Applied Energy 142 (2015) 221–228

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Carbon dioxide adsorption thermodynamics and mechanisms on MCM-41

supported polyethylenimine prepared by wet impregnation method
Weilong Wang a, Jiang Li a,⇑, Xiaolan Wei b, Jing Ding a,⇑, Haijun Feng c, Jinyue Yan d,e, Jianping Yang b
a
School of Engineering, Sun Yat-sen University, Guangzhou, China
b
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China
c
National Supercomputing Center in Shenzhen, Shenzhen, China
d
School of Business, Society and Energy, Mälardalen University, Västerås, Sweden
e
Energy Process Division, Royal Institute of Technology, Stockholm, Sweden

h i g h l i g h t s

 Molecular simulation are used to understand wet impregnation synthesis of MBS.

 The mechanism of CO2 sorption on MBS has been simulated and discussed.
 CO2-philic specific sorption sites of MBS with various sorption energy are discovered.

a r t i c l e i n f o a b s t r a c t

Article history: Amine-functionalized sorbents prepared by wet impregnation method shows great promises for CO2
Received 7 July 2014 capture from real flue gas in power plants. The objective of this work is to understand CO2 adsorption
Received in revised form 22 December 2014 thermodynamics and mechanisms at varied polyethylenimine (PEI) loadings on mesoporous MCM-41
Accepted 26 December 2014
by wet impregnation method using a computational approach for the first time. The structures of PEI/
MCM-41 sorbents were optimized using molecular dynamics (MD), and the CO2 adsorption thermody-
namics at varied PEI loadings was simulated using Grand Canonical Monte Carlo (GCMC) method. Results
Keywords:
showed a good agreement between experiments and simulation. On the surface of the MCM-41, there are
Molecular basket sorbent
CO2 adsorption
high CO2-philic sites for CO2 adsorption, which were firstly covered by PEI molecular. The functionaliza-
Molecular simulation tion groups increased the interactions of the CO2 with more PEI molecular deployed on the surface of the
Monte Carlo MCM-41, then to the center of the pore. The adsorption performance of the composite sorbents depended
MCM-41 on the adsorption cites and the space for CO2 diffusion. The CO2 adsorption thermodynamics and mech-
Polyethylenimine anisms at varied PEI loadings shed lights on tuning CO2 capture performance with amine-functionalized
sorbents for power plant greenhouse gas control.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
The rising levels of atmospheric CO2 are thought to be one cause
of globe warming and climate change, and hence CO2 capture and
sequestration (CCS) has drawn widespread attention worldwide
[1–5]. Currently, a significant portion of CO2 comes from the flue
gas generated by the fossil fuel combustion in energy-intensified
industries, such as power stations and steel plants. Current meth-
ods for capture carbon dioxide from flue gas include amine scrub-
bing, cryogenic distillation, solid sorbents adsorption, etc. [6].
Among these, amine scrubbing is employed for CO2 capture in
power plants with the advantage of high CO2 adsorption capacity.
⇑ Corresponding authors. Tel.: +86 20 39332320; fax: +86 20 39332319.
E-mail addresses: lijianggs@126.com (J. Li), dingjing@mail.sysu.edu.cn (J. Ding).
However, the drawbacks, such as huge energy consumption for sol-
vent regeneration and foaming and corrosion issues [6,7] limits its
applications. In contrast, CO2 adsorption by solid sorbents, such as
molecular sieves, metal oxides and activated carbon are thought as
an alternative technology with the promising features of non-cor-
rosion, non-toxic and high selectivity and capacity. The major chal-
lenge for solid sorbent adsorption is how to achieve high CO2
adsorption capacity and regenerability at close-to-real flue gas
conditions (at 348 K and 1 atm) to lower energy consumption.
Recently, amine-functionalized solid sorbents demonstrate
great promises for CO2 capture. Two methods, grafting methods
and wet impregnation methods are proposed and studied experi-
mentally to prepare the amine-functionalized sorbents. In the
grafting methods, amine groups are anchored on the surface of
porous materials forming chemical bonds using silane coupling

