Front. Chem. Sci. Eng.

2021, 15(2): 437–449

https://doi.org/10.1007/s11705-020-1961-6

RESEARCH ARTICLE

Effects of functional groups for CO2 capture using metal

organic frameworks

Chenkai Gu1, Yang Liu2, Weizhou Wang3, Jing Liu (✉)1, Jianbo Hu1
1 State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology,
Wuhan 430074, China
2 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0100, USA
3 Henan Key Laboratory of Function-Oriented Porous Materials, College of Chemistry and Chemical Engineering, Luoyang Normal University,
Luoyang 471934, China

© Higher Education Press 2020

Abstract Metal organic frameworks (MOFs) are promis-
ing adsorbents for CO2 capture. Functional groups on
organic linkers of MOFs play important roles in improving
the CO2 capture ability by enhancing the CO2 sorption
affinity. In this work, the functionalization effects on CO2
adsorption were systematically investigated by rationally
incorporating various functional groups including –SO3H,
–COOH, –NH2, –OH, –CN, –CH3 and –F into a MOF-177
template using computational methods. Asymmetries of
electron density on the functionalized linkers were
intensified, introducing significant enhancements of the
CO2 adsorption ability of the modified MOF-177. In
addition, three kinds of molecular interactions between
CO2 and functional groups were analyzed and summarized
in this work. Especially, our results reveal that –SO3H is
the best-performing functional group for CO2 capture in
MOFs, better than the widely used –NH2 or –F groups. The
current study provides a novel route for future MOF
modification toward CO2 capture.
Keywords metal-organic frameworks, functional groups,
CO2 capture, GCMC, DFT
1 Introduction
Carbon dioxide (CO2) from fossil fuel combustion is one
of the most important greenhouse gases which result in the
global warming [1,2]. Various methods have been
proposed to prevent the CO2 emission into the atmosphere,
among which the CO2 capture and storage (CCS) shows
Received April 3, 2020; accepted May 19, 2020
E-mail: liujing27@mail.hust.edu.cn
great potentials in short-term CO2 reduction [3]. There are
several approaches to capture CO2 from carbon emitting
sources, including amine scrubbing [4,5], membrane
separation [6,7], and sorbent adsorption [8–10]. Compared
to the other methods, capturing CO2 using porous sorbents
is especially attractive owing to the low energy consump-
tion, high economic benefit and easy tailoring [11–13].
Comparing with the traditional porous materials such as
activated carbons and zeolites, metal organic frameworks
(MOFs) show more advantages in CO2 capture due to their
highly tunable structures, porosities and chemical proper-
ties [14–16]. In order to improve the CO2 capture
capacities of MOFs, many approaches have been pro-
posed. The pore chemistry adjustment can benefit CO2
capture in MOFs, which depends strongly on pore
topology [17]. Besides, smaller pore size usually leads to
higher overlap of potential energy between CO2 molecule
and MOF, contributing to higher CO2 capture abilities. An
and Rosi [18] tuned CO2 adsorption properties of MOFs
through cation exchange and concluded that smaller pores
in MOFs may be an ideal way to condense CO2 at
temperatures of real-world application. Pal et al. [19]
reported that the selective adsorption of CO2 can be
improved by forming smaller pores via structural inter-
penetrations. Via creating the cage-within-cage architec-
ture, Zheng et al. partitioned the pore space into small
domains which are among key desirable features for
enhancing CO2 adsorption through a better size match and
stronger charged-induced forces [20].
For CO2 capture, functional groups can significantly
affect the CO2 adsorption capacities of MOFs [21,22].
Xiang et al. [23] incorporated polar acidic functionalities
into MOFs and demonstrated that this is an alternative
approach for enhancing CO2 capture. Zheng et al. [24]
found that the acylamide-decorated MOFs show higher
adsorption heat and improved CO2 adsorption capacity
438 Front. Chem. Sci. Eng. 2021, 15(2): 437–449
than unfunctionalized MOFs. An et al. [25] pointed out
that amine decoration can significantly enhance the CO2
uptake in MOFs through forming favorable interactions.
Ye et al. [26] found that MOFs with rich accessible
nitrogen sites show highly efficient CO2 capture and
separation. Li et al. [17] carried out high-through
computational screening of a large number of computer-
generated MTV-MOFs and concluded that the functiona-
