Received: 25 May 2023 Revised: 27 July 2023 Accepted: 31 July 2023

DOI: 10.1002/sus2.154

REVIEW

Screening, preparation, and prototyping of metal–organic

frameworks for adsorptive carbon capture under humid
conditions

Long Jiang1 Jinyuan Yong1 Renyu Xie1 Pengfei Xie2 Xuejun Zhang1
Zhijie Chen3 Zongbi Bao2

1 KeyLaboratory of Refrigeration and

Cryogenic Technology of Zhejiang Abstract
Province, Institute of Refrigeration and Adsorption-based carbon capture has been recognized as an attractive method
Cryogenics, Zhejiang University,
for mitigating global warming. Metal–organic frameworks (MOFs) are promis-
Hangzhou, Zhejiang, China
2 College
of Chemical and Biological
ing candidate adsorbents for this purpose due to their high adsorption uptake and
Engineering, Zhejiang University, selectivity for carbon dioxide. However, in real-world applications, such as direct
Hangzhou, Zhejiang, China air capture, the presence of moisture in the feed gas may pose a grand challenge
3 StoddartInstitute of Molecular Science,
for CO2 adsorption in MOFs. This paper aims to address the issue of water–CO2
Department of Chemistry, Zhejiang
University, Hangzhou, Zhejiang, China co-adsorption in MOFs and present screening criteria for selecting MOFs that
preferentially adsorb CO2 under humid conditions. First, we uncover a compre-
Correspondence
hensive overview of CO2 –water co-adsorption characteristics of various MOFs.
Zongbi Bao and Pengfei Xie, College of
Chemical and Biological Engineering, Then, the high-throughput screening methods are summarized. Both computa-
Zhejiang University, Hangzhou, Zhejiang tional and experimental efforts have been dedicated to identify the promising
310027, China.
Email: baozb@zju.edu.cn;
MOFs for humid CO2 capture. According to the screening results and adsorp-
pfxie@zju.edu.cn tion mechanism, the optimal preparation strategies are proposed to modulate the
effect of water on CO2 uptake in MOFs. Finally, current MOF-based CO2 capture
Funding information
National Key Research and Development prototypes are presented to evaluate their practical feasibility and performance.
Program of China, Grant/Award This work could offer valuable guidance for the development and application of
Numbers: 2022YFB4101700,
MOFs for CO2 capture in the presence of water and inspire further research in
2022YFE0128600; National Natural
Science Foundation of China, this field.
Grant/Award Numbers: 52276022,
22278365, 22225802; Basic Research Funds KEYWORDS
for the Central Government ‘Innovative carbon capture, CO2 adsorption, high-throughput screening, MOFs
Team of Zhejiang University’,
Grant/Award Number: 2022FZZX01-09

1 INTRODUCTION 400 parts per million, although the COVID-19 pandemic

has caused a drastic reduction in greenhouse gas emis-
Carbon dioxide concentration continuously refreshes the sions in recent years.1,2 The global surface temperature in
highest ever average annual level in the atmosphere, over 2021 increased by 1.12◦ C relative to 1880–1920 average value

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the
original work is properly cited.
© 2023 The Authors. SusMat published by Sichuan University and John Wiley & Sons Australia, Ltd.

SusMat. 2023;1–30. wileyonlinelibrary.com/journal/susmat 1

2 JIANG et al.
in the Goddard Institute for Space Studies analysis and
constantly reached new records.3 Carbon dioxide removal
(CDR) method plays an important role in mitigating global
warming.
Carbon capture and storage is regarded as a promis-
ing CDR approach to reduce CO2 concentrations from
large industrial plants or discrete emission sources of
atmosphere. It can be achieved by various methods, for
example, absorption, adsorption, cryogenics, membranes,
and microbial/algal systems.4 Adsorption using solid sor-
bents takes the advantage of less regeneration energy over
absorption via liquid sorbents.5 The energy penalty dra-
matically decreases by reducing evaporation heat of water
and the sensible and latent heat required for the desorption
process. Metal–organic frameworks (MOFs) is an emerg-
ing and favorable branch of solid sorbents among these
porous sorbents. It is a network of solids that are com-
posed of metal ions or metal cluster vertices and organic
linkers.6,7 Due to the modular and crystalline charac-
teristics, pore sizes, pore shapes, and surface chemical
potentials of MOFs can be easily adjusted for CO2 cap-
ture through the modifications of their metal clusters and
organic ligands. Due to the bridged/intertwined porous
structures with a high surface area, MOFs are well-defined
hosts for gas molecules.8,9 The extraordinary adsorption
capacity and selectivity, especially at high pressure, could
then be obtained, which greatly correlates with adsorp-
tion heat.10–14 In addition, some MOFs are desirable under
low CO2 concentrations and are emerging as the right
adsorbents for direct air capture (DAC).15,16 However, other
component gases in gas source may have an impact on
their adsorption characteristics of CO2 , even the stability
of original structures.
Water is a ubiquitous component in air and most large
industrial CO2 sources and cannot be completely elim-
inated through a pretreatment stage. MOFs with open
metal sites (OMS), also known as coordinatively unsat-
urated sites (CUS), prefer to bind with water over CO2
due to the permanent dipole of H2 O molecules.17–19 Due
to these hydrophilic structures with polar bonds, CO2
adsorption capacities have a dramatic drop.20 It has been
demonstrated in CO2 /H2 O mixtures for Mg-MOF-74 via
Grand Canonical Monte Carlo (GCMC) and/or density
functional theory (DFT) simulation.21–23 Some exceptions
are described as follows. For MIL-101(Cr),24 ZIF-8,25 ZIF-
Cl,26 SALEM-2,26 SGU-29,27 etc., a given amount of water
might only have a negligible impact on CO2 adsorp-
tion. Moreover, moisture-enhanced CO2 adsorption can
be observed in HKUST-1,28 MIL-100(Fe),29 InOF-1,30 UiO-
66,31 PCN-250(Fe3 ), and PCN-250(Fe2 Co).32 Therefore,
based on the properties of sorbents and particular moisture
contents, CO2 adsorption of MOFs performs differently
under humid conditions. Despite the remarkable poten-
tial of MOFs to adsorb CO2 in the aqueous environment,
there is still a lack of full understanding about adsorption
analysis, mechanism clarification, and the optimal design
of MOFs in such a hot research field. Therefore, further
research is required to fill these gaps and provide efficient
solutions to mitigating CO2 emissions in the presence of
water.
In order to describe the modification strategies for
enhancing CO2 adsorption of MOFs in a moist environ-
ment thoroughly and systematically, it is desirable to seek
high-throughput screening methods and analyze the char-
acteristics of CO2 adsorption in the presence of water. The
common traits of the screened MOFs would provide the
insights for developing MOFs for the target applications.
This review aims to conduct a comprehensive discussion
on CO2 adsorption of MOFs under the humid conditions,
and the concerning general schematic is shown in Figure 1.
First, the high-throughput screening of MOFs for CO2
adsorption is revealed in Section 2, which includes prelimi-
nary and further processes. Second, modification strategies
for the improvement of capture performance based on
adsorption mechanisms are summarized in terms of phys-
ical and chemical factors in Section 3. Finally, lab-scale
carbon capture prototypes using MOFs are presented and
verified with regard to CO2 –water co-adsorption processes
in Section 4. In real CDR plants, more water-related issues
are involved. Based on research achievements, future
challenges and perspectives of MOFs for CO2 –water co-
adsorption are revealed in the end. This work would
contribute to better CO2 adsorption performance in wet
gases by elaborating contemporary exemplary MOFs in
terms of adsorption properties and mechanisms.
2 SCREENING OF MOFS FOR CO2
ADSORPTION
CO2 adsorption by MOFs is based on van der Waals
forces, chemical bonds, or Coulombic forces from atoms
or ions of sorbents. The driving force is determined by
the surface properties of the adsorbates/adsorbents and
environmental factors, for example, working temperature
and pressure. However, the presence of other impurities in
feed gas may change adsorption sites or adsorption affin-
ity, thereby having synergistic or competitive effects on
CO2 adsorption. Table 1 lists the major gas constituents
from the post-combustion process, the pre-combustion
process, and the atmosphere. This indicates that CO2 /N2
adsorption selectivity is generally higher due to the lower
quadrupole moment of N2 , and its kinetic diameter is large
enough to separate by tailoring pore size. But water has
a smaller kinetic diameter and a higher dipole moment
when compared to other two gases. Therefore, pores in the
JIANG et al. 3

F I G U R E 1 The general schematic of the

main parts: high-throughput screening of
metal–organic frameworks (MOFs),
modification strategies to enhance CO2
adsorption in the presence of water and the
lab-scale prototype demonstration.

T A B L E 1 Physical parameters of major gas compositions under the condition of post-combustion, pre-combustion, and the
atmosphere.35–37
Post- Pre- Dipole Quadrupole
combustion combustiona DAC Kinetic moment moment Polarizability
Composition (vol%) (vol%) (vol%) diameter (Å) (D) (1040 cm2 ) (1024 cm3 )
CO2 15–16 35.5 0.038 3.30 0.00 −14.31 ± 0.74 2.91
H2 O 5–7 0.2 0.1–3.0 2.65 1.8546 ∼0.0 1.45
N2 70–75 0.25 78.08 3.64 0.00 −4.65 ± 0.08 1.74
Abbreviation: DAC, direct air capture.
a
After gas shift reaction.

adsorbent have a stronger affinity toward water. Due to the
smaller kinetic diameter of water, “molecular sieve effect”
by decreasing pore size is invalid to improve CO2 /H2 O
selectivity. Meanwhile, water molecules linked to CUS
reduce binding energy between CO2 and framework of
adsorbents.21 Water adsorption hinders CO2 capacity and
selectivity of gas mixtures in most MOFs, especially when
humidity is high.33,34 Yu and Balbuena21 investigated the
effect of water on CO2 adsorption of Mg-MOF-74. As con-
firmed by molecular simulation, coordinated water abates
CO2 interaction with framework of adsorbents, and CO2
uptake decreases as water content increases. It is still chal-
lenging to achieve selective CO2 adsorption under humid
conditions.
The CO2 uptake of various MOFs, as well as molecu-
lar sieve, carbon, and zeolite, is compiled under different
humidities, as shown in Figure 2. The larger symbols
are not limited to areas with low adsorption amounts.
Some types of MOFs have the better adsorption perfor-
mance under high humidity condition. They consist of
both physical adsorbents, such as dptz-CuTiF6 ,38 PCN-
250(Fe2 Co),32 and CO2 (dobdc),21 and chemical adsorbents
such as dmpn-Mg2 (dobpdc)39 and mmen-Mg2 (dobpdc).40
In contrast, the hydrophilic nature of zeolite 13X renders
it essentially incapable of absorbing CO2 in the presence
of water. Mg-MOF-74, MIL-96(Al), and other compounds
exhibit similar reductions in CO2 adsorption uptake. More
attention should be paid to adsorbents that exhibit a slight
4 JIANG et al.