http://dx.doi.org/10.1016/j.apenergy.2014.12.072
0306-2619/Ó 2015 Elsevier Ltd. All rights reserved.
222 W. Wang et al. / Applied Energy 142 (2015) 221–228
agents [8]. However, low adsorption capacity can be achieved due
to the limited sites for anchoring amine groups on porous materi-
als, the length and shape of chains, as well as the geometry of sur-
face [9]. In the wet impregnation methods, the sorbent is prepared
by blending the supporting materials with CO2-philic polymer in a
methanol/ethanol solution. The polymers enter the pore channel of
the supporting materials, stretch out on the inner surfaces, and fill
the pores gradually. Song’s group at Penn State University firstly
proposed ‘‘molecular basket sorbent’’ (MBS), a type of solid
amine-functionalized sorbents prepared by wet impregnation
method, which shows a high adsorption capacity up to 133 mg-
CO2/g-sorb at real-industrial flue gas conditions, as well as good
regenerability and stability [10–18]. (see Fig. 1)
Even though extensive experimental studies have been carried
out on CO2 adsorption over the MBS, the interactions between
MBS and CO2 at varied amine loading are not yet fully understood.
As a complementary technique, molecular simulation has been
introduced. Zhou [19] built a four pore hexagonal model of
MCM-41, and studied CO2 adsorption over MCM-41 by the Grand
Canonical ensemble Monte Carlo (GCMC) simulation or kinetic
Monte Carlo (KMC). Liu and Seaton [19,20] simulated the CO2
adsorption of the MCM-41-based sorbents grafted with different
kinds and different numbers of amine groups. It was found that
the difficulties in these kinds of simulation were how to simulate
the interaction between CO2 and amine groups by GCMC, which
can only calculate physical process. The improved simulation on
weak chemical interaction between CO2 and amine groups through
enhanced physical interaction was reported by Liu’s group, and the
adsorption selectivity was also investigated so far, most simulation
study limited to pre-synthesis amine-grafting sorbents [9]. To our
best knowledge, quite few works has been done to simulate the
CO2 transportation and capture in post-synthesis amine based sor-
bents. Builes proposed a simulation methodology for the design of
post-synthesis amine-functionalized sorbents based on energy bias
selection scheme, where amine groups link to the silica surface by
coupling agents [21]. However, the simulation work on CO2
adsorption on the MBS prepared by wet impregnation method is
scare. Mechanistic questions, like the impregnation process of
amine-based polymer over the porous silica support, the poly-
mer-support interactions, and effects of PEI loading on CO2 adsorp-
tion isotherms and working capacities are certainly not answered.
Herein, a mechanistic study of CO2 adsorption over a MBS, mes-
oporous MCM-41 silica supported PEI (PEI/MCM-41) prepared by
wet impregnation method has been carried out using a computa-
tional approach. A realistic MCM-41 model was constructed. The
CO2 adsorption isotherms over MCM-41 were simulated and com-
pared with experiment results to verify the model. CO2 diffusion in
MCM-41 channels was studied via the micro canonical ensemble
