Sustainable Materials and Technologies 32 (2022) e00383

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Sustainable Materials and Technologies

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Grand canonical Monte Carlo (GCMC) study on adsorption performance of

metal organic frameworks (MOFs) for carbon capture
Y.R. Tao a, b, G.H. Zhang b, H.J. Xu a, *
a
China-UK Low Carbon College, Shanghai Jiao Tong University, Shanghai 200240, China
b
School of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China

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

Keywords: Metal-Organic Frameworks (MOFs) have been proved to be promising materials for CO2 capture due to their high
Metal-organic frameworks specific surface area. In this work, molecular models of MOF-5, Mg-MOF-74, ZIF-8, CO2 and N2 were established.
Carbon capture Adsorption and separation behaviors of pure CO2 and CO2/N2 in the three MOFs were studied using Grand
Molecular simulation
Canonical Monte Carlo (GCMC) simulations. The simulated single component isotherms and corresponding
Adsorption
Separation
isosteric heat of adsorption implied underlying adsorption mechanisms of different MOFs. MOF-5 was found to
have the highest saturation adsorption capacity for pure CO2 (35 mmol/g) at room temperature while Mg-MOF-
74 has the highest CO2 uptake (11 mmol/g) under 10 bar. Meanwhile, the results also indicated that the exis­
tence of coordinated unsaturated metal sites enhanced the CO2 adsorption capacity of MOFs. In addition, their
selectivity to CO2 over that of N2 have also been studied. In the case of CO2/N2 adsorption and separation, Mg-
MOF-74 has the highest CO2 selectivity of 38 because of its strongest binding force with CO2. Moreover, in­
dustrial application potential of MOFs in swing adsorption processes for carbon capture and separation was
analyzed combining with their current prices. This work is beneficial to the selection of MOFs in post-combustion
CO2 capture.

captured and collected by a carbon capture device before it is discharged

1. Introduction
As the demand for fossil fuels continues to rise, the continuous in­
crease in carbon dioxide emissions has caused a sharp increase in the
concentration of carbon dioxide in the atmosphere. In addition to the
well-known melting of glaciers and a rise in global average annual
temperatures. In early 2021, many northern provinces of China suffered
the worst cold wave in recent years. According to the explanation of Dr.
Ding in the newspaper [1], the cold wave that hit China in 2021 was
precisely the result of global warming. On September 22, 2020, Xi
Jinping, the China president, stated at the 75th United Nations General
Assembly that China would strive to achieve “carbon peak” by 2030 and
“carbon neutrality” by 2060.
Carbon capture is a technology that separates and captures carbon
dioxide generated during combustion and other processes. It was first
used in the oil and gas industry to increase the production capacity of oil
and gas. In recent years, as the attention to climate issues continues to
increase, this technology has gradually been adopted by power gener­
ation and other industries to reduce their carbon dioxide emissions. In
Carbon Capture and Sequestration (CCS) technology, carbon dioxide is
into the atmosphere. After being compressed and stored as liquid carbon
dioxide, it is driven into the ground to reduce the concentration of
carbon dioxide in the atmosphere.
According to the sequence of carbon capture and combustion pro­
cesses, carbon capture technologies are mainly divided into three cate­
gories [2]: (a) pre-combustion capture (b) oxy-fuel combustion capture
(c) post-combustion capture. In the report [3] published by SINTEF, as
shown in Table 1, the readiness for application of post-combustion
capture were both promising was regarded as “High” and the develop­
ment potential was regarded as “Medium-High”, which means that this
method of carbon capture technique was viewed favorably in the
industry.
As one of important means to alleviate climate problems, carbon
capture technology has a huge demand for solid adsorbents that can
achieve efficient adsorption and separation of mixed gases. Various
materials for carbon capture have been investigated over the years. Two
types of CO2 adsorbents are now widely discussed [4]: chemical adsor­
bents and physical adsorbents. Currently, chemical adsorbents are used
more widely in industry due to its advanced development [5]. However,
this group of materials has the disadvantages of high toxicity, low

* Corresponding author.
E-mail address: xuhuijin@sjtu.edu.cn (H.J. Xu).

https://doi.org/10.1016/j.susmat.2021.e00383
Received 2 October 2021; Received in revised form 5 December 2021; Accepted 28 December 2021
Available online 31 December 2021
2214-9937/© 2021 Elsevier B.V. All rights reserved.
Y.R. Tao et al. Sustainable Materials and Technologies 32 (2022) e00383