lization and small pores are two beneficial factors for CO2
capture in MOFs. Among various functionalization
methods, incorporations of nitrogen atoms or nitrogen-
containing functional groups are commonly used to
enhance the CO2 interaction ability in previous work.
However, recent studies have shown that incorporating
oxygen onto organic linkers can better enhance the CO2
adsorption in MOFs [27]. Various oxygen-containing
functional groups like –OH and –COOH have been
investigated for this purpose [28,29]. However, –SO3H
containing more oxygen has not been reported for its
potential in improving CO2 capture capability of MOFs.
In this work, we investigated the functionalization effect
of –SO3H group on CO2 adsorption capacity of MOFs
using grand canonical Monte Carlo (GCMC) simulations
and density functional theory (DFT) calculations. The
incorporation of large functional groups like –SO3H
requires enough pore space in MOFs. The MOF-177 has
suitable pore size and some of the functionalized MOF-177
has been successfully synthesized in experiments [30].
Therefore, the MOF-177 was treated as the parent material
in this work. By comparing with various functional groups
including –COOH, –NH2, –OH, –CN, –CH3 and –F in
MOF-177, we verified our hypothesis that –SO3H can
greatly enhance the CO2 adsorption capacity of MOF
materials. The current study revealed a novel functional
group for benefiting the future adsorbent developments.
2 Model and simulation method
2.1 MOF structure
The initial structure of MOF-177 was obtained from the
experimental X-ray diffraction [30], as shown in Fig. 1.
MOF-177 is a porous crystalline material which consists of
Zn4O tetrahedrons connected with 1,3,5-benzenetriben-
zoate (BTB) ligands. The functional groups were intro-
duced to MOF-177, and then the whole structures were
geometry optimized using Forcite module [31]. The
MOF-177 functionalized by –F, –CH3, –NH2 has been
synthesized by Zhang et al. [30]. Besides, the –COOH and
–SO3H groups have been incorporated to some other
MOFs in experiments [32,33]. The structural properties of
functionalized MOF-177 were given in Table 1. The
accessible surface area was calculated with an equal van
der Waals diameter to N2 molecule (3.64 Å). The total pore
volume was calculated with an equal van der Waals
Fig. 1 Structure of MOF-177 (Zn, light blue tetrahedrons; O, red
spheres; C, gray spheres; and H, white spheres).
diameter to He (2.6 Å). The structural parameters
mentioned above was calculated with the tool of the
Atom Volumes & Surfaces in Materials Studio 2017 [31].
The pore diameters were obtained by using Poreblazer
v3.0.2 [34].
2.2 DFT calculations
Theoretical calculations were performed to explore the
underlying mechanisms in terms of physical chemistry
[35–38]. The entire periodic MOF structure contains
hundreds of atoms and will cost too much computational
resources to carry out DFT calculations. In order to save
computational cost, cluster models were constructed using
the method as described in our previous studies [28,29].
The models used in this work were given in Figs. S1–S8
(cf. Electronic Supplementary Material, ESM). All of the
theoretical calculations were performed using DMol3 code
with exact DFT spherical atomic orbitals [31]. This method
has already minimized the basis set superposition error
effects which strongly affects the binding energy results
[39]. The PW91 exchange-correlation functional was
applied to investigate the interactions between MOFs and
CO2 molecules [40]. The double numeric polarization
basis set was used to describe the atomic orbital [41]. The
DFT semi-core pseudo-pots [42] which was developed
specially for DMol3 calculations was used to set the core
treatment type. The convergence tolerance parameters
were 2
10–5 (energy), 4
10–3 (force) and 5
10–3
(displacement), respectively.
All initial cluster models were first optimized using the
calculation methods mentioned above and shown in Fig. 2.
The binding sites were classified and signed clearly in
Fig. 2(c). For each binding site, three different possible
orientations of CO2 molecule were investigated, marked as
parallel (P), cross (C) and vertical (V), as shown in
Fig. 2(a). Additional geometry optimizations were per-
formed to the CO2-cluster models. Finally, the single point
binding energy of CO2 around functional group was
calculated with the following equation:
 Chenkai Gu et al. Effects of functional groups for CO2 capture using metal organic frameworks 439

