Chinese Journal of Chemical Engineering, 19(5) 709=716 (2011)

Computer Simulation of Adsorption and Separation of CO

2
/CH
4
in
Modified COF-102
*
ZHU Yujun(), ZHOU Jianhai (},), HU Jun (@=), LIU Honglai (,)
**
and
HU Ying (@,)
The State Key Laboratory of Chemical Engineering and Department of Chemistry, East China University of Sci-
ence and Technology, Shanghai 200237, China
Abstract Covalent orgunic framework (COF) is a porous material with low density and 'arge BET (Brun-
auer-Emmett-Teller) surface area. They have great potential in gas adsorption and separation. In this work, the ad-
sorption of pure CO
2
and CO
2
/CH
4
mixture on modified COF-102 was simulated by using GCMC (grand canonical
Monte Carlo). Metal Li was incorporated into COF-102 through three doping methods, including charge exchange,
O

-Li
+
dipolar interaction and O

-Li
+
chemical bonding. The influence of Li doping on the adsorption of CO
2
was
studied. The results showed that among the three methods, the dipole doping is the best way to improve CO
2
ad-
sorption performance. Further, the ligands of COF-102 were replaced by extended aromatic moieties, such as di-
phenyl and pyrene. The adsorption capacity of CO
2
and CH
4
, and the selectivity of CO
2
/CH
4
on the ligand-replaced
COF-102 were studied. The capacity of CO
2
and CH
4
on the ligand-replaced COF-102 had obvious changes; hence
the selectivity of CO
2
/CH
4
can be adjusted accordingly.
Keywords gas adsorption, computer simulation, COF-102, Li doping, ligand replacing
1 INTRODUCTION
Meteorological changes caused by emission of
green house gases have been receiving significant at-
tention. To maintain the normal climate, the CO
2
con-
centration should be below 450 ulL
1
[1]. However, it
is likely that the world will continue to rely on fossil
fuels as the primary energy supply for a long period.
CO
2
capture, usage and storage (CCUS) is potentially
an effective way to reduce CO
2
emissions. Extensive
studies have been carried out worldwide on developing
cost-effective techniques to capture CO
2
, among them
the adsorption is one of the most promising methods.
The commercial molecular sieves, such as zeo-
lite 13X, 5A, and active carbons, possess high adsorp-
tion quantity, but their tolerance to the moisture is low
[2]. A lot of novel adsorbents such as metal organic
frameworks (MOFs), zeolitic imidazolate frameworks
(ZIFs) and covalent organic frameworks (COFs) have
been designed and fabricated. With the high BET sur-
face area, controllable pore structure and pore volume,
most of them have showed good performance as the
candidates for CO
2
adsorption, especially at high
pressure [3]. In recent years, Yaghi and his group made
outstanding achievements in fabrication these novel
materials [4]. For two- and three-dimensional COFs
materials, they derived a linear relation between pore
capacity and adsorption quantity [5]. Meanwhile, the
simulation work of CO
2
adsorption on MOFs and
COFs also achieved great progresses. Yang et al. [6]
systematically summarized the computer simulation in
metal organic frameworks in a recent review. Keskin
et al. [7] also gave a review on the adsorption and
separation properties of MOFs.
Metal doping is a convenient way to enhance the
gas adsorption quantity and selectivity. Mulfort et al.
[8] prepared the three dimensional MOF with metals
of Li, Na and K doped and found that the adsorption
quantities of H
2
and N
2
have an obvious increase.
Nouar et al. [9] also found that after Li and Mg ions
exchange, the adsorption quantity of H
2
on metal-ZIFs
is increased. Based on the phenomena of metal ions
existed as hydrates inside the framework, they con-
cluded that the promotion of the framework electro-