Nomenclature U system energy, J

ui uptake of component i
H enthalpy, kJ Vfree free volume of adsorbent, m3
h Planck constant
kb Boltzmann constant Greek symbols
m mass, kg Λ thermal de Broglie wave length, m
N particle number, mol εij LJ well depth, J/mol
Nab absolute adsorbed amount, mol/g ε0 dielectric constant of vacuum
Nex excess adsorbed amount, mol/g σ ij LJ size, nm
pi partial pressure of component i μ chemical potential, J/mol
Q heat exchanged, kJ ρ density, g/m3
qi charge of atom i, C Subscripts
qst isosteric heat of adsorption, kJ/mol ad adsorbed phase
rij distance between particle i and particle j, nm b bulk phase
S adsorption selectivity i, j particle types
T temperature, K

2. Models and methods

Table 1
Development potential of main CO2 capture techniques [3]. 2.1. MOFs structures
Technology Readiness for application in Development potential (next
first generation CCS schemes generation schemes) In this work, the carbon capture behaviors of three MOF materials
(MOF-5, Mg-MOF-74, and ZIF-8) are discussed towards their potential
Coal Natural gas Coal Natural gas
application. Two prototypical high surface area MOFs have been chosen,
IRCC-CCS Medium- N/A High N/A namely MOF-5 and ZIF-8, as representatives of samples whose proper­
High
IGCC-CCS N/A High N/A Low
ties are greatly determined by their pore geometries and surface area. In
Oxy-combustion Medium- Low High Medium- addition, MOFs with coordinately unsaturated metal sites (CUMs) have
High High been recorded to offer an increased binding energy to other gases such as
Post- High High Medium- Medium- H2 and CH4, and Mg-MOF-74 are reported to have extremely high per­
combustion High High
formance in CO2/CH4 selectivity [17].
MOF-5, namely IRMOF-1, belongs to the IRMOFs series which is one
diffusivity and high viscosity, leading to lower adsorption capacity and of the earliest and most representative MOFs series synthesized. The
higher pressure drop [2]. Besides, carbon capture with chemical ad­ structure of MOF-5 was first reported on Nature in 1999 [18]. MOF-5 is a
sorbents is an energy intensive process [6], which makes them might not three-dimensional framework composed of Zn2+ as the central metal ion
be practically applicable for post-combustion carbon capture. Compared and terephthalic acid (H2BDC) as the organic ligand, as shown in Fig. 1
to typical procedure using chemical adsorbents, carbon capture by (a). It is connected in the form of octahedrons. Structural parameters of
physical process has the advantages of low regeneration energy con­ MOF-5 in Table 2 show that it has high specific surface area and large
sumption [4], non-corrosive and better stability [7]. Several researches porosity. Besides, it performs well on hydrogen storage [19] and thermal
have been conducted on porous materials because of their promising stability below 400 ◦ C [20]. This MOF material has always been con­
thermal performance [8,9]. As novel porous crystalline materials, MOFs cerned and discussed by scholars because of its high adsorption capacity
also have exhibited excellent performance in gas adsorption due to their and low cost. MOF-74, especially Mg-MOF-74 with Mg2+ as the central
extremely high specific surface area [10] and strong designability [11], metal ion in Fig. 1(b), is a typical MOFs with coordinately unsaturated
and become a global research hotspot. MOFs have presented remarkable metal sites. Comparing to other MOFs without CUMs, it shows signifi­
porosity and wide application such as gas separation, gas storage and cant advantage on gas separation [21]. A large number of studies have
catalysis. Over time, various MOFs have been synthesized aiming to shown that Mg-MOF-74 exhibits extremely high carbon dioxide
arrive at a suitable formulation for efficient capture of CO2. In this study, adsorption capacity and strong carbon capture potential under room
the adsorption behaviors of pure CO2 and CO2/N2 on three MOFs (MOF- temperature and pressure conditions [22–24], though its surface area
5, Mg-MOF-74, ZIF-8) that researchers often pay attention to were and pore volume shown in Table 2 are not exceptional. Zeolite imida­
investigated with Grand Canonical Monte Carlo simulation. zolate framework (ZIF) is one of the framework material series under
Many molecular simulation studies have been conducted to investi­ MOFs, usually composed of some divalent transition metal ions (Zn2+,
gate carbon capture properties in MOFs. GCMC simulations were widely Co2+, etc.) and aromatic organic imidazole esters, as shown in Fig. 1 (c).
employed to identify strategies in designing MOFs for hydrogen, 12 ZIF-n (n = 1,2..0.12) materials with silica-alumina molecular sieve
methane and carbon dioxide storage [12,13]. Several MOFs have per­ structure were first reported on PANS in 2006 [7]. Among ZIFs, ZIF-8
formed high uptakes [14,15] and selectivity of CO2 from the gas mixture has shown good thermal stability at 550 ◦ C. Compared with tradi­
[16]. However, most of these studies have focused on high-pressure CO2 tional adsorption materials such as activated carbon, ZIF has higher
storage and CO2 selectivity under a certain pressure, discussions on the carbon dioxide adsorption selectivity. Therefore, ZIF-8 is often used as a
CO2 adsorption behavior of several MOFs in PSA carbon capture process typical comparison object in various researches of carbon dioxide solid
have been lacking. adsorbents.
This paper selects three MOFs that researchers often pay attention to, Among the molecular models used in this study, the unit cell crystal
and uses GCMC simulation technology to study the carbon capture structures of MOFs were downloaded from the Cambridge Crystallo­
ability of MOF-5, Mg-MOF-74, and ZIF-8. The adsorption isotherms and graphic Data Center (CCDC) and modified. The molecular structures of
isosteric heat of adsorption on MOFs were obtained through simulations the adsorbate gases (carbon dioxide and nitrogen) were manually
to analyze their adsorption behaviors and mechanisms. constructed.