molecular dynamics simulation. The energy distribution histogram
of CO2 adsorption isotherm over MCM-41 was addressed. PEI/
MCM-41 sorbents were built based on the verified MCM-41 model.
The impregnation process of amine-based polymer over the porous
silica support was simulated using molecular dynamics (MD)
Fig. 1. The concept of molecular basked sorbents (MBS).
methods. The CO2-MBS surface interactions were understood with
the energy distribution histogram. Effects of PEI loadings on CO2
adsorption isotherms, working capacities, and isosteric heats were
investigated using Grand Canonical Monte Carlo (GCMC) simula-
tion, and further discussed.
2. Model and methodology
2.1. MCM-41 model construction
Several MCM-41 models have been constructed in the literature
[19–20]. We build the MCM-41 atomistic models following the
work of Pellenq and Vega [22,23]. The mimetic MCM-41 is created
by carving out straight cylindrical pores in an amorphous silica
super cell. The amorphous silica model is used to build a
6.42  4.28  4.28 nm3 unit, and then two cylindrical pores are
created by removing the atoms in the volume of the carved cylin-
der. The silica atoms outside the carved cylinder are remained.
Hydroxyl groups are introduced by adding H and O atoms on the
unsaturated Si and O atom sites. Among them, Si atoms linked with
three hydroxyls are removed. The final structure generated by this
procedure is subject to molecule optimization using Forcite mod-
ule in Materials Studio via the universal force field. The atomic
charges were calculated following Zhou’s modelling method [19].
2.2. PEI/MCM-41 model construction
In the experiments, as Liquid PEI (MW = 300) has been chosen as
a CO2-philic polymer due to its low viscosity at room temperature.
Thus, in the simulation linear polyethylenimine (PEI) with poly-
merization degree of eight with a molecule weight of 346 is created
using the ‘‘Build Polymers’’ Tool in Materials Studio [24]. The poly-
mer is viscous liquid that can be loaded into the pores of MCM-41
through wet impregnation method. To mimic different PEI loadings,
amorphous cells with varied amounts of PEI molecules are created
and inserted into the pores of the MCM-41 model. The PEI/MCM-41
structures are optimized using the molecular dynamics simulation.
To ensure the PEI molecule move to the optimized position and
adhere to the MCM-41 surface, NVT is set at 348 K (75 °C).
Fig. 2 shows the snapshots of PEI/MCM-41 sorbent model pre-
pared by the wet impregnation method before- and after-optimi-
zation. As shown in Fig. 2(a), when PEI clusters enter into the
MCM-41, at the initial stage, the distribution of PEI is not reason-
able, and the configuration of PEI/MCM-41 model requires further
optimization. Based on the minimum energy rules of system, PEI/
MCM-41 model was optimized by freeing the PEI molecules to
most thermodynamically stable positions using the molecular
dynamics simulation method with NVT ensemble at the tempera-
ture of 348 K. The optimized PEI/MCM-41 structure was shown in
Fig. 2(b). The PEI molecules are observed to be well dispersed and
adhered to the MCM-41 surface due to the release of internal
stress.
 W. Wang et al. / Applied Energy 142 (2015) 221–228 223