static potential is responsible for the adsorption quan-
tity increase. The simulation work can reveal more
clearly the mechanism of the gas adsorption in
metal-doped MOF and COF. Babarao and Jiang [10]
investigated how the ZIF doped with Na
+
influences
the adsorption and separation of CO
2
/H
2
, CO
2
/CH
4
and CO
2
/N
2
in comparison with the result before dop-
ing, in which the selectivity is raised after doping. Xu
et al. [11] inserted lithium atoms into MOF-5 frame-
work through chemical bonding, also detected a great
enhancement of selectivity of CO
2
due to the electro-
static potential provided by the metal atom inside the
framework. Cao et al. [12] studied H
2
adsorption in a
three dimensional COF through Li doping, surpassing
the criterion of hydrogen storage in 2010 proposed by
DOE (department of energy) (6%, by mass) for the
doped COF. Klontzas et al. [13] analyzed the adsorp-
tion quantity of H
2
on the COF-105 doped with lith-
ium, and also found an improvement beyond the crite-
rion of DOE target in 2010. There are so many re-
searches on the metal doping in MOFs and COFs that
a comparison for them will be extremely demanded,
Received 2011-06-10, accepted 2011-07-22.
* Supported by the National Natural Science Foundation of China (20736002), the National High Technology Research and
Development Program of China (2008AA062302) and Program for Changjiang Scholars and Innovative Research Team in
University of China (IRT0721).
** To whom correspondence should be addressed. E-mail: hlliu@ecust.edu.cn
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 710
which can provide meaningful information for deep
understanding and optimization of the metal doping.
Besides the metal doping, ligand replacing is also
considered as an effective way to promote the proper-
ties of framework materials. The main factors affect-
ing the ability of storing hydrogen in the case of phy-
sisorption are surface area, pore volume, and enthalpy
of adsorption. These factors can be improved by ex-
tended aromaticity, unsaturated metal sites, and point
charges in the framework of the proposed materials.
With different ligands, IRMOF (isoreticular metal
organic framework) series [4] are the most famous
MOFs. Meanwhile, ZIF series [14] with different cage
frameworks are obtained by ligand replacing. Klont-
zas et al. [15] simulated H
2
adsorption capacity in
COF-102s with ligand replacing by different
multi-phenyl group compounds, and the adsorption
quantity of H
2
overtakes 25% (by mass) at 77 K.
In this work, we study the CO
2
adsorption per-
formance of the modified 3-D framework material
COF-102 by metal doping and ligand replacing.
COF-102 is a framework with a composition of car-
bon, oxygen and boron atoms based on triangular and
tetrahedral nodes formed by these atoms. We first es-
tablish and optimize the models of the 3-D COF-102s
framework structure. Metal Li is doped in three dif-
ferent ways, charge exchange, dipolar interaction and
chemical bonding. Besides, ligand of phenylene moie-
ties is replaced by extended aromatic moieties includ-
ing diphenyl and pyrene. The adsorption behavior of
mixture of CO
2
and CH
4
on these model materials is
then simulated. Based on the results, we will propose
some general rules to optimize the modification of
framework type materials for the gas adsorption ap-
plications.
2 MODEL AND METHODOLOGY
In the simulation process for adsorption on COFs,
the interactions between adsorbate and adsorbent, as
well as adsorbates themselves are described by the
combinations of Lennard-Jones (LJ) potential and
Coulombic potential:
1/ 2 6
0
( ) 4
4
ij
i
j
q q
u r
r r r
o| o| o |
o|
o o| o|
|
o o
c
c o|
e
e
(
| | | |
( = +
`
| |
t
(

