Article

pubs.acs.org/JPCC

Molecular Dynamics Simulations of CO2/N2 Separation through Two-

Dimensional Graphene Oxide Membranes
Wen Li,† Xin Zheng,† Zihan Dong, Chuanyong Li, Wensen Wang, Youguo Yan,* and Jun Zhang*
College of Science and Key Laboratory of New Energy Physics & Materials Science in Universities of Shandong, China University of
Petroleum, 266580 Qingdao, Shandong, People’s Republic of China
*
S Supporting Information

ABSTRACT: Graphene oxide (GO), as an ultrathin, high-flux,

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and energy-efficient separation membrane, has shown great

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potential for CO2 capture. In this study, using molecular dynamics

simulations, the separation of CO2 and N2 through the interlayer
gallery of GO membranes was studied. The preferential adsorption
of CO2 in the GO channel derived from their strong interaction is
responsible for the selectivity of CO2 over N2. Furthermore, the
influences of interlayer spacing, oxidization degree, and channel
length on the separation of CO2/N2 were investigated. Our studies
unveil the underlying mechanism of CO2/N2 separation in the interlayer GO channel, and the results may be helpful in guiding
rational design of GO membranes for gas separation.

■ INTRODUCTION
In the past decades, the increasing emission of CO2 has aroused
serious environmental problems,1−3 especially the greenhouse
effect.4,5 Meanwhile, CO2 also has widespread applications in
many industrial fields, such as enhanced oil recovery,6
microelectronics cleaning,7 and industrial extraction.8 Captur-
ing CO2 from N2, on one hand, could reduce the amount of
CO2 in the atmosphere and on the other hand could realize the
recycle of CO2. Therefore, many efforts have been devoted to
developing various strategies to separate CO2/N2.9−12
Recent investigations have shown that membrane separation
is a highly efficient approach for gas separation due to its low
energy cost.13−15 The separation membranes could be divided
into organic (polymers) membranes, inorganic (carbon, glass,
metal, ceramics) membranes, and hybrid (inorganic polymeric
or organic−inorganic) membranes. For all types of membranes,
abundant research has demonstrated that there is a trade-off
between selectivity and permeability, and the permeability of a
membrane is inversely proportional to its thickness. Moreover,
the aging and plasticization of these membrane materials is
another obstacle to maintaining the long-lived gas separation
performance. To remedy the shortages of these traditional
membrane materials, nanoporous graphene, a single atomic
layer membrane, has been used for gas separation and obtained
great success.16−20 It presents high selectivity and large
permeability simultaneously, but its separation performance is
largely dependent on the pore sizes in the graphene. Although
the use of elaborate oxidative etching or electron/ion
bombardment could drill holes in graphene, a precise, large-
area, and high-density perforation remains a technical
challenge.21−23
In contrast to graphene, its oxidized form, graphene oxide
(GO) membrane with a laminar structure shows great potential
for molecular separation.20,24−28 Unlike nanoporous graphene,
the GO membrane does not need to drill holes for gas
separation, and the interlayer spaces of the laminar GO
membrane could act as the main channels for molecular
separation. By controlling humidity, inserting nanoparticles
between adjacent layers, or modifying chemical groups with
different chain lengths, different interlayer spaces could be
achieved and used to separate various chemical species. This
might open an avenue for gas separation using low-cost GO
membrane.29
Recently, Jin et al. found that the molecular-sieving interlayer
spaces and straight diffusion pathways of GO laminates yielded
fast and selective CO2 permeation over N2,30 which was
attractive for CO2 capture. However, there are still many
questions that remain to be clarified. First, the nature of the GO
interlayer channel exhibiting the selectivity of CO2 over N2 is
unclear. Second, how the CO2 molecules pass across the
interlayer spaces of GO membranes needs to be elucidated. To
unravel these questions, a molecular-level study is urgently
needed, but conducting measurements and observations at the
molecular level is still an experimental challenge.
In the past decades, molecular dynamics (MD) simulations
have been developed to investigate microscopic interactions
that can provide detailed information about dynamic, energetic,
and structural information on complex systems at the molecular
level.31−37 Using MD simulations, the adsorption and diffusion
of water, gas, and ion in the interlayer spaces of GO laminates
have been investigated.37−39 These studies have proved that
MD simulation is an efficient method to investigate the
Received: July 11, 2016
Revised: October 28, 2016
Published: October 31, 2016