Both are adopted for the LJ interaction between adsorbent and

adsorbates, where the LJ potential parameters are reported by Pel-
lenq (see Table 1). The CO2 model is built based on Yung’s work
[26]. For the PEI model, the methyl and methylene are treated as
one particle since its accuracy effects can be neglected.
CO2 adsorption over MCM-41 is simulated by GCMC method.
The adsorption isotherms were calculated by simulating the aver-
age number of CO2 molecules at different sets of bulk pressures at
the constant temperature and volume. Ewald method is used to
calculate the sum of electrostatic interaction between different
atoms, and the computational precision is 0.001 kcal/mol. The
summation method of Van der Waals interaction is atom-based,
in which, the cut-off radius is 20 Å. The total simulation steps are
2.0  107, and the first 1.0  107 MC steps are used for equilibrium
calculation, while the remains are for the calculation of thermody-
namic properties such as adsorption isotherms.

3. Results and discussion

3.1. MCM-41 model

A reliable model of MCM-41 is the base for the adsorption pro-

cess simulation, and for the modelling of the PEI/MCM-41 sorbents
by wet impregnation method. Fig. 3 shows the optimized MCM-41
structure model, which is built by carving cylindrical channel in an
amorphous silica matrix. The radius of these pores is 15.0 Å, and
the channel is arranged hexagonally. In the construction of
MCM-41 model, hydroxyls groups are introduced onto the surface
randomly to saturate the unsaturated Si and O atoms. However,
the incorrect structure of Si atoms with three hydroxyls is also pro-
duced, which is removed to keep the MCM-41 structure accurate.
On average, about 7–8 hydroxyls per square nanometer is con-
structed on MCM-41. After that, the MCM-41 model is optimized
by molecular-mechanism methods using Forcite module. The opti-
mized lattice parameters of the MCM-41 model are listed in
Fig. 2. Snapshot of PEI /MCM-41 model before- and after-optimization. (color code:
Table 1. By comparison, it can be noted that the dimensions of
yellow, Si; red, O; white H; blue, N; grey, C). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.) the simulation unit change to 6.23  4.15  4.15 nm3, which is
decreased by <3% in each direction. No change is noticed on the
cylindrical pore shape and hexagonal array.
Based on the optimal MCM-41 structure, the atomic charges of
2.3. Adsorption simulations MCM-41, CO2, and PEI are calculated using the density-functional
theory (DFT) in Material Studio. The charge distribution of the
Energy of interactions between atoms is critical, which is calcu- framework affects the interaction between sorbents and adsor-
lated using force field in molecular simulation. The mathematics bates, especially for polar adsorbates. In this work, we follow Zhou
form and parameters of the atoms’ interactions are considered. and Jiang’s electrostatic potential (ESP) method [19] to calculate
Intra-molecular part and non-bond part are included in a common the atomic charges in Material Studio, where the electrostatic
force field, where the intra-molecular part contains bond term, potentials are fitted at grids located with equal density on different
angle term, dihedral angle term, and the non-bond part contains layers around the molecule. The Lennard-Jones potential parame-
Van der Waals term and electric potential term. ters of the atoms of MCM-41, CO2, and PEI are listed in Table 2.
In the GCMC simulation, both the adsorbate and the adsorbent
are considered as rigid bodies, and thus only the non-bond energy 3.2. CO2 adsorption in MCM-41
is calculated. The interactions between adsorbate and adsorbent, as
well as between adsorbates are described by the combinations of Fig. 4 shows the simulated CO2 adsorption isotherms in pure
Lennard-Jones (LJ) potential and Columbic potential [25]: MCM-41 at low pressure at 298 K compared to the experimental
( "   6 # ) CO2 adsorption isotherms reported by Seaton [27]. By comparison
X rab 12 rab qa qb
uij ðrÞ ¼ 4eab  þ ð1Þ of the adsorption isotherms at 298 K, the simulation results show a
r ab r ab 4pe0 rab good agreement with the experimental one, which validates the
ai
rationality of the MCM-41 model. Based on the validated MCM-
bj
41 model, the adsorption isotherm of pure MCM-41 model at
where e0 is the vacuum permittivity, rab and eab are the depth and
length of the potential, q is the charge of the atom. The Lorentz–
Table 1
Berthelot (LB) combining rule as follows,
Optimized lattice parameters of the MCM-41 model.
 
rab ¼ ra þ rb =2 ð2Þ Parameter A (nm) B (nm) C (nm) a (°) b (°) c (°)
 
eab ¼ ea eb 1=2 ð3Þ MCM-41 6.23 4.15 4.15 90.1 89.5 91.1
224 W. Wang et al. / Applied Energy 142 (2015) 221–228