MOFs
5 Co2(dobdc) ndmpn-Mg2(dobpdc)

Amount adsorbed (mol/kg)

0.2 Graph2
1

Amount adsorbed (mol· kg-1)

1%RH dmpn-Mg2(dobpdc) Ni2(dobdc)
100%RH 0.1
4 dptz-CuSiF6 Ni-MOF-74
dptz-CuTiF6 NOTT-400
0.0
0 200 400 600 800
PCN-250(Fe2Co)
3 CO2 concentration (ppm) HKUST-1
InOF-1 PCN-250(Fe 3)
Mg2(dobdc) SIFSIX-3-Ni
2 Mg-MOF-74 SIFSIX-3-Zn
MIL-100(Fe) UiO-66
MIL-101(Cr) ZIF-8
1 Zn2(dobdc)
MIL-96(Al)
mmen-CuBTTri Zn-MOF-74
0 mmen-Mg2(dobpdc) Others
mmen-Ni2(dobpdc) 1°-MCM-41
AX-21 carbon
0.00 0.10 0.12 0.14 0.16 0.18 0.20 0.22 MOF-5
PEI-MCM-41
MOF-808-Gly
CO2 partial pressure (bar) zeolite 13X
MOOFOUR-1-Ni

F I G U R E 2 A summary of CO2 adsorption capacity of metal–organic framework (MOF) materials and several other types of adsorbents
under different humidity conditions. The humidity is shown by the symbol’s size. The adsorption temperature is in the range of
298–313 K.21,24,25,29,32,33,38–48

reduction in CO2 uptake under the conditions of an ele- First, its screening methods and performance indicators
vated humidity or even perform better when exposed to are discussed. The common evaluation indicators are
water molecules. It is also critical to identify the mecha- shown in Table 2. Among these indicators, Henry con-
nism responsible for the abnormal rise in CO2 uptake. stant (KH ), Henry selectivity (SH ), and adsorption enthalpy
CO2 –water co-adsorption characteristics vary greatly (∆Hads ) are used for the preliminary screening. The work-
among different materials. Thus, it is essential to iden- ing capacity (∆N) and regenerability (R%) are the basic
tify preferable MOFs under humid conditions. High- indicators that only focus on CO2 adsorption of materials,
throughput screening via molecular simulation is an regardless of other components. The additional parame-
effective method for screening MOFs with high potential. ters include selectivity (S), percent uptake loss (PUL ), and
The evaluation criteria and material screening results are separation potential (∆Q), which are related to the per-
expounded. formance of multicomponent adsorbates’ adsorption or
separation. The adsorbent performance score (APS) is a
comprehensive evaluation indicator.
2.1 High-throughput screening
indicators
2.1.1 Indicators of preliminary screening
A large number of MOFs with the adjustable pores and
functional groups have been discovered. In the Cam- Although GCMC is an ideal method, the computational
bridge Structural Database, crystallographic information cost of the simulation for adsorption with the participa-
files of over 10 000 non-disordered MOFs are indexed.49 tion of water molecules will significantly increase because
It is convinced that variable pore sizes, functional group acceptance probabilities of insertion and deletion of water
diversities, and structural differences all have a significant molecules are very low. In addition, the accuracy of simu-
influence on CO2 adsorption properties.50 In general, the lation strongly depends on H2 O model. The TIP4P model
experimental conditions are challenging to complete large- represents each water molecule with four atoms, which
scale material screening, especially when water effect is widely used.51 Zhao et al.52 performed 1 × 107 work-
needs to be counted. Thus, with the rapid advancement ing cycles on water adsorption, but others only conducted
of computer technology, more researchers have conducted 5 × 105 cycles. With regard to computer performance and
molecular simulations to screen ideal CO2 adsorption screening efficiency, more convenient indicators should
materials under wet conditions using a high-throughput be adopted for the preliminary screening instead of wet
method that is validated by the experimental results. adsorption isotherms of materials.
High-throughput screening studies on CO2 adsorption The Henry constant is the most commonly used screen-
materials are summarized by considering water effect. ing index for the preliminary high-throughput screening
JIANG et al. 5

TA B L E 2 Evaluation indicators for material screening.

Evaluation indicators Formula Components
1 ⟨𝑊⟩
Henry’s constanta 𝐾H = (a) CO2 , H2 O
RT𝜌f ⟨𝑊 IG ⟩
( ( ) )
ln 𝐾H
Δid 𝐻 = 𝑅𝑇 2 𝜕 (b)
𝜕𝑇 𝑛

𝐾H,CO2
Henry selectivitya 𝑆H = CO2 , H2 O
𝐾H,H2 O
( )
𝜕𝑈
Adsorption enthalpya Δ𝐻ads = − ⟨𝑈g ⟩ − RT H2 O
𝜕⟨𝑁⟩ 𝑉,𝑇

Adsorbent performance scoreb APS = 𝑆 × Δ𝑁 CO2

b 𝑦𝐻2 O
Separation potential Δ𝑄m,H2 O = 𝑁ads,CO2 × − 𝑁ads,H2 O CO2 /N2 , CO2 /CH4 , CO2 /H2 O
𝑦CO2

𝑁dry −𝑁wet
Percent uptake lossb 𝑃UL = × 100% CO2
𝑁dry

𝑛CO2 ∕𝑛𝐻2 O
Selectivityb 𝑆CO2 ,H2 O = CO2 /N2 , CO2 /CH4 , CO2 /H2 O
𝑝CO2 ∕𝑝𝐻2 O

Working capacityb Δ𝑁 = 𝑁ads − 𝑁des CO2

Δ𝑁
Regenerabilityb 𝑅% = × 100% CO2
𝑁ads

a
Evaluation indicator usually used in preliminary screening.
b
Evaluation indicator usually used in further screening.

100 bulk phase concentration), but it is not suitable for high-

throughput screening. Besides, KH can also be calculated
by Widom insertion method53 or deduced from the infinite
80 dilution enthalpy,54 which could correspond to Formulas
CO2 capacity loss (wt%)

(a) and (b) in Table 2.

60
MIL-53(Al)
40
20
0 high pressure. It is obvious that interaction between adsor-
0 2 4 6
lnKH (H2O)
F I G U R E 3 The relationship between CO2 capacity loss and the
KH of H2 O. Reproduced with permission.55 Copyright 2017, Wiley.
of the materials for CO2 adsorption when considering the
influence of water. The relationship between PUL and KH
of water is indicated in Figure 3, where each point rep-
resents a kind of MOF. Except for a few MOFs, the loss
of CO2 capacity of most types shows a positive linear cor-
relation with the logarithm of 𝐾H,H2O . Several common
calculation methods can be used to obtain KH of water. One
method is to calculate the slope of the straight line region
of adsorption isotherm (ratio of gas adsorption capacity to
In the actual screening process, SH for CO2 to H2 O
is often used as an indicator of the preliminary screen-
MIL-127(Fe)
ing. Li et al.56 screened out top 15 structures with the
largest SH from CoRE MOF database, which has 5109
MOF structures.57 Figure 4A shows that SH is greater than
MIL-96(Al) that calculated by GCMC simulation in most cases. A
reasonable explanation is that KH only considers adsorp-
tion properties at low pressure but ignores the changes at
8 10 12 14
bate molecules increases at high pressure, which is almost
ignored at low pressure. Especially for water molecules, a
hydrogen bonding network formed at high pressure greatly
enhances the interaction between water molecules. Fur-
thermore, their team also investigated the influence of
different charge assignment methods on KH , as shown in
Figure 4B. KH for CO2 and N2 are slightly influenced by the
method of charge calculation. Particularly in the case of a
large KH of H2 O, the extended charge equilibration (EQeq)
method tends to underestimate its value, which also leads
to a larger SH than GCMC selectivity.
Besides, Li et al.58 studied the effect of charge assign-
ment methods on KH . Except for EQeq method, the
density-derived electrostatic and chemical methods are
adopted to assign the partial charges. A similar conclusion
6 JIANG et al.

(A) (B)

F I G U R E 4 (A) Comparison between CO2 selectivity calculated by KH and Grand Canonical Monte Carlo (GCMC) simulation. (B)
Comparison between KH calculated by extended charge equilibration (EQeq) method and REPEAT method. Reproduced with permission.56
Copyright 2016, ACS.

can be yield as follows. There is little difference between

KH of CO2 and N2 calculated by different charge meth-
ods, but a great difference between the KH of H2 O can be
found. To explain the difference, van der Waals force and
Coulomb force of three molecules are calculated, as shown
in Figure 5. Compared with CO2 and N2 , energy composi-
tion of water adsorption is significantly different, in which
the Coulomb force has a large proportion. This explains
why charge assignment method has a large influence on
the estimation of KH of H2 O. In addition to KH , ∆Hads can
also be used for the preliminary screening, which partially
reflects the strength of the interaction between adsorbate
and adsorbent. An effective screening strategy is to discard
structures, in which the enthalpy of water adsorption is
greater than evaporation heat.56

2.1.2 Indicators of further screening

After a preliminary screening of desirable adsorbents for

CO2 adsorption under humid conditions based on the
parameters of KH and ∆Hads , more accurate charge assign-
ment methods will be used. Also more detailed GCMC
simulations involving the multicomponent adsorption
isotherm and higher adsorption pressure are considered
to further explore performance differences and identify F I G U R E 5 Adsorption reaction enthalpy of (A) CO2 , (B) H2 O,
the top-performing materials. Various indicators can be and (C) N2 within the selected metal–organic frameworks (MOFs)
computed and analyzed to identify adsorption perfor- from density-derived electrostatic and chemical (DDEC)-based
mance. A comparison of the adsorbate-host interaction is screening. Reproduced with permission.58 Copyright 2017, Wiley.
required to achieve high adsorption capacity and selectiv-
ity. Figure 6A–C shows S, ∆N, APS, and R% of CO2 of the
selected MOFs from the mixed CO2 /N2 and CO2 /N2 /H2 O. four grades: A (less than 25%), B (25%–50%), C (50%–75%),
This indicates that water exerts a non-negligible impact on and D (more than 75%).
various performance indicators.59 Figure 6D compares PUL For real capture process, it is necessary to pursue a
of CO2 in the presence of water, which can be divided into high ΔN𝐶𝑂2 while minimizing adsorption uptake of other
JIANG et al. 7

(A) (D)
MIL-53(Fe) Activated sample
Active carbon Norit
Wet sample
ZIF-93
Active carbon Takeda
ScBDC
MIL-121(Fe)
UiO-66(Zr)-2Et
MIL-69(Al)
ScBDC-NO2
ZIF-8 BASF
Sc-BDC-NH2 A
ZIF-8(2)
UiO-66(Zr)-CF3
MIL-103(La)
ScBDC-Br
MIL-121(Al)
MIL-53(Cr)-Cl
ZIF-94
MIL-140A(Zr)-Br
(B) UiO-66(Zr)-2Me
MIL-163(Zr)
MIL-53(Fe)-Br
MIL-140A(Zr)
UiO-66(Zr)-Me
MIL-53(Cr)
UiO-66(Zr)-2CF3
UiO-66(Zr)
MIL-53(Cr)-Br
MIL-100(Cr)
MIL-140C(Zr)

HKUST-1
MIL-101(Cr)
UiO-66(Zr)-NH2
B
MIL-96(Al)
MIL-53(Fe)-Cl
MIL-103(Eu)
MIL-110(Al)
MIL-127(Fe)
MIL-53(Al)
(C) 100 MIL-100(Cr)-Me