Table 1 Structural and limiting CO2 adsorption properties of the MOFs studied in this work
Sacc
MOF dpore/Å rcrsy/(g$cm–3) Vpore/(cm3$g–1) void fraction –1
qst0/(kJ$mol–1)
m $g
2
m2$cm–3
MOF-177 11.99 0.422 1.925 0.811 3977 1677 – 13.41
MOF-177-NH2 11.79 0.455 1.739 0.791 3939 1792 – 16.89
MOF-177-COOH 11.36 0.519 1.475 0.765 3662 1900 – 19.00
MOF-177-CH3 11.76 0.453 1.725 0.781 4076 1845 – 14.17
MOF-177-F 11.98 0.461 1.744 0.804 3731 1722 – 14.67
MOF-177-SO3H 11.54 0.598 1.230 0.736 3260 1950 – 20.52
MOF-177-CN 11.91 0.477 1.642 0.783 3838 1830 – 15.46
MOF-177-OH 11.79 0.457 1.747 0.798 3843 1757 – 16.48

BE ¼ ECO2 cluster – ðECO2 þ Ecluster Þ: (1) 8.8542
10–12 C2$N–1$m–2, and αβ , εαβ are the collision
diameter and well depth, respectively. In this study, the
In the equation above, ECO2 represents the total energy of CO2 was modeled as a rigid linear molecule with two
CO2, Ecluster represents the total energy of cluster, and bonds in the length of 1.16 Å, taken from the transferable
ECO2-cluster represents the total energy of CO2-cluster potentials for phase equilibria force field [44]. The internal
system under equilibrium state. A negative BE corre- quadrupole moment was described through partial charges
sponds to an exothermic binding process and a higher on each charged Lennard-Jones site (qc = + 0.70 e and qo =
negative value means a stronger binding process [43]. –0.35 e). The universal force field [45] has been
successfully applied in the study of CO2 adsorption in
2.3 Force field MOFs, and was used to calculate the interactions between
The interactions considered in this simulation, including adsorbates and adsorbents in this work. All Lennard-Jones
gas-gas part and gas-adsorbent part, were calculated by parameters were mixed with Lorentz-Berthelot rules, as
combining site-site Lennard-Jones (L-J) and Coulombic shown in Table 2. For a given MOF, the determination of
potentials: framework atom charges mainly contains two steps: (1) the
X   12  6   calculation of the electrostatic potential (ESP) in the MOF
αβ αβ qα qβ
α 2 i 4εαβ
uij ðrÞ ¼ – þ , pores [46], (2) the assignment of electronic charges to
β2j gαβ gαβ 4πε0 gαβ MOF atoms to reproduce the ESP using fitting procedures
(2) such as the repeating electrostatic potential extracted
atomic [47], the molecular building block-based [48] and
where ε0 is the permittivity of the vacuum and equals to the density derived electrostatic and chemical [49]

Fig. 2 (a) V, C and P represent the orientations of “vertical”, “cross” and “parallel”; (b) the basic model for binding energy and atom
charge calculations; (c) U, F and R represent the binding site of “top”, “front” and “right”, respectively (Zn, light blue spheres; O, red
spheres; C, gray spheres; H, white spheres and functional group: purple sphere).
440 Front. Chem. Sci. Eng. 2021, 15(2): 437–449