Fig. 5. Energy distribution versus interaction energy of CO2 molecule over pure
Fig. 3. Optimized MCM-41 model. (color code: yellow, Si; red, O; white, H. The
MCM-41.
atoms in the structure are represented as Van der Waals spheres). (For interpre-
tation of the references to colour in this figure legend, the reader is referred to the
web version of this article.) interaction energies, with the integral of this histogram corre-
sponding to the adsorbate–adsorbent energy of interaction [27].
The energy distribution histogram provides model-independent
Table 2 information about the numbers of different adsorption sites and
Lennard-Jones potential parameters and atomic charges.
their respective energy-levels. The interaction energy is calculated
Molecule Site r (Å) e/kB (K) q (e) by subtracting the sum of the energy of the adsorbate and the sor-
MCM-41 Si 3.804 155.8580 0.12220 bent, from the energy of the optimized adsorbate–sorbent system.
O 3.033 48.1150 0.06157 In MC simulation, the interaction energy changes when an adsor-
H 2.846 7.6540 0.03232 bate molecule moves at any motions, such as insertion, deletion,
CO2 C 2.757 28.1290 0.78144 translation, or rotation. Adsorbate molecules show different inter-
O 3.033 80.500 –0.39072 action energy at different adsorption sites on the adsorbent. The
PEI CH2/CH3 3.905 59.409 0.24750 lower the interaction energy, the more the possibility adsorbing
N 3.300 85.589 0.9000 the adsorbate molecules is. Different adsorption sites on the adsor-
H 2.846 0.0503 0.36000 bent frame, identified by peaks at different energy positions, sug-
gest different kinds of adsorption mechanism.
Fig. 5 shows the CO2 adsorption energy distribution in MCM-41.
Two peaks and a platform in-between are observed in the energy
distribution histogram for CO2 adsorption on pure MCM-41. The
left peak appears at 8 kcal/mol representing a type of high-prob-
ability adsorption sites on MCM-41, which tends to adsorb CO2
molecules preferably.
Fig. 6 shows the snapshots of CO2 adsorption in MCM-41, which
describes the distribution of adsorbed CO2 molecules in MCM-41. It
can be observed that CO2 prefers to be accumulated on the proxim-
ity of dense silanol groups on MCM-41, as shown in the circled area
in the zoomed-in Fig. 6(b). The results suggest that dense silanol
groups on MCM-41 may be the more exothermic adsorption site
(8 kcal/mol) for the adsorption of CO2 molecules, which can be
ascribed to Van der Wals interaction. The right peak at 0 kcal/
mol in Fig. 5 stands for the interaction between CO2 molecules,
which can be confirmed in an empty unit simulation. The platform
in the histogram presents the CO2 adsorption on other sites of
MCM-41, such as less dense silanol groups. It should be mentioned
that both the high-probability adsorption sites and the low-proba-
Fig. 4. Adsorption isotherms of CO2 in pure MCM-41 from simulation and
experiments [24] at 298 K and 348 K.
bility sites on MCM-41 contribute to the total adsorption capacity,
and the high-probability adsorption site catches CO2 more readily.

348 K is simulated as shown in Fig. 4. It can be found that at 348 K,
CO2 adsorption in MCM-41 at low pressure follows the Henry
adsorption, as the adsorption capacity increases almost linearly
with pressure. The adsorption capacity of MCM-41 is 9.25 mg-
CO2/g-sorbent at 100 kPa based on the simulation results, which
is consistent with the experimental capacity of 8.6 mg-CO2/g-sor-
bent on the pure silica MCM-41, reported by Song et al. [15].
The energy distribution histogram is an effective technique to
characterize the distribution of adsorbed molecules over different
3.3. PEI/MCM-41 model
The process of loading PEI into supporting materials and its
impact on CO2 adsorption over the MBS prepared by wet impreg-
nation method are studied. Fig. 7 shows the snapshot of PEI/
MCM-41 at increasing loadings of PEI. At low PEI loading, PEI mol-
ecules firstly occupy the surface sites of MCM-41 as shown in
Fig. 7(a). As the PEI loading increases, the surface of MCM-41 is
fully covered by PEI molecules to form a monolayer rather than
 W. Wang et al. / Applied Energy 142 (2015) 221–228 225

Fig. 6. Snapshot of CO2 adsorption in MCM-41. (color code: yellow, Si; red, O; white, H; green dots, adsorbed CO2 molecules). (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)

Fig. 7. Snapshots of PEI/MCM-41 at PEI loading of 0.06 (a); 0.12 (b); 0.18 (c); 0.24 (d). (color code: yellow, Si; red, O; white H; blue, N; grey, C). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

polymer accumulation as shown in Fig. 7(b), suggesting PEI–MCM-

41 interaction is stronger than PEI–PEI interaction. It should be
mentioned that the entire system energy is decreased and the
structure becomes more stable when a monolayer of PEI is impreg-
nated onto MCM-41. By further increasing PEI loading, impreg-
nated PEI forms multilayer (Fig. 7(c)) and eventually fill the
entire pore of MCM-41 (Fig. 7(d)). In contrast, the space between
the PEI layers is greater than the first PEI layer to MCM-41 surface,
which further indicates that the interaction energy (negative
value) between the surface of MCM-41 and PEI molecules are more
exothermic than that between PEI molecules. Moreover, the spaces
between multilayers of PEI in PEI/MCM-41 provide the spaces for
the diffusion and adsorption of CO2 molecules.

