the carbon atom of CO2 and the
• Elovich kinetics model organic linkers of M-MOF-74.
The topology of the metal organic framework, subject to CO2
The pseudo first order model is based on the following assumptions. adsorption, is often crucial in determining the CC uptake values. Morris
Adsorption only occurs on localized sites and involves minimal inter­ et al. [219] extensively studied on the series of ZIFs; ZIF-7, ZIF-11,
action between adsorbate species. The energy of adsorption is inde­ ZIF-93, and ZIF-94 regarding the effects of topology on CO2 capture. All
pendent on the area of the surface covered. Maximum adsorption these ZIFs reportedly have the same metal ion and imidazolate linker but
indicates to a saturated mono-layer of adsorbate. The concentration of different topologies. It was found that MOFs with smaller pore structures
adsorbate is considered to be constant. The pseudo second order model had more CC uptake values at lower pressures while MOFs with larger
is similar to the pseudo first order model with the only difference being pores had higher uptake values at higher pressures. The smaller pores
that the overall order of the reaction is reduced to 2 instead of 1. A have stronger binding potentials than the larger ones, they were unable
similar pseudo nth order kinetics can also be explained in general using to provide multiple accommodation sites. The larger pores, however,
similar assumptions. The Elovich kinetics model, however, improves offered more room for multiple CO2 occupancies and hence had high CC
upon the previous two models significantly by taking into account values at high pressures. The same was hinted in an earlier study by Bae
additional factors. The Elovich model assumes that there is considerable et al. [220] in their study of CO2 adsorption on a large pore sized IRMOF-
interaction between adsorbed species and that energy of adsorption 16.
increases as the adsorption process progresses.
Out of the aforementioned kinetic models, pseudo first and second 6. Other aspects
orders were most prevalent. Since most MOFs are involved in chemi­
sorption, the pseudo second order kinetics is the single most common 6.1. Reactors and contactors
model encountered. Zhao et al. [212] experimented on the metal ion
uptakes on the Ce-HKUST-1 and found that they indeed followed a Basic CC equipment involving MOFs are dived to two broad cate­
pseudo second order kinetic model. Rehman et al. [112] reported the CC gories viz adsorber columns and membrane contactors. Adsorber col­
studies of piperazine loaded γCD-MOF. Apart from having promising CC umns are further divided into three categories. The first of them is the
values (12.3 wt % at 1.1 bar and 333 K), the kinetics was found to fit fixed bed type [221]. This is the simplest type of adsorber. The second
pseudo second order very well. important type is the fluidized bed type. Fluidized bed type adsorbers
Diffusion kinetic models assume that diffusion through the porous [222] use a counter-flow design in which gas typically enters the
adsorbent is the rate determining step. The three prevalent models are adsorber vessel from the bottom and flows up the column, while re­
Crank model, Weber-Morris model and Bangham model. Many kinetic generated adsorbent enters from the top and gradually moves to the
parameters were considered in the kinetic studies of MOFs. As bottom of the column. The exhausted sorbent is collected at the bottom
mentioned earlier, temperature of the adsorption process plays a sig­ of the vessel and transferred to a regeneration chamber. The third type is
nificant part in determining the CC value of an adsorbent. MOFs membrane-adsorber/contactor [223] type. Here a membrane is
generally operated well at adsorption temperatures between 273 K and employed to separate CO2 from the feed gas. MOFs have such great
353 K. Composition of the feed was also important factor in determining tunability that they can be used as membranes in membrane separators
capacity. Mostly the feed consisted of N2/CO2 and CO2/CH4. This helps as well.
in comparing the selectivity. Pressure of adsorption is another parameter Figs. 4 and 5 give a list of reactors/adsorbers that are utilized in CC.
determining the CC uptakes. The findings in Sreenivasulu et al. [224] explain the various types of
contactor technologies used in CO2 separation. The rotating packed
5.3. Computational approach to CO2 capture and factors to consider reactor was reportedly a great choice as far as adsorption CC is con­
cerned. Another good choice for is the simple packed bed reactor which
Computational approach to CO2 capture involves the identification gives a good efficiency [225].
of certain critical factors in order to properly simulate CO2 capture in
MOFs and adsorbents in general [213]. One such factor is the effect of
electrostatic interactions on CO2 adsorption. Snurr et al. [214] have 6.2. Design and morphology
explained the effects of electrostatic interactions in great details. In their
simulation studies of carbon capture by MOF-177 and IRMOF-3, this MOF morphology study consists mainly of its crystal structures and
effect was included. Similar to Snurr, Yang et al. [215] have studied the its BET surface area/BJT pore volume. Simple geometrical shapes also
effects of electrostatic interactions on the CO2 adsorption of IRMOF-14, referred to as secondary building units (SBUs) are often used to help
IRMOF-17, and MOF-177. Their results revealed that electrostatic in­ understand the crystal structures of MOFs. MOFs, which have compli­
teractions between the MOFs and CO2 increased the uptake values cated crystal structures, can be explained using these simple secondary
significantly at low pressures but only marginally at higher pressures. building units. MOFs exist in various clusters, which can be represented
Another factor to consider in adsorption simulations, is the identi­ in simple geometric shapes such as tetrahedral, octahedral, pyramid.
fication of probable adsorption sites. Pianwanit et al. [216] have studied Four basic factors, as given in Fig. 6, have widely been identified to
on the probable binding sites and energies for carbon dioxide and influence the design and morphology of MOFs. They are temperature of
methane during their adsorption on MOF-5. The inference from their synthesis, process parameters/reagents/composition, enhancers/modi­
study was that corner sites were the most probable binding sites with fiers and type of synthesis.