MIL-53(Al)-NH2
C
R% for CO2/CH4 mixture

MIL-130(Al)
in H2O loaded MOFs

MIL-68(Ga)
90 MIL-102(Cr)
MIL-100(Fe)
AFEHUO
CIFCEB
MIL-91(Ti)
D
80 Zeolite chabazite-Cs
FIRMUQ
CPO-27(Ni)
KOSLUB
Zeolite 13X
SUTBIT Mg(H2gal)
WONZIJ
70 0 5 10 15 20 25
70 80 90 100 Amount of CO2 adsorbed (wt%)
R% for CO2/CH4 mixture

F I G U R E 6 Comparison of (A) S𝐶𝑂2 ∕𝑁2 , (B) ΔN𝐶𝑂2 (mol kg−1 ) and APS (mol kg−1 ), and (C) R% of metal–organic frameworks (MOFs)
calculated for separation of the mixed CO2 /N2 and CO2 /N2 /H2 O. Reproduced with permission.59 Copyright 2017, ACS. (D) Summary of the
results obtained for the 43 MOFs and four reference materials tested. Reproduced with permission.55 Copyright 2017, ACS.

gases. Thus, S is an important indicator, for example, optimization algorithm to obtain the optimal adsorption
between CO2 /N2 , CO2 /CH4 , and CO2 /H2 O. Because sim- process setting.60
ulation processes are often simplified to binary or ternary
systems, S and ∆Q are significant for CO2 and another gas
component. However, it is also possible to include more 2.2 High-throughput screening outputs
gas components in the practical application and calculate
S between CO2 and other remaining components, which After considering the indicators for the preliminary and
is similar to the purity calculation. Since the adsorbed further screening, some MOFs appear to be the candidates
CO2 is not completely desorbed, calculating N and R% is for carbon capture under humid conditions. Table 3 sum-
preferable to comparing absolute adsorption capacity. marizes researches on high-throughput screening of MOFs
Besides, the multi-objective optimization arises in terms for CO2 adsorption in the presence of water. It reveals
of various measurement indicators and working con- that the computational screening is more rapid and effi-
ditions. A simple approach is to use a comprehensive cient to select the potential adsorbents, which has recently
evaluation indicator such as APS or a multi-objective become a hot research area. Some insights into the optimal
8 JIANG et al.

TA B L E 3 High-throughput screening studies of metal–organic frameworks (MOFs) for CO2 capture from the wet gases.
Screening
Database method Screening result Adsorbent feature Ref.
45 MOFs Experimental 4 zones with different effects ∙ Pores with different sizes or chemistry with 55
of adsorbed H2 O on CO2 “bifunctionality.”
uptake ∙ Adsorbed H2 O attract CO2 via
diploe–quadrupole interaction.
CoRE MOF Computational 15 MOF structures ∙ High van der Waals interaction between CO2 56
and MOFs.
∙ Small pore size provides strong interaction
with CO2 and prevents water cluster
formation.
CoRE MOF Computational 15 MOF structures ∙ Low surface area (<1000 m2 g−1 ). 58
∙ Small pore size (∼5 Å).
CoRE MOF Computational GaPO and AlPO zeolites ∙ The adsorption heat of CO2 is higher than 61
and IZAa H2 O at zero loading.
∙ The inter-adsorbates interaction of H2 O is
stronger than CO2 .
325 000 Computational MOFs with adsorbaphore of ∙ The parallel aromatic rings provide the 62
hypothetical type A1 favorable interaction with CO2 .
MOFs ∙ This adsorbaphore hinders hydrogen bonding
formation.
CoRE MOF Computational 13 MOF structures ∙ Generally, contain Zn ions metallic centers. 63
∙ Generally, contain alkaline nitrogen groups.
MOF-74-Mb Computational Noble metals in MOF-74 ∙ The redox characteristics of noble metals 64
enhance the interaction with CO2 and
repulse H2 O adsorption.
a
IZA: International Zeolite Association.
b
M: Be, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Nb, Ru, Rh, Pd, La, W, Os, Ir, Pt.

selection or design of adsorbents are revealed by the
existing screening results. The features of MOFs can be
classified into two types according to their top-performing
adsorption characteristics: (i) high adsorption interaction
with CO2 provided by adsorbents with superb chemical
structure or co-adsorption adsorbates and (ii) the con-
finement effect arising from appropriate pore sizes of
adsorbents.
Interaction strength between adsorbates and adsorbents
can be reflected by reaction heat. Findley and Sholl61 used
adsorption heat to screen MOFs and zeolites using Widom
insertion Monte Carlo simulations. It is demonstrated that
almost all MOFs from the 2014 CoRE MOF database are
deemed to unsuitable for DAC in the presence of water due
to the much higher adsorption heat of H2 O under humid
atmospheric conditions. This situation can be improved
in the application of higher CO2 concentrations such as
post-combustion carbon capture. Li et al.56 screened 15
MOFs from the CoRE MOF databases with high CO2 /H2 O
and CO2 /N2 selectivity, which are primarily due to strong
van der Waals interactions between CO2 and adsorbent
at 80% relative humidity (RH) for post-combustion cap-
ture. Similarly, Rogacka et al.63 revealed 13 promising MOF
structures with high CO2 /CH4 selectivity under ambient
conditions. Nine of the screened MOFs have ligands with
alkaline nitrogen groups that have a stronger chemical
interaction with CO2 . According to Canepa’s research,64
MOF-74 with the noble metals Rh, Pd, Os, Ir, and Pt
competes with water due to the redox nature of noble
metals. Boyd et al.62 identified three types of effective
CO2 adsorption sites in the screening process of MOFs
for wet CO2 capture, inspired by traditional drug molec-
ular design strategies.65,66 They are parallel aromatic rings
(A1), metal–oxygen bridges (A2), and OMS (A3). As shown
in Figure 7A,B, those materials with parallel aromatic
rings have a high 𝐾H,CO2 and a low 𝐾H,H2 O . Later, they
further studied MOFs with frz topology, which was charac-
terized by tetra-carboxylated organic ligands coordinated
to one-dimensional metal–oxygen rods and contained
the preferred adsorption sites.62 By choosing appropri-
ate metal element and parallel aromatic ring space, one
highly promising MOF material, Al2 (OH)2 (H2 TCPP) (Al-
PMOF) H2 TCPP, meso-tetra(4-carboxyphenyl)porphyrin),
was designed and experimentally validated for its good
JIANG et al. 9

F I G U R E 7 (A) KH for H2 O against those of CO2 . The colors represent three different adsorbaphores in the top-performing structures:
A1, parallel aromatic rings; A2, metal–oxygen bridges; A3, open metal sites. Some materials have both A1 and A2 sites. (B) Adsorbaphore
containing parallel aromatic rings (A1) (adapted from Ref. 62). (C) CO2 /H2 O selectivity based on the ratio of Henry’s constants against the
largest cavity diameter (LCD). Data points are colored based on accessible surface area (ASA) and (D) void fraction (VF). Reproduced with
permission.58 Copyright 2017, Wiley.

hydrophobicity, water stability, and high CO2 adsorp-
tion uptake. Other studies have reported that MOFs with
different proprietary adsorption sites can achieve better
CO2 –water co-adsorption, which is conducive to solve
competitive adsorption issues.55
The majority of small pores have a confinement effect on
CO2 adsorption and impede water cluster formation.56,58,62
Li et al.58 summarized characteristics of materials suit-
able for CO2 adsorption under wet conditions through
screening methods. The results show that the Henry selec-
tivity of CO2 /H2 O decreases as the largest cavity diameter
(LCD) increases. Materials with the lower accessible sur-
face area and void fraction usually have a higher selectivity,
as shown in Figure 7C,D. Therefore, porous materials with
smaller pore sizes may be better suited for CO2 adsorption
under wet working conditions, and these small pores can
prevent the formation of hydrogen bond networks among
water molecules.
In summary, high-throughput screening performance
indicators that are simple to calculate, such as KH , are fre-
quently evaluated for the preliminary screening to save the
computational resources, and then further simulations are
performed to obtain more effective indicators. During the
screening process, researchers investigated common char-
acteristics of adsorbents such as pore size, surface area,
pore volume, and chemical functionality, and designed
materials based on these findings.67 However, few studies
of carbon capture have focused on the effect of water based
on the high-throughput screening. The related researches
have mainly concentrated on MOFs, while other materi-
als, for example, zeolites and molecular sieves are rarely
reported.68–70 Thus, relevant databases of other sorbents
need to be extend.
The results of a high-throughput screening for CO2
adsorption in the presence of water show that prefer-
ential CO2 adsorption is related to adsorbent structures.
CO2 /H2 O adsorption selectivity is not just a simple func-
tion of MOF structure properties, for example, pore size,
surface area, etc.63 The operation conditions for adsorp-
tion processes, such as humidity, temperature, and partial
pressure should also be taken into consideration. To
understand the mechanism of MOFs with high CO2 /H2 O
selectivity based on existing researches, a comprehen-
sive review of optimization strategies for increasing CO2
adsorption in wet gases should be conducted, which could
provide some insights for material development.
10
FIGURE 8 Explanation of adsorption mechanism by using a flow chart.
3 STRATEGIES FOR THE IMPROVED
CO2 ADSORPTION
In order to obtain the materials with good adsorption
performance through screening, the internal adsorption
mechanisms should be further explored to guide material
synthesis. The mechanism is explained by a flow chart,
as shown in Figure 8. Physisorption produced by inter-
molecular interactions is favored by surface affinity and
confinement effect. However, chemisorption occurs only
through surface affinity due to the action of chemical
bonds. The confinement effect arises from the overlap of
the host–guest potential energy surface in cavities of adsor-
bent structure, which leads to CO2 adsorption in narrow
pores.71 Surface affinity is determined by the chemical
composition of the solid, which has no bearing on frame-
work topology. According to the existing research, the
promoting effect on CO2 adsorption could occur in some
sorbents via thermodynamic (surface affinity) or kinetic
(confinement effect) factors. These characteristics that
promote CO2 adsorption under humid conditions can be
classified by action mechanism as follows: (i) CO2 adsorp-
tion sites with the suitable polarization interactions72–75 ;
(ii) adsorption sites with strong chemical interactions with
CO2 76–79 ; and (iii) confinement effect of channel structure
or the coordinated H2 O molecules.28,38,80 Table 4 lists some
advanced MOFs with high CO2 uptake under humid con-
ditions. Their excellent performance is evaluated by using
adsorption mechanism.
3.1 Polarization interaction
The binding forces for CO2 adsorption include van der
Waals forces, chemical bonds, or Coulombic forces. For
physical adsorption, there is no need to consider chemical
bond formation. Adsorption enthalpy is only proportional
to intermolecular interactions, for example, van der Waals
forces and Coulombic forces.85 Physical adsorption forces
are related to the polarizability of adsorbents and adsor-
bates, which is an important fundamental fact for the
following content. The polarity of major gas compositions
can then be determined. Water with a higher polarizabil-
ity competes with CO2 for adsorption sites. Furthermore,
the dipole moment of water has an undeniable interaction
JIANG et al.
with the quadrupole moment of CO2 .55 The interaction
changes depending on the magnitude and orientation
of the intermolecular force, resulting in different effects.
The key to promoting CO2 adsorption is to erode water’s
competitive advantages or increase synergistic effects. To
improve CO2 uptake in wet gases, some approaches based
on the affinity of CO2 and H2 O to adsorbents have been
proposed: (i) increasing the hydrophobicity within MOFs
to decrease the polarity of adsorption sites; (ii) building the
specific adsorption sites; and (iii) adsorbing an appropriate
amount of H2 O to append CO2 adsorption sites.
3.1.1 Hydrophobic modification
There are two common methods for MOF modifica-
tion treatment, that is, pre-functionalization, also called
direct synthesis and in situ synthesis and post-synthetic
modification. To reduce water affinity in MOFs by pre-
functionalization, some hydrophobic groups, such as alkyl
groups, aryl groups, fluorinated alkyl groups, and aryl
groups could be introduced to protect weak coordination
bonds from hydration.86–88 Yu et al.72 investigated a series
of UiO-66 derivatives decorated by alkyl or perfluoroalkyl
groups bound to ligands of different lengths (terephthalate
or 4,4′-azobenzenedicarboxylate). This demonstrates that
increasing the number of substituents increases hydropho-
bicity. As a result of fluorination, perfluoro-alkylated
groups among the derivatives of UiO-66 exhibit more
hydrophobicity than alkyl groups. Although the polarity of
pore walls decreases, introduction of functional groups can
also increase the confinement effect to promote adsorp-
tion. This effect is more apparent in UiO-66D, which
possesses the large pores, as shown in Figure 9.
Fluorine-functionalized MOFs have a low surface
energy, which could be attributed to fluorine’s high elec-
tronegativity and relatively low electric polarizability. The
treatment of fluorinated building blocks can generate the
fabulous hydrophobic porous structures.73 MOFs contain-
ing inorganic fluorinated monoanions achieve preferential
CO2 adsorption over the interaction of F atoms and CO2 .
Noro et al.75 synthesized a flexible and hydrophobic cop-
per porous coordination polymer, which indicates a high
selectivity for CO2 over CH4 and the high stability under
humid conditions. The whole structure is composed of low
TA B L E 4 The structure, CO2 uptake, and features of advanced metal–organic frameworks (MOFs).
JIANG et al.