3.4. CO2 adsorption on PEI/MCM-41 sorbents

Song’ group studied the CO2 adsorption capacity of the PEI/
MCM-41 at different PEI loadings at 75 °C [7], which is compared
with our simulation results. The adsorption capacity is simulated
using the GCMC simulation method. Fig. 8 shows the simulated
adsorption capacity at varied PEI loadings (0–24 wt.%), in compar-
ison with the experimental results. A good agreement is observed
between the simulated and experimental results for CO2 adsorp-
Fig. 8. The simulation and experimental results of effects of the PEI loading on the
CO2 adsorption.
tion in PEI/MCM-41 sorbents, which further validates the PEI/
MCM-41 model. The CO2 adsorption capacity varies with the PEI
loading in MCM-41. It should be noticed that the CO2 adsorption
capacity does not increase when the weight ratio of PEI to MCM-
226 W. Wang et al. / Applied Energy 142 (2015) 221–228
Fig. 9. Density profiles of CO2 adsorption in MCM-41. (color code: yellow, Si; red, O; white H; blue, N; grey, C). (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
41 is lower than 6 wt.%. When the PEI loading in the MCM-41 is
greater than 6 wt.% (but <24 wt.%), the CO2 adsorption capacity
increases with PEI loading until the pores of MCM-41 are fully
filled with PEI, which can be observed from both the experiments
and the simulation. As stated earlier in Figs. 5 and 6, CO2 adsorbs
preferably on specific sites of pore MCM-41, rather than uniformly.
These specific sites are occupied preferably when PEI is loaded over
MCM-41. Therefore, at the initial stage of PEI loading, the specific
sites are occupied by PEI molecules and thus not available for
CO2 adsorption anymore. Even though the CO2 adsorption over
the amine sites on PEI (9 kcal/mol) is much more exothermic
than most sites on the surfaces and the internal channels of pure
MCM-41, but it is similar as the high-probability sites (8 kcal/
mol) occupied by PEI initially during impregnation. Therefore, at
low PEI loading, CO2 adsorption capacity does not increase due to
the compensation of lost adsorption sites on pure MCM-41 support
with the introduced PEI sites. Except the loss of these adsorption
sites on MCM-41, the increased amine sites on PEI/MCM-41 by
Fig. 10. Adsorption isotherms of CO2 over PEI/MCM-41 sorbent at different PEI
loadings.
increasing PEI loading result in increased CO2 adsorption capacity,
as suggested in Fig. 8.
Fig. 9 displays the density profiles of CO2 adsorption in PEI/
MCM-41 sorbents with different PEI loading. Most CO2 molecules
are adsorbed at the surface of the pore with low energy and the
sites of the amine groups for the strong interaction between CO2
molecule and amine groups. At the higher PEI loading, the large
free spaces between multilayers of PEI provide the spaces for the
diffusion and adsorption of CO2 molecules. The result suggests
most NH2- groups on the polymer can be accessed by CO2 mole-
cules, and thus the MBS achieves higher adsorption capacity in
the experiments.
Fig. 10 shows the simulated adsorption isotherms of sorbents at
various pressure with different PEI loadings (6–24 wt.%). The
adsorption capacity increases with PEI loading. The adsorption iso-
therms are linear and the adsorption capacity increases with the
CO2 pressure. In experiments, CO2 adsorption isotherms over
amine-based sorbents are close to a reverse-L shape [8,14], which
Fig. 11. Sorption heat of CO2 over PEI/MCM-41 at different PEI loadings.
 W. Wang et al. / Applied Energy 142 (2015) 221–228
Fig. 12. Energy distribution of CO2 sorption in PEI/MCM-41 at different PEI loadings: (a) 0.06; (b) 0.12; (c) 0.18; (d) 0.24.
suggests CO2 adsorption reaches saturation capacity at quite low
pressures. In the simulation, electronic interaction, rather than
chemical interaction is used to represent the CO2–amine interac-
tion. Therefore, the adsorption capacity is lower in the modelling
at low pressures compared to the experiment values. The enhanced
physical adsorption simulation, which has been used to describe
chemisorptions in modelling, may improve the modelling to be
more accurate, and it will be studied in the future.