2
Y.R. Tao et al. Sustainable Materials and Technologies 32 (2022) e00383

Fig. 1. Crystal structures for MOFs under investigation: (a) MOF-5; (b) Mg-MOF-74; (c) ZIF-8. Color code: carbon (grey), hydrogen (white), oxygen (red), nitrogen
(blue) and magnesium (green).

Table 2 →′ ( { [ ( →′ ) ( )]})
r → r ) = min 1, exp − β U ( r )N − U (→
acc(→ r )N (2)
Structural parameters of MOFs under consideration.
Structure BET surface area Pore volume References
( )
V
(m2/g) (cm3/g) acc(N→N + 1) = min 1, exp{ − β[μ − U(N + 1) + U(N) ] }
Λ3 (N + 1)
MOF-5 3500 1.31 [17]
(3)
Mg-MOF-74 1332 0.61 [25]
ZIF-8 1980 0.65 [17] ( )
Λ3 N
acc(N→N − 1) = min 1, exp{ − β[μ + U(N − 1) − U(N) ] } (4)
V
2.2. Computational method
2.2.2. Force fields
2.2.1. The GCMC method When calculating the total potential energy of the system, since only
The molecular simulation method used in this paper is the Grand intermolecular interactions between unbound atoms, Van Der Waals
Canonical Monte Carlo method, which uses the grand canonical interactions and electrostatic interactions are involved in the calculation
ensemble to change the number of molecules in the simulation process of the total potential energy U of the system, the Lennard-Jones (LJ) +
to perform MC simulation calculations. Coulomb potentials were used to describe these interactions, as follows
The GCMC method was first proposed by Adams in 1975 [26]. In [28]:
addition to energy exchange between systems, this method can also [( ) ( )6 ]
exchange the number of particles. Therefore, it is mainly used in systems σ ij 12 σij qi qj
Uij = 4εij − + (5)
where the number of particles in the system changes with changes in rij rij 4πε0 rij
external conditions. The partition function for a system of N particles at √̅̅̅̅̅̅̅
In Eq. (5), εij = εi εj is the LJ well depth, σ ij = i 2 j is the LJ size, rij is
σ +σ
→r in volume V can be expressed as [27]:
∫ the distance between the particles, ε0 is the dielectric constant of vac­
∑∞
Ξ(μ, V, T) =
exp(βμN)V N [ (
r )N exp − βU (→
d(→ r )N
)]
(1) uum, qi and qj are the charges of atoms i and j, respectively.
In this work, the LJ parameters for all the MOFs atoms studied were
3N
N=0 Λ N!
assigned Based on the DREIDING force field [29] and the UFF force field
In Eq. (1), μ is chemical potential, T is temperature, β = kb1T where kb
√̅̅̅̅̅̅̅̅̅̅̅ [30]. The TraPPE force field [31] was chosen to describe the interactions
is the Boltzmann constant, Λ = 2πmk h2
is the thermal de Broglie wave between atoms in CO2 molecule. The LJ parameters and the charge of
bT

length where m is the mass of particles and h is the Planck constant, U is the N atom in N2 molecule were determined by the experiment of
Murthy [32]. The charge of each atom in MOFs was derived from DFT
the energy of the system.
Each GCMC move contains 3 kinds of trials: the random displace­ calculation [33].
ment of a randomly chosen atom, the insertion of a solute particle at a
2.2.3. Computational details
randomly selected position and the deletion of a randomly chosen atom.
GCMC method was used to simulate the isotherm adsorption process
The acceptable probabilities of displacement, insertion and deletion are
of pure CO2 and CO2/N2 mixture in MOF-5, Mg-MOF-74, and ZIF-8 at
as followed, respectively.
298 K.