CO2 Adsorption
pressure temperature CO2 uptake
MOFs Metal Ligands Components (kPa) (K) (mol kg−1 ) Features Ref.
Mg-MOF-74-COOH Mg DHTP-COOH CO2 /H2 O (50/50 vol%) 50.5 298 51.1 (N u.c.−1 ) The carboxyl groups have weakly interacted with 23
water molecules.
MIL-101 (Cr) Cr BDC CO2 /N2 /H2 O 10 298 0.509 The increase electrostatic interactions between 24
(10/90 vol%/10% RH) coordinated water and quadrupole moment of
CO2 .
MIL-100 Fe BTC CO2 /N2 /H2 O 20 298 2.32 Water adsorption on the CUS leads to stronger 29
(20/80 vol%/40% RH) adsorption sites for CO2 and it would seem that
the CO2 displaces some water.
UiO-66 Zr BDC CO2 /pre-adsorbed H2 O 100 298 3.2 Pre-adsorbing water favors dipole–quadrupole 31
(1.8 wt%) interaction and molecule–framework
interaction toward CO2 .
PCN-250 (Fe3 ) Fe ABTC CO2 /N2 /H2 O 15 298 1.82 The plier effect of coordinated H2 O. 32
(15/85 vol%/50% RH)
PCN-250 (Fe2 Co) Fe, Co ABTC CO2 /N2 /H2 O 15 298 2.23 The plier effect of coordinated H2 O and the higher 32
(15/85 vol%/50% RH) ionic character of the Co–O bond forms
stronger interaction with CO2 .
Mg-CUK-1 Mg 2,4-PCD CO2 /H2 O (18% RH) 100 303 3.3 Favorable intermolecular interactions between 81
CO2 and H2 O.
MIL-53 Al BDC CO2 /H2 O (20% RH) 100 303 1.18 Confinement effect induced by H2 O and directing 82
effect of the hydroxo functional groups.
InOF-1 In BPTC CO2 /H2 O (20% RH) 100 303 2.5 Confinement effect induced by H2 O and directing 83
effect of the hydroxo functional groups.
NOTT400 Sc BPTC CO2 /H2 O (20% RH) 100 303 2.32 Confinement effect induced by H2 O. 45
[Cu(PF6)2 (BPP)2 ] Cu PF6 − , BPP CO2 /CH4 /H2 O 300 298 1.4 Low electric polarizability of fluorine. 75
(39.98/59.66/0.06 mol)
een– Mg2 (dobpdc)/Al–Si Mg een, H4dobpdc CO2 /He/H2 O 15 353 2.5 Diamine grafting and silane coating. 84
(15/81.25/3.7 vol%)
NOTT401 Sc TDA CO2 /H2 O (5% RH) 100 303 0.89 Confinement effect of H2 O and hydrogen bond 46
formation between H2 O and CO2 .
Note: ABTC: 3,3′,5,5′-azobenzenetetracarboxylate; BDC: 1,4-benzenedicarboxylate; BPTC: 3,3′,5,5′-biphenyltetracarboxylate; BPP: 1,3-bis(4-pyridyl)propane; BTC: benzene-1,3,5-tricarboxylate; DHTP:
2,5-dihydroxyterephthaliate; een: N-ethylethylenediamine; PCD: pyridinecarboxylate; TDA: thiophene-2,5-dicarboxylate.
Abbreviations: CUS, coordinatively unsaturated sites; RH, relative humidity.
11
12
F I G U R E 9 Water sorption isotherms measured at 298 K. (A) UiO-66 derivatives; (B) UiO-66D derivatives. UiO-66D represents a longer
UiO-66 analog, in which ligand is exchanged by 4,4′-azobenzenedicarboxylate linkers (adapted from Refs. 72, 89).
polar ligands, fluorinated PF6 − anions, BPP containing
two pyridine moieties and one cross-linking −(CH2 )3 −
moiety without any strong Lewis acid and base sites.
Another viable method for post-synthetic exchange that
allows for simple modification of existing MOFs is coating
the crystals with hydrophobic polymers. Qian et al.90
fabricated an organosilicon coating on surface of various
MOFs via facile solution-immersion process and obtained
water-stable MOFs with a high contact angle. Choe et al.84
synthesized Mg2 (dobpdc)–alumina composite microbeads
(MOF/Al) through spray dry method, and then further
functionalized MOF/Al with een and coated with long
alkyl chain silanes to obtain splendid MOFs with the
high carbon capture capacity under humid conditions.
As shown in Figure 10, een–MOF/Al–Si exhibits the
best stability and the lowest affinity toward water when
compared to MOFs without a hydrophobic silane coating.
Nanochannels of MOFs can also be used as the desir-
able spaces for polymerization, which belongs to in situ
synthetic modification.91 Ding et al.92 developed a new
strategy to partition the channels of MOF-5 into the con-
fined compartments by in situ polymerization of aromatic
acetylene to improve the stability of the framework to
moisture, as shown in Figure 11A,B, respectively. Recently,
Yu’s group proposed a novel in situ microencapsulated syn-
thesis method to synthesize MOF-based hybrid sorbents.93
As shown in Figure 11C,D, three fluids flow through glass
double-capillary devices: precursors of MOFs (inner fluid),
hydrophobic ultraviolet photopolymerizable silicone (shell
fluid), and an aqueous surfactant-containing carrier fluid,
which are used to form MOF-based hybrid adsorbents with
excellent hydrophobicity (outer fluid). It is demonstrated
that CO2 adsorption capacity of the encapsulated HKUST-1
was slightly lower than that of HKUST-1, but the encapsu-
lated HKUST-1 showed the good recyclability and stability
after 10 working cycles.
JIANG et al.
Besides, some MOF-derived porous materials are stable
in wet gas. Kim et al.94 studied CO2 adsorption of porous
carbon materials zinc-containing MOFs. Due to the intrin-
sic hydrophobic feature of porous carbon and lack of metal
sites, the breakthrough curves of CO2 and N2 are identical
under dry and wet conditions. Also, some zeolitic imida-
zolate frameworks (ZIFs) have been reported to have the
high thermal and chemical stability in refluxing organic
and aqueous media.95 Nguyen et al.96 synthesized three
hydrophobic ZIFs by incorporating two distinct imidazo-
late links. These materials exhibit remarkable hydrophobic
properties and CO2 uptakes. Additionally, the series ZIF
exhibits significant CO2 separation performance over three
working cycles from a ternary mixture of N2 and water
without degradation of ZIF structure or performance. Hu
et al.26 also reported a series of ZIFs with the same sodalite
(SOD) topology with different functional groups. The pres-
ence of water is found to have a negligible effect on
CO2 adsorption in terms of ZIF-8, ZIF-Cl, and SALEM-
2, which contain no or weakly polar groups. Therefore,
ZIFs are the potential candidates for the hydrophobic
treatment.
3.1.2 Pores with the specific adsorption sites
In most cases, water has an influence on CO2 adsorption
due to the higher affinity toward adsorption sites. Recently,
some researchers discovered MOFs with CO2 -specific
sites, such as amine groups, which perform exceptionally
well under humid conditions.74 There is less interaction
between the adsorption of gases in MOFs with distinct
adsorption sites due to the varied pore sizes or bifunc-
tionality. Benoit et al.33 also found a similar principle
through the experiments and GCMC simulations for MIL-
96(Al) to investigate its adsorption behavior. Although CO2
JIANG et al. 13

(A) 5 (B) 25
140°C een-MOF
120°C een-MOF/Al
4 100°C 20 een-MOF/Al-Si

CO2 adsorbed (mmol· g-1)

H2O adsorbed (mmol· g-1)

80°C
60°C
3 15
40°C

2 10

1 5

0 0
0.01 0.1 1 10 100 1000 0.0 0.2 0.4 0.6 0.8
Pressure (mbar) P·P-1
0

(C) (D)
16
16
CO2 adsorbed (wt%)

12

CO2 adsorbed (wt%)

12

8
8

een-MOF 4 een-MOF
4
een-MOF/Al een-MOF/Al
een-MOF/Al-Si een-MOF/Al-Si
0 0
0 12 24 36 48 60 72 0 3 6 9 12 15
Exposure time (day) Exposure time (day)

F I G U R E 1 0 (A) Adsorption CO2 isotherms for een–MOF/Al–Si at various temperatures. (B) Water vapor isotherms of een–MOF,
een–MOF/Al, and een–MOF/Al–Si. (C) CO2 adsorption capacity of een–MOF, een–MOF/Al, and een–MOF/Al–Si after exposure to ambient
air. (D) CO2 adsorption capacity of een–MOF, een–MOF/Al, and een–MOF/Al–Si after exposure to 10% H2 O and 90% CO2 at 140◦ C. The flow
rate is 50 cm3 min−1 . Reproduced with permission.84 Copyright 2021, Springer Nature. MOF, metal–organic framework.

uptake significantly decreases in moisture, CO2 adsorp-
tion enthalpy displays a maximum value at 10% RH with
regard to the higher confinement effect and interaction
of pre-adsorbed molecules. Moreover, MIL-96(Al) con-
tains more hydrophilic groups, that is, Al(1)–H2 Oterminal ,
Al(3′)–OHterminal , and Al(3)–H2 Oterminal , which leads to
the adsorption of CO2 molecules at the remaining sites
with the lower polarity, as shown in Figure 12.
Similarly, Datta et al.27 reported a highly stable micro-
porous coppersilicate that has the square bipyramidal
crystal morphology (SGU-29). From Fourier transform
infrared spectra of SGU-29 in Figure 13, the growth rates,
peak shapes, and intensities of adsorbed CO2 peaks in wet
gases could be comparable to those observed in the absence
of H2 O, which only shows a broad peak of the adsorbed
water. The results verify that there are CO2 -specific and
H2 O-specific sites but no sharing sites; thus, moisture does
not influence CO2 capture ability of SGU-29. This kind
of sorbent can be seriously considered as a promising
candidate for binary adsorption. The exploration of CO2 -
specific sites is the key to filling existing research gaps.
Moreover, the mechanism of specific sites requires more
research.
3.1.3 New sites generated by pre-adsorbed
water
The adsorbed water molecules exhibit the antagonistic
effects to some degree, which block intrinsic CO2 adsorp-
tion sites while also having the potential to become
new CO2 adsorption sites. Several recent studies have
shown that pre-adsorption of a spot of water prefer-
entially interacts with hydroxyl groups within the pore
wall of MOFs, resulting in a significant increase in CO2
adsorption enthalpy due to an increase in co-adsorbate
interactions.33,81 As shown in Figure 14, it is verified by
the molecular simulation that CO2 can interact with H2 O,
but the interaction is relatively weak and has only a tiny
promoting effect.
In 2009, Yazaydın et al.98 initially discovered that water
molecules can promote CO2 uptake due to the increased
14 JIANG et al.