Table 2 Lennard-Jones parameters used in this work

3 Results and discussion
Atom types s/Å ε/(kb$K–1)
CO2–C 2.800 27 3.1 Electrostatic fields and orbitals of the linkers
CO2–O 3.050 79
MOF–Zn 2.462 62.397 The cluster model was geometry optimized followed by
MOF–N 3.261 34.721 calculating the ESP charges as listed in Tables S1–S8 (cf.
MOF–S 3.595 137.877 ESM). For all the MOFs, although the Zn and surrounding
MOF–F 2.997 25.16 O in metal clusters have larger charges than the other atoms
of frameworks, the corner space formed by metal clusters
MOF–C 3.431 52.836
is rather limited for strong CO2 binding. As shown in the
MOF–O 3.118 30.192 tables, introducing functional groups can significantly
MOF–H 2.571 22.141 affect the electrostatic field as evidenced by the changed
atomic charges on the organic linkers. Taking MOF-177-
SO3H as an example, the absolute values of atom charges
methods. In this work, the ESP charges of the MOF in –SO3H group range from 0.338 e to 0.484 e (as shown in
frameworks were calculated via typical MOF-representa- Table S8). These charges are much larger than those of
tive models which have been successfully used in previous other nonmetal atoms with value ranging from –0.229 e to
work [50–52]. + 0.117 e, leading to the enhancement of electrostatic
interactions between CO2 molecules and organic linkers.
2.4 GCMC simulation
Besides, the incorporation of –SO3H group into MOFs will
result in the decrease of pore sizes. This will lead to the
The GCMC simulation was performed to investigate the
stronger overlap of the potential energy fields for CO2
adsorption of CO2 in MOF-177. The simulation box of
molecules. Consequently, the CO2 capture performance
MOF-177 containing 8 (2
2
2) unit cells with periodic
will be highly improved especially at low pressure.
boundary conditions was applied in this work. The
To study the change transfer between CO2 and organic
frameworks studied in this work were treated as rigid
linkers, the lowest unoccupied molecular orbitals
with atoms frozen at their crystallographic positions during
(LUMOs) of functionalized organic linkers are shown in
calculations. A cutoff radius was set to 12.8 Å for the van
Fig. 3. Compared to nonpolar groups like –H and –CH3,
de Waals interactions, and the long-range electrostatic
polar groups like –CN and –SO3H can significantly
interactions were handled using the Ewald summation
intensify the asymmetry of electron density and change
method with the tinfoil boundary condition. The GCMC
the delocalization of electron density. Notably, the –SO3H
calculation in each point consists of 2.0
107 steps. The
group shows more significance on enhancing the deloca-
former half part was used to guarantee the equilibration
lization of LUMO in organic linkers, which further
and the latter half part was used to sample the desired
strengthens the interactions with the orbitals of CO2
thermodynamics properties. The input fugacity was
molecules.
calculated with the state equation of Peng-Robinson. The
isosteric heat qst was determined by the statistical average
3.2 Configurations of CO2 interacting with functionalized
of CO2 binding energies at various sites which contain
linkers
both the sites around functional groups and some other
sites in MOFs, as the following equation:
To explore the binding mechanisms, the configurations of
hUff N i – hUff ihN i hUsf N i – hUsf ihN i CO2 binding around functional groups and metal clusters
qst ¼ RT – – , (3) were analyzed after DFT optimizations. All the stable
hN 2 i – hN ihN i hN 2 i – hN ihN i
configurations and the corresponding binding energies
where N represents the number of adsorbed molecules, R (BEs) are listed in the Supplementary Material (as shown
represent the gas constant, and h i means the ensemble in Figs. S10–S18, cf. ESM). The name of each configura-
average. The first term is the contribution from molecular tion contains three terms. The first term is the functional
thermal energy, the second term is the contribution from group. The second term represents the initial binding site
the interaction energy among adsorbates Uff, and the third before optimizations (U: on the top of functional group; F:
term is the contribution from the adsorbent-adsorbate in front of functional group; R: on the right of functional
interaction energy Usf. The qst0 represents the adsorption group). The third term is the initial orientation before
heat in infinite dilution calculated by NVT simulations optimizations (V: vertical; C: cross; P: parallel). Figure 4
with a single CO2 molecule. In general, the adsorption heat shows several representative configurations of unfunctio-
shows a positive correlation with DFT binding energy, as nalized linkers. In configuration (–H)–F–V, the CO2
shown in Fig. S9 (cf. ESM). All the GCMC simulations molecule was located aside the benzene ring vertically
were performed with the Sorption code [31]. with a distance of 2.812 Å between H atom and C(CO2)
 Chenkai Gu et al. Effects of functional groups for CO2 capture using metal organic frameworks 441