3
Y.R. Tao et al.
During the simulation, a cutoff radius of 12.8 Å was applied to the LJ
potentials. The number of the unit cells of MOF-5, Mg-MOF-74 and ZIF-8
adopted in the simulation cell were 1 × 1 × 1, 2 × 2 × 4, 2 × 2 × 2,
respectively, to guarantee the simulation accuracy. The long-range
electrostatic interactions were processed by the Ewald & Group sum­
mation method, while the Van Der Waals interactions were handled
using the Atom based summation method. Periodic boundary conditions
were applied in all three directions. For each state point, 10 million steps
were used for both equilibration and production.
For pure CO2 adsorption, pressure range is set to 0.1 bar to 35 bar.
For CO2/N2 mixture, considering the pressure condition of carbon cap­
ture for practical combustion process, such as pressure swing adsorption
which is commonly used, the mixed gas pressure is set to 1– 6 bar. As­
sume that CO2 accounts for 20% of the mixed gas and N2 accounts for
80%. Therefore, the partial pressure range of CO2 gas is 0.2 bar to1.2
bar, and the partial pressure range of N2 gas is 0.8 bar to 4.8 bar.
Since the fugacity was used during simulation instead of pressure
during the calculation, the Peng-Robinson equation of state needed to be
used to convert between gas-phase pressure and fugacity before and
after the simulation. To achieve two-way conversion of pressure and
fugacity, the Peng-Robinson EoS function written by Serna [34] was
utilized.
Fig. 2. Force field verification for CO2 adsorption in (a) MOF-5, (b) Mg-MOF-74 and (c) ZIF-8 [1 mmol = 10−
4
Sustainable Materials and Technologies 32 (2022) e00383
3. Results and discussion
3.1. Pure CO2 adsorption
3.1.1. Force field effectiveness
After simulating the adsorption of the three MOFs, simulated
adsorption isotherms should be compared with experimentally
measured results to verify the applicability of the force field used to the
MOFs materials. The adsorption amount obtained by GCMC simulation
is absolute adsorbed amount (Nab) and the data obtained in experiment
is excess adsorbed amount (Nex). The relationship between them can be
written as
Nab = Nex + ρVfree (6)
In Eq. (6), ρ is the density of adsorbate gas, and Vfree is the free
volume of adsorbent.
To verify the applicability of models constructed, the excess simu­
lation amount was compared with experimentally measured amount of
MOF-5, Mg-MOF-74 [17] and ZIF-8 [35], as shown in Fig. 2.
For Mg-MOF-74, the simulation and the experimentally measured
CO2 adsorption amount are relatively consistent in the pressure range of
0.1 bar to 35 bar. For MOF-5 and ZIF-8, the simulation results are
consistent with the experimental data at 0.1 bar to 10 bar. Therefore, it
can be inferred that the potential energy model and force field param­
eters used are reliable to predict the adsorption of CO2 in MOFs within
3
mol].
Y.R. Tao et al.
the pressure range of 0.1 bar to 10 bar and the slight differences at low
pressure between the simulated and experimental results suggest that
impurities or defects were present in samples. When the pressure ex­
ceeds 10 bar, there exists a significant difference between the simulated
and experimental results for MOF-5 and ZIF-8 as the force field selected
cannot accurately describe the complete adsorption process of the MOF
materials at high pressure.
3.1.2. Adsorption isotherms
Fig. 3 presents adsorption isotherms for CO2 adsorption in MOFs at
298 K. For MOF-5 and ZIF-8, the simulation and the experimentally
measured CO2 adsorption amount are different when the pressure ex­
ceeds 10 bar. However, they are still worth analyzing since the shapes of
their isotherms are similar.
Referring to the classification of solid-gas adsorption isotherms [36],
as shown in Fig. 4, the adsorption isotherm of MOF-5 belongs to the rare
type V adsorption isotherm which is also known as S-shape isotherm.
Type III and type V adsorption isotherms often appear when adsorbent-
adsorbate attraction is smaller than adsorbate-adsorbate attraction.
However, type III isotherm appears more often in multi-molecule
adsorption on hydrophobic surfaces, such as water vapor adsorption
on graphite surfaces or hydrophobic non-porous metal oxides. Type V is
more observed in the adsorption of porous solids, such as the adsorption
of water vapor on activated carbon or hydrophobic silica gel. Walton
proposed an understanding of this adsorption behavior [37], that is,
under the action of the electrostatic force between CO2 gas molecules,
the accumulation of CO2 in the MOF-5 pores may lead to a decrease in
the growth rate of adsorption capacity in the later stage of adsorption.
Also, the ZIF-8 isotherm can be found to have a similar but less pro­
nounced S-shape, which means ZIF-8 possesses a similar CO2 adsorption
mechanism.
The adsorption isotherm of Mg-MOF-74 belongs to type I isotherm
which is more common. Type I isotherms can be divided into two types:
I-A and I–B [38]. Type I-A and Type I–B own the same shape of
isotherm curves while the adsorption mechanisms hidden behind are
different. Type I-A occurs in the case of monolayer adsorption when
adsorbent-adsorbate attraction is much greater than adsorbate-
adsorbate attraction. And the single molecule adsorption [39] occurs,
so it is also called Langmuir type adsorption isotherm. Type I–B often
occurs in solid materials with ultra-microporous and ultra-microporous.
Since the outer surface area is much lower than the inner surface area of
the pores, the adsorption in the micropores occurs when the pressure is
low, which causes the adsorption curve to rise rapidly. When the pres­
sure is higher, the adsorption on the outer surface then occurs, and the
Fig. 3. Adsorption isotherms for CO2 adsorption in MOFs at 298 K.
5
Sustainable Materials and Technologies 32 (2022) e00383
adsorption curve tends to be flat. Therefore, the adsorption mechanism
of Mg-MOF-74 belongs to type I–B as MOFs are new porous materials.