F I G U R E 1 1 (A) Illustration of the competitive adsorption of CO2 against H2 O at the surface and edge of polynaphthylene (PN). (B)
Polymerization of 1,2-diethynylbenzene (DEB) in metal–organic frameworks (MOFs). Reproduced with permission.92 Copyright 2016, ACS.
(C) Schematic of the microfluidic system for in situ encapsulated synthesis of MOFs. (D) The overall CO2 sorption and desorption steps by the
encapsulated MOFs. Reproduced with permission.93 Copyright 2021, KeAi.

F I G U R E 1 2 Maps of the occupied positions of (A) CO2 (orange), (B) N2 (blue), and (C) H2 O (cyan) in 1000 equilibrated frames extracted
from the Grand Canonical Monte Carlo (GCMC) simulations for co-adsorption of CO2 /N2 (20/80) in MIL-96(Al) at 303 K and 1.0 bar in the
presence of humidity, relative humidity (RH) = 8.5% (adapted from Ref. 33).

interactions between the quadruple moment of CO2 and
the electric field of the hydrated framework. In Figure 15A,
both non-Coulombic energy and Coulomb energy increase
by introducing the coordinated water molecules to MOF
structure, and the latter plays a leading role in energy
rise. The simulation results support a greater interaction
between CO2 and adsorbent, in which water interacts
with the coordinatively unsaturated Cu sites. Besides, the
coordinated water blocks the pores for nonpolar CH4 /N2 ,
and a breathing effect takes place, which could open
the pores in favor of CO2 . As a result, CO2 selectivity
rises, as depicted in Figure 15B. Jajko et al.31 revealed
that the CO2 loading is enhanced by pre-adsorption of
water in UiO-66. To understand adsorption mechanism of
performance enhancement in CO2 adsorption, the inter-
molecular adsorption energy is calculated, which includes
JIANG et al. 15

(A) 3
min
40
2 20
10
5
1 3

Absorbance (a.u.)
1
0
(B) 3
40
2 20
10
5
1 3
1
0
0
4000 3600 3200 2800 2400 2000 2450 2400 2350 2300 2250
Wavenumber (cm-1)

F I G U R E 1 3 The effect of adsorbed water on the adsorbed CO2 . Progressive change in the Fourier transform infrared spectra of dried
SGU-29 with time (as indicated) under the flow of (A) the dry flue gas and (B) the humid flue gas. Dry flue gas consists of CO2 , O2 , and N2
(100/190/723 mbar, respectively), and humid flue gas consists of H2 O, CO2 , O2 , and N2 (29/97/185/702 mbar, respectively) at 298 K. The flow
rate is equal to 5 mL min−1 . Reproduced with permission.27 Copyright 2015, AAAS.

F I G U R E 1 4 (A) The radial distribution functions calculated by Grand Canonical Monte Carlo (GCMC) simulations at 1 bar and 303 K
for the pair OCO2 –Hw of hydrated Mg-CUK-1. (B) The representative snapshot showing the interactions between CO2 and the atoms of
metal–organic framework (MOF) pore wall. The dashed lines in the snapshots denote interactions between CO2 molecules and the
surrounding atoms at distances below 3 Å (adapted from Ref. 81).

CO2 –CO2 , CO2 –H2 O, and CO2 –UiO-66. It is indicated that
adsorption energy of CO2 –H2 O is greater than that of CO2 –
CO2 at pressures of 0–1 bar. This demonstrates that the
interaction of pre-adsorbed water increases CO2 adsorp-
tion capacity. The average occupational density profiles are
also calculated, and the results show that water molecules
adsorb in the corners of octahedrons, which is explained
by entropy impact of the size and shape of water molecules.
CO2 molecules begin to fill the octahedral cages after water
adsorption, which is different from pure gas adsorption. It
is concluded that water transforms unfavorable sites into
favorable sites for CO2 adsorption. Thus, water promotes
the interaction of CO2 adsorption. Similarly, the hydrated
MIL-101 exhibits a higher CO2 adsorption capacity than
that of the dehydrated MIL-101 at low pressure because
the terminal water molecules act as extra CO2 adsorption
sites, which increases the interaction between quadrupole
moment of CO2 and dipole moment of adsorbents.97
It is worth noting that pre-adsorption may not accurately
reflect the real situation of carbon capture from humid
streams. After water saturation, the moisture content does
not remain stable during adsorption process, which will
cause a slight underestimate of CO2 uptake, particularly
when only using gravimetric method to monitor CO2 –
water co-adsorption. Other methods for measurement, for
example, monitoring outlet gas concentration by using gas
chromatography, are more reliable to obtain a reasonable
CO2 adsorption capacity.
16
(A) 25
20
Energy (kJ· mol-1)
15
Lennard-Jones (hydrated)
Lennard-Jones (dry)
10 Coulombic (hydrated)
Coulombic (dry)
5
0 0
0 5 10 15 20 25
CO2 loading (molecules·unit cell-1)
F I G U R E 1 5 (A) Interaction energies between CO2 and dry Cu-BTC and hydrated Cu-BTC (4 wt%) from Grand Canonical Monte Carlo
(GCMC) simulations at 298 K. To convert molecules per unit cell to milligrams of gas adsorbed per gram of sorbent, multiply by 4.3557. (B)
CO2 selectivity from the simulations of the equimolar mixtures of CO2 /CH4 and CO2 /N2 at 298 K. Reproduced with permission.98 Copyright
2009, ACS. BTC, benzene-1,3,5-tricarboxylate.
3.2 Chemical interaction
To overcome the drawbacks of physisorption, amine
functional solid adsorbents have attracted considerable
interest due to their exceptional chemisorption prop-
erties, especially under humid conditions, which are
also considered in MOF functionalization.99,100 Amine-
functionalized MOFs are prepared in three general routes,
that is, in situ synthesis, post-modification, and physical
mixing of unfunctionalized MOFs and polyamines.101 A
common method for in situ synthesis is to use ligands
with amine. There are myriad pathways to decorate MOFs
according to the type of amine functional groups, the
position, the possibility of coordination to node, and the
environmental conditions.102
The stability, polarity, alkalinity, and pore structure,
can be influenced by introducing functional groups to
pores. Free electrons located on amino nitrogen result
in a remarkably high affinity toward CO2 due to Lewis
acid–base interactions and non-covalent interactions.102
Ethiraj et al.76 synthesized a series of the mixed-ligand
UiO-66 through two different methods. The volumetric
CO2 isotherms show a higher CO2 capacity in terms of low-
temperature synthesis since the larger surface area could
be obtained. The results also demonstrate that the affin-
ity toward CO2 increases with the increase in NH2 content
in samples. The heteroaromatic amines that have nitro-
gen atoms in aromatic rings also exhibit the high CO2
adsorption capacity. Cui et al.77 synthesized a zeolite-like
microporous tetrazole-based MOF, which is composed of
flexible tetrazole derivative ligands and Zn2+ ions. It has
a high CO2 adsorption capacity of up to 8.09 mmol g−1
at 273 K and ambient pressure. This can be attributed to
JIANG et al.
(B) 35
CO2/N2 (hydrated 4 wt%)
30 CO2/N2 (dry)
CO2/CH4 (hydrated 4 wt%)
25
CO2/CH4 (dry)
Selectivity
20
15
10
5
30 35 40 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Partial pressure (bar)
multipoint interactions of framework toward CO2 , which
includes π-quadrupole system of aromatic rings and CO2 ,
potentially exposed nitrogen atoms and C atom of CO2 ,
and partial C–H bonds and O atoms of CO2 . Besides,
post-synthesis can prepare amine-functionalized MOFs.
Bahamon et al.78 investigated six amine models of dif-
ferent chain lengths and substitutions grafted onto the
unsaturated metal sites of M2 (dobpdc) by using molecu-
lar simulation. The results show that mmen/Mg/dobpdc
has a higher CO2 adsorption capacity and cycling perfor-
mance than MOFs with other structures. However, due to
an increase in steric hindrances, additional amine func-
tional groups or full functionalization of metal centers do
not show the improvement in CO2 separation capabili-
ties. Hence, functionalizing MOFs by amino groups could
occupy the partial pore sites and result in the decrease in
void space and surface area, which is not conducive to
CO2 adsorption. This is the reason why no enhancement
of adsorption capacity is found in MIL-101(Cr) –NH2 .103
However, MIL-101(Fe)–NH2 displays 1.4-fold increase in
CO2 adsorption capacity than MIL-101(Fe) at 4 MPa and
is more stable against water and ethanol.104 Mahdipoor
et al.104 also deduced the mechanism of CO2 adsorption
by amino functional groups based on three factors: elec-
tric field generated by different charges, hydrogen bonding
between CO2 and NH2 functional groups, and dipolar ion
(zwitterion) formation by the acidic CO2 and basic NH2
groups.
Regarding adsorption performance in the pres-
ence of water, many researches have observed an
enhanced CO2 capture capacity under various humid
conditions.42,79,105–107 Lee et al.106 prepared a diamine-
functionalized MOF by grafting the primary amine to
JIANG et al. 17

(A) 1.0
0.9 MOF-808-Gly adsorption (dry)
0.8 MOF-808-Gly adsorption (RH 10%)

CO2 uptake (mmol· g-1)

0.7
0.6
0.5
0.4 (C)
0.3
0.2
0.1 15%
4%
0.0
0 5 10 15
Absolute pressure (kPa)

(B)
10
MOF-808 (RH 0%)
MOF-808 (RH 15%)
CO2 effluent/Influent (%)

8
MOF-808-FR (RH 0%)
MOF-808-FR (RH 15%)
6 MOF-808-Gly (RH 0%)
MOF-808-Gly (RH 15%)
4

0
-10 0 10 20 30 40 50 60 70
Normalized Time (min·g-1)

F I G U R E 1 6 (A) Overlay of CO2 /H2 O binary adsorption isotherm and dry CO2 isotherm at 25◦ C. (B) The dynamic CO2 breakthrough
curve comparison among MOF-808, MOF-808-FR, and MOF-808-Gly, in dry and humid (relative humidity [RH] 15%) conditions at 25◦ C. (C)
The proposed chemisorption mechanism of CO2 uptake in MOF-808-AAs with (humid) and without (dry) the presence of water. Reproduced
with permission.42 Copyright 2022, ACS. MOF, metal–organic framework.