atom. In configuration (–H)–U–C, the CO2 molecule was
lying over the plane of benzene, and the distance between
H atom and C(CO2) atom is 2.971 Å. The highest binding
energies are –21.14 and –21.83 kJ/mol for (–H)–F–V and
(–H)–U–C, respectively.
The following section is mainly about the configurations
of functionalized MOF-177 (given in Figs. 5 and 6).
Except the dispersion forces, we analyzed three kinds of
interactions between CO2 and frameworks: (i) the hydro-
gen bond interactions between carbon atoms in CO2
molecules and the hydrogen atoms in acidic groups or
amino groups; (ii) the electrostatic interactions between
lone pair electrons and the carbon atoms in CO2 molecules;
(iii) the induced dipolar interactions between halogen
atoms and the carbon atoms in CO2 molecules.
Hydrogen bond interaction is a kind of strong interaction
during the adsorption process and can be observed in
configurations of (–SO3H)–F–P, (–COOH)–U–C, (–OH)–
F–P, and (–NH2)–R–C from Fig. 5. Here, the configuration
(–SO3H)–F–P was taken as an example. In this configura-
tion, the CO2 molecule locates in the middle of the two
S = O bonds and pointing directly to the H atom, which
ensured that the CO2 molecule can obtain interactions from
H atom and O atoms of –SO3H group simultaneously. The
distance between O(CO2) and H(–SO3H) is 1.881 Å, which
denotes a relatively strong interaction. The H  O = C
angle is 157.9° within the range of hydrogen bond from
120° to 180° [53]. The existence of hydrogen bond could
significantly improve the affinity of organic linker, which
is also supported by the large binding energy of
–33.29 kJ/mol between CO2 molecule and organic linker
in configuration (–SO3H)–F–P.
Apart from hydrogen bond interaction, the electrostatic
interactions between the lone pair electrons and the carbon
atoms in quadrupole CO2 molecules also play an important
role. The quadrupole-lonepair interactions can be observed

Fig. 3 LUMOs of linkers decorated with –CH3, –CN and –SO3H (C, gray; H, white; O, red; N, dark blue; S, yellow).

Fig. 4 DFT optimized structures of the CO2-linkers in MOF-177 (O, red spheres; C, gray spheres and H, white spheres).
442 Front. Chem. Sci. Eng. 2021, 15(2): 437–449
Fig. 5 DFT optimized structures of the CO2-linkers modified with –SO3H, –COOH, –OH, and –NH2 (S, yellow spheres; O, red spheres;
C, gray spheres; N, dark blue spheres; H, white spheres).
in configurations of (–COOH)–F–V, (–CN)–F–V, (–OH)–
U–P, (–SO3H)–U–P, and (–NH2)–U–P as listed in Fig. 6.
Taking configuration (–COOH)–F–V as an example, the
CO2 molecule is tilted in front of the –COOH group with a
distance of 3.062 Å between O(–OH) and C(CO2). The
O(–OH) is protruding outward and forming a quadrupole-
lonepair interaction with C(CO2). The binding energy here is
–26.43 kJ/mol. There are no hydrogen bond interactions in
this configuration, because the H(–COOH) is pointing away
from the CO2 molecule.
In addition, the C–F  C = O interaction also contributes
to the CO2 binding affinity in a different way. In this
configuration (–F)–F–C of Fig. 6, the fluorine atom is
pointing to the C(CO2) atom with an approximately
orthogonal orientation. The value of characteristic angle
is (C–F  C) = 173°. This suggests an induced dipolar
interaction between fluorine atoms and the carbon atoms in
CO2 molecules [54]. The total binding energy between
CO2 molecule and organic linker is –25.39 kJ/mol. The
configuration (–F)–F–V is mainly different from config-
uration (–F)–F–C in terms of the initial orientations of CO2
molecules before optimizations. The CO2 molecules tend
to stabilize with a final “vertical” orientation after
optimization at the site in front of the fluorine atom.
Considering calculation errors, these two configurations
can be regarded as the same terminal configurations, as
shown in Fig. S16 (cf. ESM).
Based on the above analysis, the CO2 binding affinity of
organic linkers can be significantly enhanced owing to
enlarged intermolecular interactions after introducing
functional groups. In some configurations, two different
types of interactions can exist simultaneously. For
example, the (–CN)–F–V and (–F)–F–C configurations
contain both electrostatic and induce dipolar interactions.
Besides, hydrogen bond interactions and quadrupole-
lonepair interactions occurred simultaneously between
CO2 molecules and the organic linkers of MOF–177–
SO3H. Moreover, –SO3H groups contain more O atoms
 Chenkai Gu et al. Effects of functional groups for CO2 capture using metal organic frameworks 443