Fig. 5 shows that the saturation uptake of pure CO2 gas in MOF-5 is
much higher than that of Mg-MOF-74 and ZIF-8. This also confirms the
conclusion that the saturation uptake for each material correlates
reasonably well with the specific surface area and pore volume at high
pressure [17]. However, the presence of coordinated unsaturated metal
sites in MOFs will bring higher adsorbate density and consequently
higher saturation uptake. Therefore, MOFs with CUMs structure such as
Mg-MOF-74 have relative higher saturation uptake.
Although the saturation capacity of MOF-5 (35 mmol/g) at room
temperature is relatively high, the specific curvature in its isotherm
makes this material less applicable to low pressure adsorption in gen­
eral. Only when the pressure is higher than 10 bar, the adsorption ca­
pacity of MOF-5 for CO2 will gradually show its advantages.
At low pressure, Mg-MOF-74 with coordinated unsaturated metal
sites (or open metal sites) exhibits significantly stronger adsorption ca­
pacity (11 mmol/g). The underlying mechanism can be understood in
conjunction with the isosteric heat of adsorption.
3.1.3. Isosteric heat of adsorption
The isosteric heat of adsorption (qst) is defined as the difference be­
tween the partial molar enthalpies of the adsorbed and bulk phases [40],
or the heat generated when a single adsorbate molecule transforms from
the bulk gas phase to the adsorption phase at a constant temperature.
The calculation expression is as follows [28]:
( ) ( ) ( )
Q ∂Hb ∂Had
qst = = − (7)
∂Nad T,p ∂Nb T,p ∂Nad T,p
In Eq. (7), Q is the heat exchanged, N is the particle number, and H is
the enthalpy.
After the gas changes from a higher-energy gaseous state to a lower-
energy adsorption state, the reduced energy will be released into the
environment in the form of heat. Therefore, the stronger the adsorbent-
adsorbate attraction and the adsorbate-adsorbate attraction, the lower
the energy of the adsorbate molecules in the adsorbed state, and the
higher the heat of adsorption released. Based on the understanding
above, the mechanism of CO2 adsorption in each MOF material can be
further analyzed with the help of isosteric adsorption heat curves.
Fig. 6 shows that Mg-MOF-74 has a significantly higher isosteric heat
of adsorption, while MOF-5, which has a higher saturation capacity,
shows a smaller isosteric heat of adsorption under the same adsorption
capacity. This difference supports the point stated in the previous sec­
tion, that is, Mg-MOF-74 with CUMs structure exhibits extremely strong
adsorption capacity at low pressure.
Experimental studies from other research groups have shown that
MOFs with open metal sites (PCN-11, PCN-16, HKUST-1, Mg-MOF-74)
will exhibit significantly higher isosteric heat of adsorption and stron­
ger adsorption capacity at low pressure comparing to MOFs with satu­
rated coordination (MOF-5, ZIF-8) [17,25]. That’s why the pressure
required to reach the same adsorption capacity of Mg-MOF-74 is smaller
than those of MOF-5 and ZIF-8. This also verifies the rising law of the
adsorption isotherms of the three MOF materials in the previous section
from another angle.
In addition, although the change in the value of isosteric heat of
adsorption of Mg-MOF-74 in this simulation is relatively insignificant, a
similar phenomenon to the Simmons experiment can still be observed
through careful observation, that is, the isosteric heat of adsorption
values of Mg-MOF-74 shows a process of falling first and then rising (as
shown in Fig. 7). At low pressure, the adsorption of CO2 in Mg-MOF-74 is
dominated by the solid-gas (adsorbent-adsorbent) interactions. As the
adsorption capacity continues to rise, adsorption sites with strong
binding force, namely CUMs, are gradually filled, then the adsorbate gas
molecules can only be adsorbed on secondary adsorption sites with
weaker remaining binding force, resulting in the gradual decrease of the
Y.R. Tao et al.
Fig. 4. Five types of van der Waals adsorption isotherms [36].
Fig. 5. Relation between saturation uptake of MOFs and their structural parameters: (a) specific surface area, and (b) pore volume.
adsorption heat of the material in the initial stage of adsorption. When
the adsorption capacity of Mg-MOF-74 reaches a certain level (approx­
imately 5 mmol/g), as the density of the adsorbate in the pores in­
creases, gas-gas (adsorbate-adsorbate) interactions start to dominate the
adsorption process, and the isosteric heat of adsorption begins to rise
gradually at the same time. However, MOFs with coordination satura­
tion such as MOF-5 and ZIF-8 have a monotonically increasing adsorp­
tion heat curve, which shows that for coordination saturation MOFs, the
solid-gas binding force of CO2-MOF is much smaller than that of CO2-
CO2. The gas-gas binding force is so high that the latter dominates the
adsorption at low pressure. This is also mutually confirmed with the
adsorption mechanism behind the type V adsorption isotherm to which
MOF-5 and ZIF-8 belong in the previous section.
3.2. CO2/N2 mixture adsorption
3.2.1. Force field effectiveness
In the previous part, it has been verified that the potential energy
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Sustainable Materials and Technologies 32 (2022) e00383
model and force field parameters of MOF-5, Mg-MOF-74, ZIF-8, and CO2
used can simulate the adsorption of carbon dioxide well in the pressure
range of 0.1 bar to 10 bar. Since this part introduces a new molecular
model: the molecular model of N2, force field verification is needed to
test the applicability of this new model. Adsorptions of pure N2 in MOF-
5, Mg-MOF-74, ZIF-8 at 0.8 bar to 4.8 bar were separately simulated.
After converting the data of the absolute adsorption amount of N2
obtained by the simulation into the excess adsorption amount, it was
compared with other scholars’ experimentally measured amount
[35,41,42]. Results are shown in Fig. 8.