open coordination sites of Mg2 (dobpdc). The material has formation can be removed by vacuum process, which is
a significant CO2 uptake (2.83 mmol g−1 ) at ambient CO2 desirable for vacuum swing adsorption (VSA).
pressure. Notably, it can retain CO2 adsorption capacity Siegelman et al.79 reported a diamine-appended
after exposure to humidity. However, this structure is not Mg2 (dobpdc) MOF with a high CO2 capacity under humid
stable enough in which H2 O and CO2 usually compete conditions. DFT calculations show that the pre-adsorbed
with metal sites and therefore it loses original grafted water increases CO2 binding energy by 18 kJ mol−1 , as
amine. To avoid this, Lyu et al.42 used a robust MOF-808 shown in Figure 17. This is because ammonium carbamate
system to append amino acids through carboxylates to chains can form easily due to the hydron bonding inter-
Zr centers, which forms a strong MOF backbone and action provided by water molecules and the carbamate
prevents water or CO2 from breaking the bonds between nitrogen atoms of nearby ammonium carbamate chains.
metal atoms and the carboxylates with amino acids. Both Introduction of the basic amine functional groups onto
CO2 adsorption isotherm and dynamic CO2 breakthrough the surface of a solid material can increase the interac-
curve reveal a significant increase in CO2 uptake in tion between CO2 and solid surface by physisorption and
MOF-808-Gly upon humidification of stream, as shown chemisorption. For CO2 –water co-adsorption, the increase
in Figure 16A,B. Later, they used solid-state nuclear in CO2 adsorption occurs mainly with the increase in
magnetic resonance to explore the mechanism behind the amine efficiency. The presence of water also changes
binary adsorption. As demonstrated in Figure 16C, bicar- adsorption heat, which affects the affinity toward CO2 .
bonate formation under humid conditions only needs an Furthermore, grafting amine functional groups reduces
amine to adsorb each CO2 molecule from natural gas flue pore sites and surface area. Water molecules as impurities
emissions, which is less than what is needed when the can clog some adsorption sites and decrease CO2 adsorp-
conditions are dry. Moreover, it is noted that bicarbonate tion capacity. A balance is considered by tuning up the
18 JIANG et al.

F I G U R E 1 7 Projections along pore axis and first coordination spheres of Mg(II) sites for van der Waal (vdW)-corrected, density
functional theory (DFT) calculated structures of evacuated L-2-ampd-R-Mg2 (dobpdc) (top left) and the framework following CO2 insertion
(bottom left), water adsorption (top right), and co-adsorption of CO2 and H2 O (bottom right). The vdW-corrected, DFT-calculated binding
energies (ΔE) are provided for each adsorption process, and the available experimental differential binding enthalpies (ΔHads ) are included in
parentheses. Green, blue, gray, red, and white spheres represent Mg, N, C, O, and H atoms, respectively. Reproduced with permission.79
Copyright 2019, ACS.

amount of amine grafted. Besides, the long-term stability
of amine-functionalized adsorbents is necessary to avoid
the loss of amine.
3.3 Confinement effect
Adsorption sites are classified into two types: binding sites
via electrostatic interaction that dominates CO2 adsorption
and pore sites through confinement effect.108 The excel-
lent adsorption capacity of pores with confinement effect
can promote CO2 uptake in some MOFs with optimal pore
sizes. The confinement effect, termed as nest effect, was
initially proposed by Derouane,109 which represents that
a molecule and its environment tend to reciprocally opti-
mize their intermolecular force. This effect is related to
crystal topology and the auxiliary effects of atom dispersive
interactions on cavity walls.71 The confinement impact of
the channel construction and the adsorbed H2 O molecules
should be considered in the binary adsorption of CO2 and
H2 O.
3.3.1 Confinement effect of framework
topology
Some researchers have dedicated their efforts to deter-
mining the ideal pore size for gas separation. Gomez
et al.71 discovered new adsorption regions around inor-
ganic building units, resulting in the large H2 uptake in
PCN-12, NOTT-103, NOTT-112, and HKUST-1 due to the
confinement effect caused by small pore size (D ≤ 8.5 Å)
or narrow windows in cavities. For MOF-5 and MOF177
with larger pore sizes (10.8 and 11.2 Å), no adsorption site
is ascribed to confinement effect, which is confirmed by
first-principle calculations. It can be inferred that confine-
ment effect could happen in MOFs with the appropriate
pore sizes. Apparently, the pore size must be larger than
dynamic diameter of adsorbate. Based on existing stud-
ies on CO2 adsorption of MOFs, it is concluded that the
rapid and strong CO2 adsorption could be attributed to
the combination of high charge density and the optimal
pore size.110–114 With an appropriate channel size, zinc-
based Calgary Framework 20 (CALF-20) may selectively
physisorb CO2 .80 The CO2 binding sites are in the middle
of the pores, which may prevent the creation of networks
of hydrogen bonds between water molecules. Liang et al.38
used an interpenetration approach to develop a fluorinated
MOF with ideal pore aperture and channel sizes (4.5–6
Å). It allows for favorable CO2 adsorption versus N2 and
reduces adsorption heat because of the strong interaction
via confinement effect. Besides, it indicates the extraordi-
nary resistance to moisture, as shown in Figure 18, which
is presumably due to the nucleophilic nature of TiF6 2−
pillars. The sieving effect is a useful technique for gas sep-
aration that involves changing the pore window and size
JIANG et al. 19

(A) 1.6 (B) (C)

He N2
CO2 (298 K, dry) CO2 (298 K, 74% RH)
CO2 (328 K, dry) CO2 (328 K, 74% RH)
1.2
CA /C0

0.8

65.6 cm 3·g-1
64.0 cm3·g -1
m ·g -1

31.8 cm3·g -1
27.6 c 3
0.4

0.0
0 20 40 60 80 100 120
Time (min·g-1)

F I G U R E 1 8 (A) Dynamic column breakthrough tests for dptz-CuTiF6 with a gas mixture of 10% CO2 and 90% N2 (8 cm3 min−1 flow
rate) at 298 or 328 K and 1 bar under dry and humid conditions. Direct visualization of CO2 molecules inside the crystal structure of
dptz-CuTiF6 , as viewed along the (B) c-axis and (C) b-axis. This highlights the optimal arrangement of the CO2 molecules within the
square-shaped channels. Reproduced with permission.38 Copyright 2019, Elsevier.

F I G U R E 1 9 (A) Synthesis procedure of three isoreticular metal–organic frameworks (MOFs). (B) Views of site I and (C) site II in
activated NbOFFIVE-dps-Cu, GeFSIX-dps-Cu, SIFSIX-dps-Cu, and UTSA-300a with varied pore aperture sizes. Color code: Cu, green; F, light
green; S, bright yellow; N, light blue; C, gray; Si, orange; Ge, navy blue; Nb, wine red; solvent molecules are omitted for the clarity.
Reproduced with permission.117 Copyright 2022, Springer Nature.