Fig. 11 shows the adsorption heats of PEI/MCM-41 at different
PEI loadings. Adsorption heat of the PEI/MCM-41 is greater than
pure MCM-41, which means that in the MBS, CO2 adsorption is
strengthened. Moreover, it shows that the heat of adsorption
increases with the PEI loading. When the PEI loading increases
from 0 to 12 wt.%, small change is observed on the adsorption heat,
which agrees well with the results showed in Fig. 7. At the PEI
loading of 12 wt.%, the CO2-philic specific sites of MCM-41 is fully
covered by PEI, and the compensation of CO2-philic specific sites
with amine sites results in the lower adsorption heat. At higher
PEI loading, the increased amine sites increase the CO2 adsorption
heat gradually. It should be mentioned that Fig. 11 also shows that
the isosteric heat drops with the increased pressures due to the dif-
ferent stages of the adsorption. CO2 molecule is first adsorbed at
the CO2-philic specific sites on MCM-41, and the amine sites for
the strong CO2–amine interaction. After these adsorption sites
are occupied, multilayer CO2 adsorption occurs. Since the interac-
tion between CO2 molecules is much weaker, the isosteric heat
decreases.
Fig. 12 shows the energy distribution of CO2 adsorption in PEI/
MCM-41 at different PEI loadings. At PEI loading of 6 wt.% as
shown in Fig. 12(a), no peak shows up at 8 kcal/mol (stands for
the MCM-41 strong-probability adsorption sites on pure MCM-
227
41), and it confirms these sites are indeed occupied by loaded
PEI. Meanwhile, a new peak at 9 kcal/mol appears, representing
the interaction between amine sites on PEI/MCM-41 and CO2 mol-
ecules. The peak at 9 kcal/mol becomes larger with the increase
in PEI loading. When the PEI loading reaches 24 wt.% in
Fig. 12(d), only a shape peak at 9 kcal/mol can be noticed, sug-
gesting all the adsorption capacity comes from the amine sites
on loaded PEI. It should be mentioned that an overlapped peak at
the interaction energy of around 5 kcal/mol appears in
Fig. 12(b) and (c), which may be due to the amine–CO2 interaction
in 1 to 1 ratio, which is weaker than amine–CO2 interaction in 2 to
1 ratio with adsorption energy of 9 kcal/mol. It should also be
noted that the CO2–amine interaction carried out in this study is
based on the electronic interaction of CO2–amine, which is rela-
tively lower than the chemical interaction of CO2–amine in reality.
4. Conclusions
A MCM-41 model is constructed by carving the cylindrical pores
in an amorphous silica matrix and optimized by molecular-mech-
anism methods using Forcite module. The model is validated by
the consistency of the simulated CO2 adsorption isotherms with
the reported experimental results. Energy distribution of CO2
adsorption over unsupported MCM-41 suggests the presence of
strong CO2-philic specific sites on MCM-41, which is confirmed
as the dense silanol sites on MCM-41 surface. The GCMC simula-
tion on CO2 adsorption thermodynamics suggests that (a) on
unsupported MCM-41, the surface silanol sites act as the CO2-phi-
lic sites to adsorb CO2 preferably, with an adsorption energy of
8 kcal/mol; (b) at low PEI loadings (<6 wt.%), the CO2 adsorption
228 W. Wang et al. / Applied Energy 142 (2015) 221–228
capacity does not improve until all the silanol sites on MCM-41
support are buried by PEI molecules; (c) at higher PEI loadings
(6–24 wt.%), the CO2 adsorption capacity is dominated by the
accessible amine sites on PEI/MCM-41(adsorption energy of
9 kcal/mol), which increases with PEI loadings over MCM-41.
The CO2 adsorption process disclosed in the simulation study pro-
vide insights to tune amine-functional sorbents for power plant
greenhouse gas control.
Acknowledgements
Author would like to thank the funding support by National
Natural Science Foundation of China (51106185), NSFC-Guangdong
Joint Fund Project (U1034005), and Nature Science Foundation of
Guangdong Province (S2012040007694), Fundamental Research
Funds for the Central Universities (12lgpy23), and National Basic
Research Program of China (2012CB720404).
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