For MOF-5, the difference between the adsorption amount obtained
by simulation and experiment is about 20%, so the N2 force field pa­
rameters used has strong reliability in the adsorption of N2 in MOF-5.
For Mg-MOF-74, the adsorption amount data obtained by simulation
is quite different from the experimental data in the reference. Therefore,
the N2 force field parameter used is the adsorption of N2 in Mg-MOF-74
at a pressure of 0.8 bar to 4.8 bar. The simulation reliability here is poor,
and the numerical value of the simulation result itself has no reference
Y.R. Tao et al.
Fig. 6. Isosteric heat of adsorption for CO2 adsorption in MOFs at 298 K [1 kJ
= 103 J].
Fig. 7. Isosteric heat of adsorption for CO2 in Mg-MOF-74.
value. For ZIF-8, there is a certain error between the adsorption amount
obtained by simulation and the experimental data in the reference.
Therefore, the N2 force field parameters used have moderate reliability
in the adsorption of N2 in ZIF-8. The value of the simulation result itself
has a certain reference value.
3.2.2. Adsorption isotherms
The isotherm of MOF-5 (as shown in Fig. 9) implies that MOF-5 show
slight difference in the adsorption capacity of CO2 and N2 in the mixed
gas, that is, the adsorption selectivity of MOF-5 to CO2/N2 is poor. So, it
can be preliminarily inferred that this material is not suitable for carbon
capture of flue gas after combustion in the pressure range of 1 bar to 6
bar.
Mg-MOF-74 exhibits excellent CO2 adsorption capacity and CO2/N2
adsorption selectivity for mixed gases at the same pressure. It is unde­
niable that the Mg-MOF-74 molecular model used in this simulation
shows a big difference in the adsorption of N2 from the experimental
data. However, compared with the extremely high CO2 adsorption ca­
pacity of Mg-MOF-74 in the pressure range of 1 to 6 bar, this difference
can be compensated to a certain extent. Therefore, it can be inferred that
Mg-MOF-74 has considerable carbon capture potential in the pressure
range of 1 bar to 6 bar.
7
Sustainable Materials and Technologies 32 (2022) e00383
The performance of ZIF-8 is slightly moderate compared to the above
two MOFs materials. The potential of this material in carbon capture
needs further analysis.
3.2.3. Adsorption selectivity
In the process of gas separation of mixed gases, the adsorption
selectivity S is one of the important parameters for evaluating the gas
separation performance of porous materials. For binary gas mixtures,
the selectivity of component 1 to component 2 is defined as [23]:
u1 /u2
S= (8)
p1 /p2
In Eq. (8), ui is the uptake and pi is the partial pressure of component
i.
Therefore, if the adsorption selectivity is greater than 1, it means that
component 1 is more easily adsorbed by the porous material. The higher
the value of S, the stronger the adsorption and separation performance
of the porous material for mixed gas.
Since the adsorption selectivity coefficient S are all greater than 1, as
shown in Fig. 10, CO2 exhibits a stronger interaction force than N2 in the
three MOF materials studied, making CO2 more preferentially adsorbed
in the adsorption sites of MOF materials. Furthermore, Fig. 10 shows
that the adsorption selectivity of Mg-MOF-74 is the most prominent, ZIF-
8 is in the middle, and MOF-5 is inferior. This indicates that the LJ well
of CO2 binding sites in Mg-MOF-74 is deeper than other materials, but its
size is relatively small, resulting in a decrease in selectivity. However,
the adsorption selectivity of MOF-5 and ZIF-8 is low, indicating that the
LJ well of CO2 binding sites in these two MOF materials is relatively
shallow. The adsorption selectivity gradually increases with the increase
of pressure, indicating that MOF-5 and ZIF-8 have larger LJ well size.
3.2.4. Isosteric heat of adsorption
Based on the previous analysis, it can be known that the heat of
adsorption can be used to investigate the magnitude of the adsorbate-
adsorbent or adsorbate-adsorbent interaction. The stronger the
adsorbent-adsorbate interaction and the adsorbate-adsorbate interac­
tion, the lower the energy of the adsorbate molecules in the adsorbed
state, and the higher the heat of adsorption released. For a two-
component mixed gas, the greater the difference in the isosteric heat
of adsorption of CO2 and N2 in a certain MOF material, the greater the
difference in the binding effect of different gas molecules in the
adsorption process, and the better the gas adsorption and separation
effect. Therefore, analyzing the difference of the isosteric heat of
adsorption of CO2 and N2 in the same MOFs material can help us to
further analyze the gas selectivity of this MOF material.
The isosteric heat of adsorption of the three MOF materials change
little under 1 to 6 bar (lower than 7%) (as shown in Fig. 11), so calculate
their average values and compare their relative difference to get the
adsorption selectivity of different MOF materials to the CO2/N2 mixture,
as shown in Fig. 11.
The order of the difference in the isosteric heat of adsorption be­
tween CO2 and N2 is: Mg-MOF-74 > MOF-5 > ZIF-8. This conclusion is
similar to the previous one. On the other hand, the isosteric heat of
adsorption for both adsorbates (CO2 and N2) on MOFs shows similar
order of Mg-MOF-74 > ZIF-8 > MOF-5, which matches well with the
adsorption amount under low pressure, as shown in Fig. 3.
3.3. Application potential on PSA and VSA
In the actual application process, the material performance and its
cost need to be weighed. According to the MOFs Sigma-Aldrich Trading
Company, the prices of the three MOFs studied are shown in Table 3.
Based on the price inquired, it can be found that the price of Mg-MOF-
74, which has strong adsorption capacity at low pressure, is much
higher than that of MOF-5 and ZIF-8 discovered earlier. In addition, the
small packaging size of Mg-MOF-74 reflects that this MOFs material is
Y.R. Tao et al. Sustainable Materials and Technologies 32 (2022) e00383