to better match the size of the gas molecules.115 Pore topol- specific binding sites for C2 H2 /CO2 separation, as shown
ogy plays a crucial role in the capacity and selectivity of in Figure 19. This reveals that [Cu(dps)2 (SiF6 )] has the
adsorbents for multicomponent adsorption. highest C2 H2 uptake and selectivity for C2 H2 /CO2 . Simi-
Tuning the pore size can be achieved by controlling the larly, Cui et al.118 reported several “SIFSIX” materials with
size of metal ions or clusters and adjusting the lengths different pore structures, which were tuned by changing
of ligands.116 Wang et al.117 displayed a fine pore engi- organic linkers, metal nodes, or framework interpenetra-
neering by altering anionic linkers and metal nodes in tion. The best sorbent could be found with the ideal hybrid
[Zn(dps)2 (SiF6 )] to explore appropriate pore sizes and the pore chemistry and the optimal pore size to form gas
20
clusters. Li et al.119 designated this method as “single-
molecule trap.” This group also successfully synthesized
a cage-type structure with the desired size and strong
electrostatic interactions with CO2 molecules. Similar
techniques may likely be applied to separate additional
gases. Nevertheless, studies on tuning pore size for bet-
ter separation of CO2 and H2 O are rarely reported. It can
be explained by the fact that H2 O has a smaller kinetic
diameter (2.65 Å) than CO2 (3.30 Å), and consequently,
the sieving effect for CO2 capture in wet conditions is
invalid. However, most high-performing MOFs with good
CO2 /H2 O selectivity have narrow pores, which result in
the confinement effect and prevent the formation of water
clusters via hydrogen binding networks. According to the
study from Li’s group,58 pore size of ∼5 Å can attain the
highest CO2 /H2 O selectivity in most MOFs based on 1627
MOFs in CoRE MOF database. Thus, further research on
pore topology is required to focus on this range of pore
diameters.
3.3.2 Confinement effect of the coordinated
H2 O molecules
The confinement of small amounts of polar molecules
such as water and alcohols or non-polar molecules such as
hydrocarbons within MOFs can also increase CO2 uptake,
which proposes a novel method to address the issues of
CO2 –water co-adsorption.43 It occurs inside the pores,
which leads to the diffusional limitations and structural
constraints on the transition state.108 Also, pre-adsorbed
molecules can interact with CO2 .120 Numerous investi-
gations have found a trend of increased CO2 uptake in
co-adsorption when compared to that under dry condi-
tions.
It is noted that CO2 adsorption capacities of some
MOFs increase first and then decrease with the increase
in the humidity, such as HKUST-1,28 MIL-101(Cr),97 MIL-
100(Fe),29 Mg-CUK-1,81 InOF-1,30 and UiO-66.31 Liu et al.28
studied the equilibrium of CO2 /H2 O binary adsorption
of two types of MOFs: HKUST-1 (Cu-BTC) and Ni/dobdc
(CPO-27-Ni or Ni/MOF-74). Water adsorption progress on
HKUST-1 is reversible. A small amount of the adsorbed
water does not inhibit CO2 adsorption but may promote
adsorption capacity of HKUST-1, which contributes to
the addition of Coulombic interactions between CO2 and
H2 O molecules. However, there is no enhancement of
CO2 adsorption capacity in Ni/dobdc after introducing
H2 O molecules into feed gases. Zhao et al.121 reached a
similar conclusion. HKUST-1 slightly degrades, and
Ni/dobdc exhibits a better stability after several working
cycles, which could be ascribed to higher transition state
JIANG et al.
energies of Ni/dobdc for hydration.122 Soubeyrand-Lenoir
et al.29 investigated adsorption uptake and enthalpy of
three topical porous MOFs. The results show that water is
not conducive to CO2 adsorption capacity of UiO-66(Zr)
under different RHs, which is inconsistent with the find-
ing from the research by Jajko et al.31 MIL-100(Fe) exhibits
a striking fivefold improvement in CO2 uptake with the
increase in RH. Given the poor MIL-100(Fe) test results,
this conclusion is dubious. Álvarez et al.45 demonstrated
NOTT-400 that pre-adsorbed water could enhance CO2
uptake via confinement effect. The CO2 uptake presents
an approximate 2.5-fold increase after exposure to 20%
RH conditions. Adsorbed water molecules form strong
hydrogen bonds with the bridging hydroxo functional
groups (μ2 -OH) in NOTT-400, which leads to the aug-
mented CO2 sequestration. Likewise, PCN-250(Fe3 ) and
PCN-250(Fe2 Co) represent moisture-enhanced features.32
Water can have strong interactions with the hydroxo func-
tional groups (μ3 -O) in their framework. The coordinated
H2 O molecule acts as a plier that clamps CO2 on accessible
adsorption site. Furthermore, it is demonstrated that CO2
moves closer to OMS when hydroxo functional groups
(μ3 -O) are coordinated with H2 O by GCMC. González-
Zamora and Ibarra44 concluded that water molecules
can strongly interact with hydroxo functional groups via
hydrogen bonding, which leads to a confinement effect
allowing for more efficient CO2 packing.
Water loading amount is critical to the effectiveness of
the confinement effect. The directing effect of hydroxo
functional groups is greatly reduced at high RH due to an
increase in water disorder caused by thermal agitation.44
It is essential to determine the optimal water loading
of confinement effect on CO2 . Sánchez-González et al.41
explored the structural transformation of Mg-CUK-1 at dif-
ferent H2 O loadings by using powder X-ray diffraction and
refined it by the Le Bail strategy in Figure 20. With eight
hydrogen-bonded H2 O molecules per unit cell, the window
dimension was reduced to 2.56 Å inducing non-accessible
for CO2 . A window reduction is also resulted by four or
two H2 O molecules per unit cell and thereby the diffu-
sion of CO2 is restrained. CO2 has enough free space to
interact with adsorbent and adsorbate only when there is
one H2 O molecule per unit cell, which results in “bottle-
neck effect.” Indeed, Mg-CUK-1 exhibits a 1.8-fold increase
in CO2 uptake at 18% RH (one hydrogen-bonded H2 O
molecule per unit cell) due to pore windows partially con-
strained by water. Soubeyrand-Lenoir et al.29 elucidated
the mechanism of the confinement effect in a mesoporous
architecture. Pre-equilibrated water initially fills microp-
orous pockets in MIL-100(Fe), as shown in Figure 21A.
CO2 molecules are then adsorbed at the accessible sites
(Figure 21B) and even displace some water (Figure 21C),
JIANG et al.
F I G U R E 2 0 Crystal structures of Mg-CUK-1 with different
H2 O molecule loadings, from top to bottom, 0, 1, 2, 4, and 8 water
molecules per unit cell. (A) View through the a-axis showing the
hydrogen-bonded H2 O molecules to the hydroxo functional groups
(H2 O⋅⋅⋅OH-μ3), and (B) side view of the channel (through the
c-axis) and accessible surface, yellow circles represent CO2 kinetic
diameter. Reproduced with permission.41 Copyright 2020, PMC.
which would not happen under anhydrous condition.
Nevertheless, some MOFs have no accessible microporos-
ity after water absorption (Figure 21D). As a result, there is
no increase in CO2 adsorption uptake.
High-throughput screening results indicate that a small
pore size (LCD of around 5 Å) is better for CO2 /H2 O sepa-
ration, which satisfies CO2 diffusion and obstructs water
cluster formation. Moreover, the pre-installing water of
MOFs can also cause a confinement effect, thus changing
the interaction between CO2 and sorbent. The confine-
ment effect is definitely a novel approach to develop MOFs
with a suitable framework for carbon capture in practical
humid working conditions.
It is noted that not all water loadings give rise to more
efficient CO2 molecule accommodation by using the above
methods. For the methods of changing the polarization
interaction of surface or creating confinement effects can
only be used in low humidity ranges because adsorption
type is still physisorption. The presence of extra water can
occupy partial adsorption sites, which leads to a reduction
in adsorption amount. Relatively, the chemical method
can be employed for larger water contents because the
chemisorption force is stronger. However, as Figure 2
shows, there are also some exceptions. Thus, we herein
cannot offer a quantitative description.
21
3.4 Hydrolytic stability
Along with the aforementioned techniques to improve
CO2 adsorption selectivity, it is also important for MOFs
to have the high stability and resistance to irreversible
reactions with water in moisture gases.123 If the MOF struc-
ture collapses under humid conditions, its durability and
application will be limited. The hydrolytic reactivity and
initial decomposition pathway of MOFs depend on the
specific type of ligand and second building unit (SBU).124
MOFs with various metal ions and ligands have been
investigated, which involves water-labile and water-stable
MOFs.122,125–127 For water-stable MOFs, the stronger bonds
between metal clusters and organic linkers can be found to
possess a structure with greater stability in moisture.28
Water can react with MOFs via ligand displacement
and/or hydrolysis.122 As shown in Equation (1), ligand dis-
placement inserts an H2 O molecule into a metal–ligand
bond. The hydrolysis reaction involves water dissocia-
tion into a hydroxide ion and a hydrion. Bond formation
between a metal with hydroxide ion and a ligand with
hydrion is shown in Equation (2).
M − L + H2 O → M − (OH2 ) ⋯ L (1)
M − L + H2 O → M − (OH) + LH (2)
Many hydrolytic stability factors, such as metal compo-
sition and coordination, chemical functionality of organic
ligands, framework dimensionality, and interpenetration,
have an influence MOF stability from an aspect of ther-
modynamic or kinetics.127 To explore the stabilities of
various MOFs, Low et al.122 conducted an experimental
test together with molecular modeling. A steam stabil-
ity map is shown in Figure 22. It is found that MOFs
bridged by carboxylates need less activation and reac-
tion energy since the metal–ligand bonds are weaker than
those of imidazolates, which is linked to imidazolates’
greater basicity.128 Hence, MOFs bridged by imidazolates
such as ZIF-8 tend to be more hydrolytically stable than
those bridged by carboxylates. Besides, it is significant to
regard the stability of SBUs in the MOF structure. The
higher oxidation of metals or metal ions, the better stabil-
ity toward hydrolysis becomes. In general, metals with the
higher metal valence are discovered to be more resistant
to hydration. For instance, the relative positive charge per
Zn of Zn4 O6+ cluster in MOF-5 is 1.5, which is less than
metal valence in HKUST-1 and MIL-101. It is suggested
that HKUST-1 and MIL-101 could form stronger metal–
linker bonds than MOF-5, which can prevent the collapse
structures.122 Although a small amount of water (0.5 mole
equivalent) has no impact on the network structure sta-
bility of HKUST-1, higher water adsorption may cause the
22 JIANG et al.

F I G U R E 2 1 (A–D) Schematic diagram of the possible mechanisms of CO2 adsorption in the presence of water. Reproduced with
permission.29 Copyright 2012, ACS.

F I G U R E 2 2 Map of steam stability for four metal–organic frameworks (MOFs). Position of the structure for an MOF represents its
maximum structural stability by X-ray diffraction (XRD) measurement, while activation energy for ligand displacement by a water molecule
determined by molecular modeling is represented by a magenta number (in kcal mol−1 ). Reproduced with permission.122 Copyright 2009,
ACS.

network structure to be partially broken at Cu–O coor-
dination sites.129 Besides, chemical stability to water can
be increased with the increased inertness of central metal
ions.130 For example, the chemical stability of isotypic
MOFs such as Al-BDC (Al-benzenedicarboxylate called
MIL-53-Al), Cr-BDC (MIL-53-Cr), and V-BDC (MIL-47-V)
decreases in the order, Cr-BDC > Al-BDC > V-BDC.130
Thus, it is possible to enhance water stability of
MOFs by strengthening metal–ligand interactions from
a thermodynamic perspective, or enhancing hydropho-
bicity or steric hindrance from a kinetic perspective.
From a thermodynamic aspect, the enhanced strength
of metal–ligand bonds can be achieved by replacing
metal ions with the higher valence cations or more inert
metal ions since cation–ligand bonds are inclined to
hydrolyze for low-valent metals.72 Alternatively, chang-
ing the ligand can improve the bond energy. Colombo
et al.131 applied polyazolate-bridging ligands in MOFs,
which leads to strong metal–nitrogen bonds when com-
pared to carboxylate-based counterparts. This indicates
JIANG et al.
that strength of M–N bonds is related to pressure required
for the deprotonation of N–H bonds. Thus, frameworks
generated from organic ligands functionalized with 1,2,3-
triazole (pKa = 13.9) have greater thermal stability than
analogs based upon tetrazole (pKa = 4.9).132
For the kinetic aspect, it is effective to increase water sta-
bility by synthesizing highly hydrophobic surfaces or coat-
ing MOFs with appropriate polymers to increase structure
steric hindrance and hydrophobicity.133,134 For instance,
some MOFs with water-repellent groups such as methyl
groups incorporated into organic ligands exhibit excellent
stability under humid conditions. Wu et al.135 reported an
MOF by strategically with non-polar functional groups,
trifluoromethoxy, in the frameworks. Trifluoromethoxy
groups in MOFs prevent water intrusion into framework
structures, which improves the stability in the humid
air. Linkers modified by either polar or non-polar groups
enhance the overall stability of the lattice by drawing water
toward new adsorption sites, thus hindering water from
reaching the metal center.136 Besides, steric hindrance is
an undeniable factor in reducing hydrolysis. MOFs with
high coordination numbers, such as UiO-66(Zr)137 and
MIL-125(Ti),138 have high connectivity and provide steric
shielding against water for SBUs. This factor can also be
confirmed in research by Tang et al.139 Ca-based MOFs
are stable up to 98% RH due to ligand distortion, which
causes more steric hindrance effect of benzene rings to
protect Ca2+ ions from water attack. Moreover, contract-
ing or rigidifying the ligands can also enhance the rigidity
of framework and consequently water stability.140,141 Lv
et al.142 constructed 13 Zr-MOFs consisting of three classes
of ligands. The results imply that rigid linkers with lower
degree of rotational freedom have a self-repair mechanism
after water substitution, and this effect is more effective
with the higher connectivity. Moreover, shorter linkers can
have greater deformation energy barrier due to the larger
angle during framework destruction.143
4 PROTOTYPE VERIFICATION
To address the large energy penalty of common aque-
ous monoethanolamine solution scrubbing technology for
post-combustion carbon capture, adsorbents and process
design need to be more effective and energy intensive.
Porous solid sorbents offer the advantage of lower regen-
eration heat when compared to aqueous amine solvents.
When desorption heat is assumed to be consistent, a higher
sorbent operating capacity can lead to a lower thermal
energy input.144 Several promising adsorbents have been
proposed for carbon capture, which have high CO2 selec-
tive adsorption capacity under wet conditions. Besides,
the capture process of sorbent in the reactor should also
23
be evaluated when considering real heat and mass trans-
fer processes. In order to evaluate adsorbent features
that more closely resemble actual use, this section aims
to present simplified prototype testbeds using MOFs for
carbon capture.
Adsorption CO2 removal can be achieved by tempera-
ture swing adsorption (TSA), pressure swing adsorption
(PSA), VSA, or other hybrid working processes. For CO2
and H2 O binary adsorption, VSA and TSA are more com-
monly used to achieve higher CO2 purities than PSA.145
Under the circumstances of simulated coal flue gas, Lyu
et al.42 investigated MOF-808-Gly’s performance of car-
bon capture with a specially designed VSA apparatus,
as shown in Figure 23. The inlet of sorption reactor is
connected to flue gases, and the outlet is used to expel CO2 -
lean stream. The inlet transforms into an outlet CO2 -rich
stream during the regeneration process. To avoid water
condensation on the gas sensor and to increase the purity
of product gas, a membrane drier is installed along the
regeneration branch. The simulated flue gases are bal-
anced in N2 at 20◦ C–23◦ C, which contain 15% CO2 at
an RH of 20%. The regeneration process of the system
starts once CO2 concentration reaches more than 2%. A
glycine-filled MOF-808-Gly-functionalized sorption reac-
tor displays good cycle stability at 80 cycles with an average
CO2 uptake of 0.42 mmol g−1 h−1 . Likewise, Hossain
et al.146 investigated similar volumetric system to test mul-
ticomponent isotherms of UiO-66 with three distinct water
loadings (low, pore filling, and saturation). The results
indicate that CO2 uptake slightly increases at low water
loading (1.5 mol kg−1 ), which is consistent with the results
from Jajko et al.’s study,31 and then gradually decreases
as water loading increases. The cooperative effect of low
adsorbed water can be attributed to the confinement effect
and affinity toward CO2 . When water loading approaches
saturation, CO2 uptake will decrease by up to 60% from 0 to
5 kPa. However, the flue gases will be nearly saturated with
water when dropping to ambient temperature since water
content in flue gases is almost 7%, which has been ignored
in most researches. Thus, the simulated flue gases with sat-
uration water loadings at a moderate temperature require
additional attention. In this work, we are just concerned
with the adsorption properties of capacity and selectivity.
Other aspects such as adsorption kinetics, thermal conduc-
tivity, and adsorption heat should also be considered for
process metrics such as productivity, specific energy, and
purity.147
The zero length column (ZLC) technique, which is effec-
tive in obtaining transient desorption curves, has gained
application in the determination of the effect of water.
In a ZLC experiment, the exterior mass and heat trans-
fer resistance of sorption bed can be ignored. Hu’s team148
assessed the behavior of M/dobdc (M = Co, Ni, Mg) and
24 JIANG et al.