\ . \ . )

where
0
= 8.854210
12
C
2
N
1
m
2
is the vacuum
diffusivity;

and

are the depth and length of the

potential, respectively. The inner quadrupolar moment
of CO
2
can be characterized by endowing carbon and
oxygen atoms with different charges of 0.576e and
0.288e, respectively, and the bond length of C O is
1.18A. The TraPPE force field [16] is used to depict
these atoms. The universal force field (UFF) [17] with
geometrical combinational rule of
ij i j
o o o = and
ij i j
c c c = is adopted for the LJ interaction between
framework and adsorbates. United atoms of TraPPE
force field [18] can be employed to picture the force field
of CH
4
. As shown in Fig. 1, the structures of COF-102
and COF-108 built from cif files are downloaded from
CCDC database through Material Studio 4.3 [19].
Figure 1 Unit cells of COF-102
Key: grey, carbon; black, oxygen; white, hydrogen; light grey,
boron
Table 1 The force field constants and charges
used to describe adsorbates
/nm (/k
B
)/K q
CH
4
0.373 148.0 0
C(in CO
2
) 0.280 27 +0.576e
O(in CO
2
) 0.305 79 0.288e
The uncountable amounts of the atoms in the
framework of COF make it difficult to adopt the first
principle to do the precise calculation. In order to ob-
tain the data of atomic charge in the framework, the
cluster model is usually used to calculate the probable
charge distribution of the whole structure. Here, we
adopted Dmol
3
module of the cluster model to calcu-
late the ESP (electrostatic scalar potential) charge by
using GGA (general gradient appoximation) and PBE
(Perdew-Burke-Ernzerh) functions, with DNP (double
numerical plus polarization) basis and a cutoff radius
of 0.55nm.
Grand canonical Monte Carlo (GCMC) method
is used to simulate the gas adsorption in the modified
three-dimensional COFs. Ewald method is adopted to
calculate the sum of electrostatic interaction between
different atoms in the framework, in which, the cutoff
radius is 1.28 nm and the computational precision is
0.001 kcalmol
1
. The total simulation steps are 210
7
,
and the first 110
7
steps are for making the system in
equilibrium, while the remaining is used for obtaining
different thermodynamic properties. The selectivity of
gas A to gas B in a mixture is defined as S =
(x
A
/x
B
)(y
B
/y
A
), where x
A
and x
B
are the molar fractions
of A and B in the adsorptive phase, respectively, y
A
and y
B
are the corresponding molar fractions in the
bulk adsorbate phase. Similar simulations are also
held for the unmodified COFs to ascertain the effec-
tiveness of the proposed modifications to enhance gas
adsorption.
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 711
3 RESULTS AND DISCUSSION
3.1 COF-102 doped with Li ions
The classical simulation method of the metal
doping is by introducing the metallic atoms into the
framework of porous materials, then by exchanging
charges between the metallic atoms and the frame-
work atoms to maintain the neutrality of the whole
structure. It is easy to understand and operate for the
computer simulation, but for realistic synthesis, it is
very hard and almost impossible. Mavrandonakis et al.
[20] reported a novel methodology by introducing nega-
tive charge groups, such as
1
3
SO

, in the ligands,
then metallic cations can be reasonably doped into the
framework to keep the neutrality of the whole structure.
Due to the large size of the COF-102 cell, as
shown in Fig. 1, the model system must be reduced in
size. The reduction can be achieved reasonably by
treating the organic ligand as an individual system. Li
is doped into the organic ligand cluster model in three
different ways for comparison.
3.1.1 Charge exchange doping
Figure 2 shows the cluster model by the simple
charge exchange doping denoted as Li-COF-102-
exchange. The charge balance between ligand and Li
atom mainly depends on the charge exchange. The
simulation result shows that the exchangeable charge
between Li and the framework is 0.628e. In Fig. 2,
charges of each atom in Li-COF-102-exchange cluster
model by the charge exchange doping are marked.
Figure 2 ESP charges of each atom in Li-COF-102-
exchange cluster model by the charge exchange doping
Key: grey, carbon; black, oxygen; white, hydrogen; light grey,
boron; lithium is inside the 6C ring with the charge of 0.628
3.1.2 O

-Li
+
dipolar interaction doping
When a hydrogen atom of the ligand of COF-102
is replaced by a negative oxygen ion, the framework
possesses negative charges. Thus a certain amount of
lithium cations can be doped into the framework to
counterpoise the negative charges of the whole struc-
ture, and the neutrality is kept. The cluster model by
this kind of O-Li
+
dipolar interaction doping as shown
in Fig. 3 is denoted as Li-COF-102-dipole.
Through the dipolar interactions between Li
cations and the framework [20], Li doping provides
more active sites in the framework, and consequently
increases the adsorption ability. Because the negative
charges of the framework come from the introduction
of negative oxygen ions, the exchange charge between
Li and the framework is small enough to be ignored,
and the charge of Li cations is still considered as +1.
3.1.3 O

-Li
+
chemical bonding doping
Not only dipolar interactions occur between Li
cations and the negative charged framework, but also
the chemical bonding can form between O

and Li
+
when a hydrogen atom of the ligand of COF-102 is
replaced by a negative oxygen ion. As shown in Fig. 4,
the O