Fig. 6 DFT optimized structures of the CO2-linkers modified with –COOH, –CN, –OH, –SO3H, –NH2 and –F (S, yellow spheres; O, red
spheres; C, gray spheres; N, dark blue spheres; H, white spheres and F, cyan spheres).

than other functional groups. These O atoms contained
lone pair electrons which can form stronger quadrupole-
lonepair interactions with C(CO2) atom. This is consistent
with its larger binding energy than the others. The energy
decomposition analyses were also performed to provide
some insights of the interactions between CO2 and
functionalized organic linker. The symmetry-adapted
perturbation theory (SAPT) [55] were carried out with
MP2/6-31 ++ G(d,p) using Q-Chem computational suites
[56]. The functionalized benzene ring is chosen as the
basic sorbent model for energy decomposition analysis,
which has been treated as a useful method in previous
works [57–59]. The energy components including the
electrostatic energy (Ees), the exchange repulsion energy
(Eexch), the effective dispersion energy (Edisp) and the
effective induction energy (Eind) are summarized in
Table 3. Among all the functional groups, the incorpora-
tion of –SO3H can significantly improve the total sorbent–
CO2 binding energy (BE) up to 4 times. The largest
contributions come from the electrostatic interactions
between –SO3H group and CO2 molecules ( – 35.46
kJ/mol) which is much higher than those of the other
configurations. It suggests that MOF-177–SO3H is a
promising material in CO2 capture.
3.3 CO2 adsorption performance in functionalized MOFs
To quantify the enhancement on the binding energies of
CO2 with the functionalized MOFs, GCMC simulations
were performed to calculate the CO2 adsorption properties
in all the functionalized MOF-177 at 298 K and pressure
up to 100 kPa. Specifically, the CO2 capture capacity in
MOF-177–SO3H was calculated with the pressure up to
4000 kPa. To confirm the reliability of the force field and
444 Front. Chem. Sci. Eng. 2021, 15(2): 437–449

Table 3 SAPT interaction energy decompositions (kJ/mol) between CO2 and functionalized linkers
Functioal
Configurations Total BE Ees Eexch Eind* Edisp*
groups