Rotameter
CO2 Volumetric
RH T CO2
Rotameter Flow Meter Simulated
Vacuum Gauge
N2 Flue Gas
Rotameter Stream
Solenoid Solenoid Pressure
Valve Valve Relief Valve
S S

Regeneration
Branch
Saturator Cell
Isothermal Bath RH T RH T CO2
MFC CO2-Rich
Legends Stream
Diaphragm
Gas Line
Pump
Sorption In-Line
Stream Type Bed Dryer Membrane
CO2
Dryer
Adsorption
Branch
Branch Name Compressed Humid
Air Air
RH Sensor
In-Line Adsorption RH T CO2
Filter S Branch MFC CO2-Lean
Stream
Solenoid Piston
Valve Pump

F I G U R E 2 3 Schematic diagram of the practical vacuum swing adsorption (VSA) testing apparatus. Reproduced with permission.42
Copyright 2022, ACS.

commercial 13X zeolite pellets in ZLC with 1% (v/v) water.
The water content was purposefully adjusted to a low
value, presuming that flue gas had already been dried for
physical sorbents. Co/dobdc and Mg/dobdc lack stability
to moisture, but Ni/dobdc is less sensitive to water. How-
ever, when exposed to wet flue gas conditions, adsorption
capacity of Ni/dobdc declines as the duration of the expo-
sure increases. Co/dobdc appears to require a longer time
for the regeneration process; that is, it only has a slight
loss in CO2 uptake after exposure to wet flue gas. This
is in line with Kizzie’s work, which finds that Co/dobdc
had the highest CO2 capacity (85% of that of pristine
samples) at 70% RH among M/dobdc.149 Also, Mangano
et al.150 employed ZLC to investigate water stability. For
water stability of Mg-CPO-27 and Ni-CPO-27, Mg-CPO-27
is deactivated in the presence of water. However, Ni-CPO-
27 passes water-stable test and remains at a reduced and
steady CO2 capacity in the moist flue gas.
The performance of MOFs in the volumetric system
is basically comparable to that of gravimetric apparatus.
One issue that needs to be pointed out in the volumet-
ric experiment is the transformation of the morphology
of MOF. MOFs in pellets have the less uptake and slower
adsorption kinetics when compared to pure powder. This
issue cannot be avoided if real carbon capture progress
proceeds. More CO2 –water co-adsorption factors should
be considered in a practical CDR facility, as shown in
Figure 24. For example, after the nitrogen oxides, partic-
ulates, and sulfur oxides have been removed, the flue gas
will be cooled using cooling water from power plant’s cool-
ing tower. The temperature of the flue gas will fall below
40◦ C, and its water content will be reduced by at least
75% until it reaches saturation. Therefore, we should con-
sider CO2 –water co-adsorption and energy consumption of
regeneration. Meanwhile, a water zone may be formed in
the adsorption bed and alter thermal profiles.151 More heat
or vacuum degrees are required to desorb the water zone.
The water that comes along with the CO2 -rich stream is
collected in the vacuum pump or other drying devices. This
system is only appropriate for MOFs on which the satu-
rated water has a favorable or insignificant effect on CO2
adsorption ability. For other MOFs with a dramatic decline
in CO2 adsorption capacity under humid conditions, mul-
tiple stages might be a viable option to pre-adsorbed water
vapor in flue gases.
5 CONCLUSIONS AND FUTURE
PERSPECTIVES
Nanoporous MOFs have great potential for carbon capture
because of their customizable and adjustable pore sur-
face, high porosity, structure diversity, etc. To find MOFs
with excellent adsorption performance under humid
JIANG et al.
F I G U R E 2 4 Schematic diagram of
metal–organic framework (MOF)-based CO2
capture system process (adapted from Ref.
152).
Flue Gas
from FGD
Feed
Compressor
(for PSA)
conditions, it is feasible and convenient to perform numer-
ical screenings of MOFs based on their structures for selec-
tive adsorption. The Henry constant, Henry selectivity, and
adsorption enthalpy are three more practical indicators
that can be used in the initial screening. Then, depending
on the specific capture objectives, more targeted indica-
tors such as separation potential, percent uptake loss, and
selectivity should be analyzed for top-performing MOFs.
The screening results of CO2 adsorption in the presence
of water show that high surface affinity toward CO2 pro-
vided by adsorbents with superb chemical structures or
co-adsorption adsorbates and suitable pore sizes results in
good CO2 /H2 O selectivity.
CO2 uptake or selectivity can be improved through
these methods. The higher polarization interaction for
CO2 than H2 O can come from hydrophobic modification,
pores with specific- CO2 adsorption sites, or new adsorp-
tion sites generated by pre-adsorbed water. However, the
extremely strong hydrophobicity leads to poor CO2 adsorp-
tion capacity. In addition, amine functional sorbents with
chemisorption ability have drawn wide attention due to
their remarkable CO2 capacity, especially in humid con-
ditions, which could be attributed to the increase in amine
efficiency and promotion of ammonium carbamate chain
formation via hydrogen bonding interactions. However,
the desorption process also faces larger energy barriers.
The confinement effect is another condition that can
increase CO2 uptake in wet gases. This is caused by water
pre-adsorption and leads to diffusional restriction and
structural constraints. Due to physisorption, they also have
a low desorption heat, but their CO2 adsorption capacity
at relatively low partial pressure is not very impressive.
Researches on changing the pore window and size to
improve the confinement effect of cavities in MOFs for
CO2 adsorption and prevent water cluster formation are
still needed for further exploration. Moreover, the struc-
ture of MOFs should be robust enough to avoid structure
collapse in the presence of water. The water stability can
be improved by increasing the strength of the metal–linker
bond by replacing more stable metal ions or ligands from
25
Cooled CO2 to
Flue Gas Storage
CO2 and
Feed Sorption Water CO2 compression
Cooler bed and Drying
Water Raffinate Evacuation Water
Compressor
(for VSA)
a thermodynamic aspect, or it can be refined by hydropho-
bic treatment or/and enhancing the steric hindrance with
respect to adsorption kinetics.
For the simplified prototype testbeds, working capac-
ity of MOFs is also related to heat and mass transfer
rate and actual operating conditions. It is not involved
in this review, which is only concerned with humidity
impact. It should be noted that the change in humid-
ity level depends on the application circumstance. If flue
gases are pretreated to remove moisture, sorbents with
confinement effect are suitable under the condition of
low humidity since water vapor cannot be completely
removed. Without pretreatment or in DAC, the porous
amine-functionalized MOFs are emphasized as having a
higher binding strength to collect CO2 in conditions of
high RH or/and the extremely low CO2 partial pressure.
After water–CO2 co-adsorption, the regeneration energy of
water and drying of product gas should both be considered.
In summary, various modification methods have been
applied for carbon capture in the presence of water. The
intrinsic properties of adsorbents are very important to
enhance the affinity of CO2 , which can be tuned by alter-
ing the constituent elements and topologies of MOFs. It is
also crucial to strike a balance between a low affinity for
H2 O and a strong affinity for CO2 . This work undoubtedly
offers practical and useful guidelines to choose and design
MOFs in the near future.
AC K N OW L E D G M E N T S
This research was supported by the National Key
Research and Development Program of China (Nos.
2022YFB4101700 and 2022YFE0128600), the National
Natural Science Foundation of China (Nos. 52276022,
22278365, and 22225802), and the Basic Research Funds
for the Central Government ‘Innovative Team of Zhejiang
University’ under contract number 2022FZZX01-09. Long
Jiang and Jinyuan Yong contributed equally to this work.
C O N F L I C T O F I N T E R E S T S TAT E M E N T
The authors declare no conflicts of interest.
26
ORCID
Zongbi Bao https://orcid.org/0000-0003-4327-3028
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How to cite this article: Jiang L, Yong J, Xie R,
et al. Screening, preparation, and prototyping of
metal–organic frameworks for adsorptive carbon
capture under humid conditions. SusMat.
2023;1-30. https://doi.org/10.1002/sus2.154
AU T H O R B I O G R A P H I E S
Dr. Long Jiang is currently a
researcher at Zhejiang University’s
“Hundred Talents Program.” He
was graduated from Shanghai Jiao
Tong University in 2015 with a PhD
in Refrigeration and Cryogenic
Engineering. From 2015 to 2020, he
held postdoctoral, research asso-
JIANG et al.
ciate, assistant professor, and lecturer positions at
Shanghai Jiao Tong University, Newcastle University,
Durham University, and the University of Aberdeen,
and mainly engaged in basic scientific and applied tech-
nology research in areas such as efficient heat and cold
storage technology, carbon capture and resource uti-
lization technology, efficient food drying technology,
and waste heat power generation technology.
Jinyuan Yong graduated from
Chongqing University in 2021 wiht
a a bachelor’s degree. Currently,
she is pursuing a master’s degree
at Zhejiang University under the
supervision of Dr. Long Jiang. Her
research focuses on carbon cap-
ture from wet flue gas using a
diamine-appended metal-organic framework.
Zongbi Bao is a professor at Zhe-
jiang University. He received his
Bachelor’s and PhD degrees in
Chemical Engineering from Zhe-
jiang University in 2003 and 2008,
respectively. He then worked as a
postdoc at Zhejiang University and
New Mexico State University from
2009 to 2010 and joined the College of Chemical and
Biological Engineering at Zhejiang University in 2011.
His research interests include (1) synthesis and appli-
cations of MOFs, carbon-based materials, and chiral
stationary phase for adsorption and chromatography;
(2) adsorption processes for gas separation and purifi-
cation; (3) green separation processes in ionic liquids or
supercritical fluids; and (4) extraction and purification
of bioactive compounds from biomass.