-Li
+
chemical bonding in the framework can be
simulated as one hydrogen atom of the ligand of
COF-102 replaced by an O

-Li
+
group, and the neu-
trality of the whole structure still remains. Because Li
cations now are joined into the whole framework
structure, the charge of Li cations would not be +1 any
more. After the optimized calculation for the charge
distribution by Dmol3, the charge of lithium cations is
turned out to be 0.790. We denote this kind of
COF-102 as Li -COF-102-bond.
Figure 4 ESP charges of each atom in Li-COF-102-bond
cluster model by the O-Li
+
chemical bonding doping
Key: grey, carbon; black, oxygen; white, hydrogen; light grey,
boron; lithium is linked by an oxygen black ball with the
charge of 0.790
The unit cell of three kinds of Li doped COF-102s
is shown in Fig. 5. All the three framework structures
of Li-COF-102s are the same except the different
doped positions of Li atoms or cations. However, the
Figure 3 ESP charges of each atom in Li-COF-102-dipole
cluster model by the O-Li
+
dipolar interaction doping
Key: grey, carbon; black, oxygen; white, hydrogen; light grey,
boron; lithium is the ball beside COF-102 with the charge of
1.00
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 712
effects of Li doping on the adsorption capacity of CO
2
by three different ways are quite different. As shown
in Fig. 6, compared with the original COF-102, the
adsorption capacity of CO
2
on all the three Li doped
COF-102s increase obviously. Among them, the doping
method through dipolar doping and bonding doping
are notably better than others, while the former is the
best when the pressure is less than 100 kPa as shown
in the insert diagram. As pressure increases, the adsorp-
tion capacities of CO
2
on Li doped COF-102s through
dipolar doping and chemical bonding doping ways are
similar, much higher than that through charge ex-
change doping. When the pressure is as high as 1000
kPa, three curves tend to merge with each other.
To understand the adsorption mechanism, the ad-
sorption process can be divided into two stages with
different control parameters: solid-fluid interactions
and fluid-fluid interactions [21]. At low pressure, the
interaction between the positive charged Li cations
and the negative charged O of the quadrupolar CO
2
is
the dominant effect on the adsorption capacity en-
hancement; whereas at high pressure with the density
of CO
2
increasing, the interaction between CO
2
mole-
cules and the free volume of framework turn to be
controller.
For the dipolar interaction doping method, the
introduction of the negative oxygen ions into the
framework make less charge exchange between Li
cations and the framework, and Li cations with the
positive charge of about +1 become the most active
sites among three different Li-COF-102s. Conse-
quently, at low pressure, the strong interaction be-
tween the quadrupolar CO
2
and Li-COF-102-dipole
yields higher adsorption capacity. On the contrary, for
the charge exchange doping method, the charge of Li
atoms and the number of Li atoms in a unit cell are the
lowest among three different Li-COF-102s. With the
weakest interaction between Li atoms and CO
2
mole-
cules, the adsorption capacity of Li-COF-102-exchange
is obviously low. For the sample of Li-COF-102-bond,
the doping method reduces the charge of active Li
sites more or less, and the moderate interaction weak-
ens the CO
2
adsorption capacity a little bit.
Since the volume of Li atom or cation is so small,

(a) (b) (c)
Figure 5 Unit cells of Li-COF-102-exchange (a), Li-COF-102-dipole (b), and Li-COF-102-bond (c)
Figure 6 Adsorption capacity of CO
2
on three kinds of metal doping Li-COF-102s in comparison with the original COF-102
the insert: the low pressure behavior
M Li-COF-102-exchange; & Li-COF-102-bond; Li-COF-102-dipole; * COF-102
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 713
no matter which ways is adopted, the free volume of
unit cell does not change so much. At high pressure, the
adsorption capacity depends much on the free volume
of the COF-102, hence, the enhancement caused by all
three kinds of doping methods tends to be the same.
3.2 The replacement of ligands of COF-102
Extending aromaticity is another way to enhance
the surface area and pore volume of the framework
structure materials. We substitute the phenylene moie-
ties of COF-102 by other extended aromatic moieties
such as diphenyl and pyrene molecules without
changing the net topology, as shown in Fig. 7. The
corresponding COF-102s after replacement is denoted
as di-COF-102 and py-COF-102.
The optimized structures of di-COF-102 and
py-COF-102 are presented in Fig. 8. The properties of
the crystal cells are listed in Table 2. Besides, the cells
are simplified to the cluster models as shown in Fig. 9
by treating the organic ligand as an individual system.