None –5.05 –11.48 18.89 –1.71 –10.75

–SO3H –10.43 –16.32 18.43 –1.60 –10.94

–SO3H –23.94 –35.46 29.96 –7.19 –11.26

–COOH –13.77 –18.79 16.11 –2.07 –9.02

–COOH –11.22 –22.20 30.09 –4.03 –15.09

–COOH –16.43 –21.76 16.64 –2.77 –8.53

–F –5.06 –8.42 11.21 –0.83 –7.01

–F –9.51 –12.70 10.96 –1.21 –6.57

–NH2 –12.92 –21.77 23.46 –2.35 –12.25

–OH –9.05 –15.43 19.00 –1.80 –10.81

–CH3 –7.25 –13.00 20.50 –1.79 –12.97

–CN –11.21 –14.85 10.35 –1.82 –4.89

–CN –11.96 –16.84 14.82 –2.09 –7.86

 Chenkai Gu et al. Effects of functional groups for CO2 capture using metal organic frameworks
the method for calculating atomic partial charges employed
in this work, the adsorption isotherms of CO2 in MOF-177
were simulated and compared with available experimental
data, as shown in Fig. 7. As can be seen from this figure,
the simulated adsorption isotherm showed good agreement
with experimental data [60], which proved the validity of
the force field.
Fig. 7 Comparison of simulated CO2 isotherms and experimen-
tal data in MOF-177 up to 4000 kPa at 298 K.
Figure 8 shows the gravimetric CO2 uptake amounts in
MOF-177 functionalized by different groups at low
pressure. We can observe an enhancement of CO2
adsorption amount for all functionalized MOF-177
compared to unfunctionalized form, which indicated that
the substitution of functional groups is one of the
approaches to increase the CO2 adsorption amount in
MOFs at low pressure. The order of the CO2 loading
amount is shown as the following: –SO3H > –COOH >
–NH2 > –OH > –CN > –F > –CH3. This order is consis-
tent with the order of adsorption heats in infinite dilution
(qst0 in Table 1). Therefore, it was indicated that the
adsorption heat plays an important role on CO2 adsorption
in MOFs at low pressure. The –SO3H, –COOH and –NH2
Fig. 8 CO2 adsorption isotherms of MOF-177 and its functio-
nalized derivatives at low pressure.
445
can significantly improve CO2 adsorption capacity, which
is attributed to their relatively stronger polarity than that of
the others. Among these groups, the –SO3H makes the
largest contribution and its CO2 adsorption amount is
105.11 mg/g at 1 bar. This value is about 3 times higher
than that of the parent MOF-177, larger than the ZIF-78
(91 mg/g) [61], comparable to the uptake on HKUST-1
(150 mg/g) [62] at the same condition. Because, hydrogen
bond interactions and quadrupole-lonepair interactions
occurred simultaneously in MOF-177–SO3H, which will
enhance the binding energy during the CO2 adsorption
process.
Figure 9 shows the contribution of these functional
groups, including CO2 adsorption amount as well as
isosteric heat increasement rate. The increased percentages
of CO2 adsorption amount at 1 kPa was defined as, (Nlater –
Npre)/Npre where the Nlater and Npre denote the amount of
CO2 molecules adsorbed in functionalized and unfunctio-
nalized MOF-177, respectively. The increased percentages
of isosteric heat at initial dilution was defined as
ðq0st – later – q0st – pre Þ=q0st – pre , where the q0st – later and q0st – pre
represent the isosteric heat in functionalized and unfunc-
tionalized MOF-177. The CO2 adsorption amount rises
with the increasement of isosteric heat. This indicated that
isosteric heat can affect the adsorption amount significantly
at low pressure, and the adsorption amount can be enlarged
by improving the isosteric heat. In addition, the contribu-
tions of different functional groups are various owing to
their different internal characteristics. Among all func-
tional groups, the –SO3H group shows the largest
improvement on CO2 adsorption amount. The increased
percentage of CO2 adsorption amount is much higher than
that of –CH3 group and reach up to 176% at 1 kPa. This
value is 32 times higher than that of –CH3 (only about
5.5%), which demonstrates the potential of –SO3H group
in improving CO2 adsorption capability. Therefore, we
further investigated the CO2 adsorption in MOF-177–
SO3H at pressure up to 4000 kPa.
Fig. 9 Contribution of functional groups: yellow columns
represent increased percentages of isosteric heat at initial dilution;
blue columns represent increased percentages of CO2 adsorption
amount at 1 kPa.
446 Front. Chem. Sci. Eng. 2021, 15(2): 437–449