Fig. 8. Force field verification for CO2/N2 mixture adsorption in (a) MOF-5, (b) Mg-MOF-74, and (c) ZIF-8.

still in a small research stage and has not yet reached the level of in­
dustrial application.
Pressure swing adsorption (PSA) usually adsorbs at an inlet pressure
close to 6 bar and desorbs at an outlet pressure of 1 bar [43]. Therefore,
the difference between the CO2 adsorption capacity of MOFs at 1 bar and
6 bar can be regarded as the amount of CO2 captured during the PSA
process. The principle of vacuum swing adsorption (VSA) is similar to
that of pressure swing adsorption (PSA). It usually adsorbs at an inlet
pressure of about 1.5 bar and desorbs at an outlet pressure of 0.05 bar.
Therefore, the difference between the CO2 adsorption capacity of MOFs
at 0.05 bar and 1.5 bar can be regarded as the amount of CO2 captured
during the VSA process. The specific capacities calculated of the MOFs
studied are presented in Table 4. Besides presenting data for the carbon
capture efficiencies based on the adsorption simulation of pure CO2 gas,
Table 4 also exhibits the capture capacities assuming a 20% partial
pressure of CO2 in hypothetical flue gas.
Among the MOFs studied here, Mg-MOF-74 shows the highest
theoretical CO2 capture capacity under all conditions, However,
considering the simulation error of Mg-MOF-74 at low pressure and its
current high price, the industrial application potential of this MOF
Fig. 9. Adsorption isotherms for CO2/N2 adsorption in MOFs at 298 K.
material needs to be further considered. Comparing MOF-5 and ZIF-8
whose prices are relatively cheap, it is found that MOF-5 exhibits
strong CO2 adsorption efficiencies under pure-CO2 PSA conditions and
its performance under CO2/N2 PSA conditions is also better than ZIF-8.