(a) (b)
Figure 7 Structures of diphenyl (a) and pyrene moieties (b)
Key: grey, carbon; white, hydrogen

(a) (b)
Figure 8 Unit cells of di-COF-102 (a) and py-COF-102 (b)
Key: grey, carbon; black, oxygen; white, hydrogen; light grey, boron
Table 2 Properties of di-COF-102 and py-COF-102
Material Specific area/m
2
g
1
Mass/gmol
1
Unit cell volume/nm
3
a = b = c/nm Free volume /cm
3
g
1
Porosity
di-COF-102 5005.9 8736 76.7683 4.25005 4.71 0.890
py-COF-102 4865.2 10570 77.2786 4.25945 3.95 0.899
COF-102 4434.5 5083 20.0729 2.71771 1.81 0.762
(a) (b)
Figure 9 ESP charges of simplified clusters models for di-COF-102 (a) and py-COF-102 (b)
Key: grey, carbon; black, oxygen; white, hydrogen; light grey, boron
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 714
ESP charge of the cluster models of the di-COF-102
and py-COF-102 are calculated by Dmol
3
module.
The unit cell volume and the free volume of
di-COF-102 and py-COF-102 are increased obviously
compared to those of original COF-102 due to the
much bigger size of the moieties. However, the free
volume of py-COF-102 is smaller than that of
di-COF-102 due to the fact that pyrene molecule itself
occupies too much volume. Meanwhile, both specific
area and porosity also increase, which is favorable for
the improvement of adsorption quantity. The replace-
ment of ligands also has great influence on the charge
of the central carbon atom, it is 1.788 and 0.801,
respectively for di-COF-102 and py-COF-102, much
lower than 4.464 in the original COF-102 [22]. Con-
taining one more aromatic t-cloud in diphenyl and
pyrene, the charge of the central carbon atom can be
distributed more dispersedly among the electron
clouds of multi-aromatic rings.
Figure 10 shows the corresponding profiles of
adsorption isotherms of CO
2
and CH
4
on COF-102s
before and after moiety replacement. Among all the
three COF-102s, di-COF-102 shows the best CO
2
and
CH
4
adsorption performance, while py-COF-102 does
not show much increase in CO
2
adsorption quantity
compared with COF-102, even more, it descends a
little at high pressure although it has a little enhance-
ment for the adsorption quantity of CH
4
. These results
coincide well with the H
2
adsorption results reported
by Klontzas et al. [15]. For the quadrupolar CO
2
molecule adsorption, the adsorption depends on the
interactions between CO
2
and framework when the
pressure is low. After the replacement of ligands, the
topological structure does not change so much, so the
quantities of the adsorption are similar with each other.
However, at high pressure, it depends much on the
interactions between CO
2
molecules themselves, where
the free volume is the dominant factor. The higher the
free volume, the higher the adsorption quantity. Among
the three COF-102s, di-COF-102 has the largest free
volume, improving the CO
2
adsorption capacity dra-
matically. When the pressure is 4000 kPa, the CO
2
adsorption quantity on di-COF-102 is almost twice
that of the original one. Since the unit of capacity is in
per gram of adsorbents, higher relative molecular
mass of the adsorbent will reduce the adsorption ca-
pacity somehow. The large pyrene moiety makes the
molar mass of py-COF-102 almost double to the
original COF-102; so the enhancement of adsorption
quantity caused by the free volume is counteracted by
the increase of molecular mass, the adsorption quan-
tity of CO
2
in py-COF-102 does not raise so much.
Different from the CO
2
adsorption mechanism, the
packing effect plays an important role in the CH
4
ad-
sorption. The adsorption capacity of CH
4
is mainly
determined by the free volume, as well as the number
of cross central sites (deposit sites) in the pore. For a
mixture of CO
2
and CH
4
gases, the preferably adsorp-
tive CO
2
can provide more deposit sites for CH
4
. The
higher adsorption quantity of CO
2
on di-COF-102 also
yields higher deposit density of CH
4
. Hence, the ad-
sorption isotherm of CH
4
on di-COF-102 increases