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R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Fig. 4. CC equipment summary.

6.2.1. Effect of temperature has a cube like crystal structure with smooth morphology and good CC
The first of them is temperature of synthesis. Jiang et al. [226] potential. MOFs synthesized at lower temperatures lower dimension­
explained how temperature of synthesis affected the morphology of ality although there is no concrete relationship [228].
Co-MOF-74. In this study, Co-MOF-74 was synthesized at four different
temperatures 373 K, 393 K, 408 K and 428 K, out of which the one 6.2.2. Effect of reagents, process parameters and composition
synthesized at 373 K showed the best morphology needed for CC. Like temperature, reagents and process parameters have a great in­
Mulyati et al. [227] also synthesized MOF-5 at three different temper­ fluence on the crystal structure and morphology of MOFs. Liu et al.
atures 383 K, 393 K and 413 K. MOF-5 synthesized at 393 K and 413 K [229] reported the manipulation in structure of ZIF-78 with just change

20
R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

Fig. 5. CC equipment summary continued.

in solvent compositions. A wide range of structures starting from long morphology of the obtained MOF. Forgan [232], in his review of
rod type to squatting type was observed with just a change in ligand modulated assembly of MOFs, reported that enhancers influence crys­
amount. Similarly Guo et al. [230] has reported a change in crystal sizes tallinity, particle size, defectiveness and crystalline phases. Rosnes et al.
of the MOF Dy(btc)H2O by just manipulating the amount of sodium [233] reported that a MOF CPO-27 was synthesized with different ad­
acetate in feed. Wide ranges of crystal sizes from 55 μm to 50 nm were ditives of benzoic acid and acetic acid. Smaller needle shaped
observed with changes in pH. Abazari et al. [231] also elaborates the morphology was observed for a large amount of benzoic acid, while a
effects of pH on drug carrying abilities of the MOF DUT-32-K. hexagonal shape was observed with acetic acid. It was also commented
in Rosnes et al. however that enhancers only affect these properties in a
6.2.3. Effect of enhancers/modifiers minor way.
Enhancers/modifiers added during synthesis process influence the