8
Y.R. Tao et al. Sustainable Materials and Technologies 32 (2022) e00383

Fig. 10. Adsorption selectivity towards CO2/N2 in (a) MOF-5, (b) Mg-MOF-74 and (c) ZIF-8.

Table 3
The price of MOFs (on the website of Sigma-Aldrich).
Structure Pack size (g) Price (CNY) Minimum unit price (CNY/g)

MOF-5 5 327.54 0.009618

100 395.78
500 438.09
Mg-MOF-74 5 1795.89 247.9836
25 6199.59
ZIF-8 100 332.02 1.8883
500 944.16

Table 4
Swing adsorption capacities.
Structure PSA VSA

Pure CO2 CO2/N2 Pure CO2 CO2/N2

(mmol/g) (mmol/g) (mmol/g) (mmol/g)

MOF-5 4.74 1.13 1.22 0.32

Mg-MOF-74 5.48 4.16 5.89 2.01
Fig. 11. Isosteric heat of adsorption for CO2/N2 adsorption in MOFs at 298 K. ZIF-8 3.62 1.04 1.66 0.32

9
Y.R. Tao et al.
Therefore, MOF-5 has more application prospects in a PSA process
compared to ZIF-8.
4. Conclusions
In this work, molecular models of CO2, and N2 are constructed and a
computational study is performed to figure out application potential of
MOFs for carbon capture at room temperature. The main conclusions are
drawn as follows:
(1) The saturation capacity of CO2 in MOF-5 is much higher than that
of Mg-MOF-74 and ZIF-8 due to its big specific surface area and
high pore volume, while this MOF material requires pressure
higher than 35 bar to reach adsorption saturation. Therefore,
MOF-5 is more suitable for CO2 storage under high pressure
rather than gas adsorption and separation under low pressure.
(2) Mg-MOF-74 presents an excellent performance on CO2 adsorp­
tion under 10 bar. Its underlying mechanisms are further studied
and it is concluded that the presence of CUMs in Mg-MOF-74 can
strengthen the binding effect of MOFs on CO2, leading to faster
growth rate of adsorption capacity and higher isosteric heat of
adsorption.
(3) In the case of CO2/N2 separation at low pressure, it has also been
shown that Mg-MOF-74 has strongest adsorption selectivity of
CO2 from CO2/N2 mixture, followed by ZIF-8 and MOF-5.
Therefore, Mg-MOF-74 has the potential to be used in CO2 sep­
aration work.
(4) CO2 uptakes of these MOFs are calculated and compared under
PSA and VSA conditions. The results have shown that Mg-MOF-
74 performed best despite its current high price, while the low
cost of MOF-5 makes it possible to be directly used in industries
even its adsorption selectivity is inferior than that of Mg-MOF-74.
This work utilized GCMC simulations as an effective tool to study the
adsorption and separation behaviors of CO2 in MOFs, which can further
guide experimental studies on carbon capture and numerical in­
vestigations on other gases.
Author statement
Y.R. Tao and H.J. Xu led the writing of the paper. Y.R. Tao, G.H.
Zhang and H.J. Xu conducted the data analyses. The first version was
drafted by Y.R. Tao, G.H. Zhang and H.J. Xu. All authors contributed to
the writing and revisions of this paper.
Declaration of Competing Interest
None.
Acknowledgement
This work is supported by National Natural Science Foundation of
China (51876118).
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