linearly with the pressure. Although the adsorption
quantity of CO
2
in py-COF-102 does not change so
much, the large pyrene moiety can supply more zigzag
deposit sites for CH
4
, as a result, the overall adsorp-
tion quantity of CH
4
on py-COF-102 increases a little
compared with that of the original COF-102.
Because of the above various phenomena, the
adsorption selectivity based on the adsorption capaci-
ties of CO
2
and CH
4
becomes complex. As shown in
Fig. 11, the adsorption selectivity of CO
2
/CH
4
on
ligand replaced COF-102s are lower than that of (a)
(b)
Figure 10 Adsorption isotherms of CO
2
(a) and CH
4
(b)
on COF-102s before and after moiety replacement
M di-COF-102; & py-COF-102; A COF-102
Figure 11 Adsorption selectivity of CO
2
/CH
4
on COF-102s
before and after moiety replacement
M di-COF-102; & py-COF-102; A COF-102
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 715
original one, among them, di-COF-102 is the lowest.
It holds almost as a constant at whatever pressure,
which indicates that the enhancement of the adsorp-
tion capacities of CO
2
and CH
4
on di-COF-102 has a
fixed linear relationship. However, the selectivity of
py-COF-102 decreases a little with the increase of
pressure. Duren and Snurr [23] reckoned that small
channels can enhance the selectivity, while the
enlargement of channel would decrease the selectivity.
The pore size of COF-102 is smaller than that of
di-COF-102 and py-COF-102, so the selectivity of
COF-102 is higher. Besides, the adsorption capacity of
CH
4
is mainly determined by the free volume and the
number of cross central sites in the pore, so COF-102
have the smallest free volume among these three kinds
of COFs and the smallest adsorption quantity of CH
4
between 0 kPa to 4000 kPa, which contributes to the
highest selectivity in comparison with di-COF-102
and py-COF-102 in this range.
4 CONCLUSIONS
COFs have great potential in the gas adsorption
and separation. By computer simulation based on
GCMC, two modification approaches of Li doping
and ligand replacing were adopted to enhance the CO
2
adsorption performance on COF-102s. First, metal Li
was doped in three different ways, i.e., charge exchange,
dipolar interaction and chemical bonding. Among them,
the dipolar interaction doping method by introducing
negative oxygen ions into the framework resulted in
less charge exchange between Li cations and the
framework, therefore, the higher positive charged Li
cations improved the CO
2
adsorption capacity mostly
at lower pressure. Besides, the ligand of phenylene
moiety was replaced by extended aromatic moieties of
diphenyl and pyrene. At high pressure, the adsorption
capacity of CO
2
on di-COF-102 had an obvious in-
crease due to its larger free volume and surface area,
so the capacity of CH
4
had an increase even more,
which made the selectivity of CO
2
/CH
4
decrease.
The simulation results reveal that there are two
stages in gas adsorption in these 3D COFs. At low
pressure, the solid-fluid interactions dominates, so the
metal dipolar interaction doping method, which is re-
alized by introducing the anions in the framework first,
can effectively improve the CO
2
adsorption perform-
ance. At high pressure, the fluid-fluid interactions
plays a control role, the free volume is then the most
important parameter. Consequently, the ligand replac-
ing by the suitable moiety can obviously increase the
adsorption quantity of single component. However,
the selectivity depends on the properties of gaseous
mixtures; especially those with the adsorption mecha-
nism differed from component to component.
NOMENCLATURE
a, b, c unit cell parameters of COF-102, nm
N loading in adsorbent, mmol/g
p pressure, kPa
q partial charge
r interaction potential
S selectivity
u distance between atoms
energy parameter of LJ potential, J
diameter parameter of LJ potential, nm
Subscripts
, mark of single molecule
i,j mark of molecular types
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