Figure 10 shows the gravimetric and volumetric CO2
uptake amounts in MOF-177 and MOF-177–SO3H at
pressure up to 4000 kPa. At low pressure, both gravimetric
and volumetric CO2 adsorption amounts in MOF-177–
SO3H are higher than that in parent MOF-177 owing to the
larger isosteric heat (Table 1). At high pressure, MOF-177–
SO3H shows lower gravimetric CO2 adsorption capacity,
which can be mainly attributed to both lower crystal
density and total free volume (as shown in Table 1).
However, the volumetric CO2 adsorption capacity of
MOF-177–SO3H is higher than that of MOF-177 with the
increasing pressure. This is because the MOF-177–SO3H
has relatively higher volumetric surface area.
Figure 11 shows the probability distributions of COM of
CO2 in MOF-177 and MOF-177–SO3H at 298 K with 3
different pressures: 1, 100 and 4000 kPa. In the case of
MOF-177, the CO2 molecules were firstly adsorbed around
the metal clusters and then gradually adsorbed at the BTB
linkers with the increasing pressure, which indicated metal
sites were the prior adsorption sites. This is also supported
by the higher CO2 binding energy on metal cluster than
that on BTB linker, as shown in Figs. S17 and S18 (cf.
ESM). For the MOF-177–SO3H, the density of CO2
molecules is higher than that in the non-modified form.
Moreover, the CO2 molecules prefer to the sites around the
metal clusters and –SO3H groups, which indicates that the
binding affinity of –SO3H can significantly improve the
adsorption performance in CO2 adsorption. With the
increasing pressure, the CO2 molecule turned to occupy
the whole pore space in MOF–SO3H. It is also observed
that the incorporation of –SO3H groups can lead to the
decrease of CO2 binding energy on metal clusters, as
shown in Fig. S18. However, this negative effect was offset
by the improved CO2 affinity of organic linkers modified
by –SO3H groups and an increased CO2 adsorption
amount was observed especially at low pressure. It should

Fig. 10 CO2 adsorption isotherms in MOF-177 and MOF-177–SO3H at 298 K with pressure up to 4000 kPa: (a) gravimetric adsorption
isotherms and (b) volumetric adsorption isotherms.

Fig. 11 Probability distribution plots of COM of CO2 in MOF-177 and MOF-177–SO3H (Zn, light blue spheres; C, gray spheres; H,
white spheres; O, red spheres; S, yellow spheres).
 Chenkai Gu et al. Effects of functional groups for CO2 capture using metal organic frameworks
be noted that the CO2 capture of MOFs will also be
affected by pore sizes or topologies when these functional
groups are introduced to other MOFs [63]. Our findings
may not apply to all of the MOFs since we only chose
MOF-177 as a parent material to compare the CO2 binding
energies of different functional groups.
4 Conclusions
Due to the functionalization effect, the atomic charge
distributions on the linker of MOF-177 were significantly
intensified according to LUMO analysis. Three different
intermolecular interactions were found between CO2
molecules and functional groups, including hydrogen
bond interaction, quadrupole-lonepair interaction and
induced dipolar interaction. It is beneficial to incorporate
groups containing lone pair electrons, acidic hydrogens or
halogen atoms to induce forming the interactions men-
tioned above to improve the CO2 affinity of linkers.
Moreover, a trend of adsorption ability at low pressure was
formed as following: –SO 3 H > –COOH > –NH 2 >
–OH > –CN > –F > –CH 3 . Among these functional
groups, the –SO3H group brought the strongest promotion
to CO2 adsorption, and was further studied. The CO2
adsorption capacity of MOF-177 at high pressure declines
as a result of decreasing total free volume after introducing
–SO3H group. However, it still shows a remarkable
improvement on CO2 capture at the pressure less than
1000 kPa, and thus has the potential to be a promising CO2
capture material in this pressure range.
Acknowledgements This work was supported by the National Natural
Science Foundation of China (Grant Nos. 51676079 and 21773104),
Fundamental Research Funds for the Central Universities (No. 2019kfyR-
CPY021) and China Scholarship Council (No. 201906160014).
Electronic Supplementary Material Supplementary material is available
in the online version of this article at https://doi.org/10.1007/s11705-020-
1961-6 and is accessible for authorized users.
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