21
R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

adsorption also take in moisture and hence obstruct possible CC. Affinity
towards CO2 is another factor that plays a crucial role in CC. Fortunately
many studies have revealed that most MOFs have an innate ability to
attract acidic gases and that includes CO2 as well. Morphology makes up
for the MOFs tendency to trap gases. Innate crystal defects, chemical
composition and crystal structures often dictate the amount and type of
adsorption. Cyclic stability and regenerability are also crucial economic
factors that dictate whether a given adsorbent can be scaled up to a
macro-sized industry. In this regard however, MOFs have certain dis­
advantages over other adsorbents like activated carbons. The low innate
thermal stability of MOFs makes it hard to regenerate and employ them
for cyclic studies at high temperatures. Similarly, another area in which
MOFs need to be optimized is in finding new innovative ways of syn­
thesis on even a large lab scale.
Fig. 6. Factors affecting the morphology of MOFs.
Screening techniques include majorly three types of experimental,
computational and a hybrid of both experimental and computational
6.2.4. Effect of synthesis type
methods. Experimental screening [213] consists of checking the CC
Three known ways of synthesis affect MOF morphology and design
ability of MOFs with good set of experiments considering various pa­
exist. They are deprotonation regulation synthesis, coordination mod­
rameters. Computational screening [238] involves numerical and soft­
ulation synthesis and surfactant modulation synthesis. In deprotonation
ware related methods to identify the perfect MOFs tailored for each
regulation synthesis [234] multiple process parameters such as tem­
specific process. Computational screening, especially high throughput
perature, composition and time of synthesis vary. Coordination modu­
screening [239] is extremely helpful in scouring through a wide range of
lation synthesis [235] is the variation of concentrations of solvents,
MOFs to determine the ones best suited for the specific process. Song Li
reagents and additives during the process of synthesis. Lastly in sur­
et al. [240] have used throughput screening over a database of 10,000
factant modulation synthesis [236], surfactants are employed, at the
MOF structures to determine the most useful ones.
time of synthesis, to greatly alter MOF morphologies.
7. Conclusions
6.3. Screening and selection
In conclusion, MOFs are a very interesting prospect for large scale CC
Screening of MOFs is based on many factors. It is the process of and other gas separation processes in general. However, MOFs face a few
choosing appropriate adsorbents for CC. Fig. 7 illustrates all the major challenges that prevent them breaking into the commercial scene. They
factors required for a good adsorbent in CC conditions. are
Most studies and reviews [237] found that there are mainly six
important criteria whilst screening MOFs for CC. They are selectivity, • They have well defined methods synthesis like solvothermal, ultra-
hydrophobicity, CO2 affinity, morphology, regenerability and ease of sonication etcetera. However, most of these methods are suited for
synthesis. Selectivity towards CO2 is a very important factor in CC small scale and laboratory experiments. No optimization is available
studies. Abid et al. [137] explained how a MOF MIL-96(Al) had as of yet to scale them up for industrial production. Ultra-sonication,
increased CO2 selectivity to a factor of 60. Hydrophobicity is a very microwave assisted synthesis were found to be very much useful in
important factor that has to be addressed always. MOFs being good at obtaining good topologies and crystallinity. Nevertheless, both these
methods are energy intensive at large scale. Novel hybrid methods
such as microwave assisted solvothermal method and solvent assis­
ted mechano-thermal methods have shown potential to be projected
at a large-scale projection.
• MOFs inherently have good affinity towards carbon dioxide, which
in turn result in good separation processes. However, a notable
drawback is lack of thermal stability. This impacts both cyclic studies
and regenerability. It means that MOFs cannot be used in repeated
CC studies, which impacts longevity. Another notable drawback is
their tendency to attract moisture. As explained earlier, moisture
leads to a complete or near complete collapse of the crystal structures
of most MOFs. A possible future solution to address both these issues
is to increase the available open metal sites. Another promising so­
lution is to increase the functional affinity towards carbon dioxide
with suitable agents.
• Kinetic studies indicate that MOF adsorption processes mostly follow
pseudo-first order and pseudo second order reactions. Pseudo second
order in particular, explains most CO2 adsorption on MOFs. Lang­
muir and Toth adsorption isotherms hold good in explaining the
processes as whole. Further research in terms of increasing the heat
of desorption and making the process more spontaneous is required
with both modelling and synthesis methods. Simulations, in
consideration with various factors such as effect of electrostatic in­
teractions, effect of topologies, active sites etcetera
• Screening methods of MOFs involve both experimental and compu­
tational methods. High-throughput screening in particular was found
Fig. 7. Factors deciding MOF morphology. to extremely convenient and efficient in determining the most

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R. Aniruddha et al. Journal of CO2 Utilization 42 (2020) 101297

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