© 2016 American Chemical Society 26061 DOI: 10.1021/acs.jpcc.6b06940

J. Phys. Chem. C 2016, 120, 26061−26066
The Journal of Physical Chemistry C
Figure 1. (a) Structure of GO with modified groups of hydroxyl and epoxy. (b) Atomic structures of CO2 and N2. (c) Model of the built box. White,
blue, cyan, and red balls denote hydrogen, nitrogen, carbon, and oxygen, respectively.
Figure 2. (a) Time evolution of the amount of gas in the three regions as labeled in Figure 1c. (b) Number density distributions of CO2 and N2
along the Z direction.
transport behavior of gas in the GO membrane. Therefore, in
this paper, we performed molecular dynamics simulations to
investigate the separation mechanism of CO2/N2 in the GO
membrane. Furthermore, the influences of oxidation degree,
interlayer spacing, and channel length of the GO membrane on
its separation performance were also studied.
■
MODELS AND METHODS
According to the experimental evidence40 and Lerf−Klinowski
model,41 the GO flake mainly includes oxygenic functional
groups of hydroxyl, epoxy, and carboxyl. The hydroxyl and
epoxy primarily locate on the basic plane, while the carboxyl
mostly distributes on the edges. In this work, the gas molecules
mainly pass through the membrane along the interlayer spaces,
and the modified groups on the edges have negligible effect on
the gas-transport performance. Correspondingly, for simplicity,
the constructed GO sheet only contains the randomly
distributed hydroxyl and epoxy groups on the two basal planes,
as shown in Figure 1a. The oxidization degree is denoted as
RO/C = NO/NC with typical ranges of 0−60%. Here, the NO and
NC represent the number of oxygen atoms and carbon atoms,
respectively. Figure 1b shows the molecular structures of CO2
and N2. Figure 1c displays the initial model with dimensions of
29.52 Å × 42.61 Å × 300.00 Å. As shown, two GO sheets were
placed onto two sides of a slit to construct a horizontal channel.
The interlayer spacing is defined as the vertical distance
between upper and lower basal planes of GO sheets. Two
graphene slabs were placed on the leftmost and rightmost sides.
In the simulation, the channel was fixed apart from the
modified hydroxyl and epoxy groups. The rightmost graphene
slab was fixed, and the leftmost graphene will be applied a force
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to push gases passing across the channel. Finally, 80 CO2 and
80 N2 were put inside the left chamber.
In this study, the systems were simulated with LAMMPS
software.42 A constant velocity (1.5 Å/ns) was applied onto the
leftmost graphene slab to push the gas passing across the
channel. During the simulation, all-atom optimized potential
OPLS-AA was used for GO.43 The 12−6 Lennard-Jones
potential 4εc−o[(σc‑o/r)12 − (σc−o/r)6] was used to calculate the
van der Waals interactions between gas and GO with
parameters listed in Table S1.37,44 Here, r presents the distance
between two atoms. The cutoff distance of the van der Waals
interactions was set as 12 Å. In this study, the electrostatic
interactions were especially considered. The preferable three-
site model with three partial charges was adopted for CO2,45
while the well-known Lennard-Jones potential was adopted to
model the neutral N2.46 The detailed partial charges on the gas
molecules and GO were also shown in Table S1. The long-
range Coulomb interactions were computed by using the
particle−particle particle−mesh (PPPM) algorithm. Periodic
boundary conditions were applied in all directions. All of the
simulations were conducted in a canonical ensemble (NVT) at
298 K controlled by the Nose−Hoover thermostat method.
The time step was set as 1 fs, and a total of 10 ns simulation
was conducted for each model. The data were collected every 2
ps, and a full-precision trajectory was recorded.
■
RESULTS AND DISCUSSION
Separation Performance. Generally, the typical GO
multilayer membranes have interlayer spacing of 7.3 Å and
oxidation degrees ranging from 30% to 60% determined by the
experimental conditions. Therefore, we first performed
DOI: 10.1021/acs.jpcc.6b06940
J. Phys. Chem. C 2016, 120, 26061−26066
The Journal of Physical Chemistry C
simulations for systems with interlayer spacing of 7.3 Å and
oxidization degree of 30%. To present the separation
performance of this system, time evolution of the number of
gases in the three regions in Figure 1c was recorded in Figure
2a. Figure 2a gives the results: (1) the N2 almost cannot pass
through the channel; (2) the CO2 first fills the channel, and
then, when the channel is saturated, the CO2 starts to enter into
the right chamber. These results indicate that the interlayer
channel of GO multilayer could efficiently separate the CO2
and N2. In addition, a quantitative characterization of gas
distribution at 10 ns is represented in Figure 2b, which further
confirms the gas-transport behavior.
Separation Mechanism. Figure 2a indicates the GO
channel was preferentially occupied by the CO2. To understand
the different affinity between CO2 and N2 with the GO channel,
we calculated the interaction energy between the GO and CO2
(N2) as displayed in Figure 3. It shows that the attraction
Figure 3. Time evolution of interaction energy between GO and CO2
(N2).
intensity between the GO and CO2 are far larger than that
between GO and N2. Therefore, the CO2 could preferentially
adsorb onto the GO channel, and then the CO2-saturated
channel allows the subsequent CO2 passage while suppressing
the passage of N2. To prove it, pure N2 was adopted in this
system. Figure S1 clearly demonstrates that the N2 could enter
into and pass across the channel. The above discussions
confirm that the competitive adsorption between CO2 and N2
accounts for the separation of the CO2/N2.
Furthermore, the microscopic transport process was studied.
In the GO channel, there are three types of regions with
different interlayer spaces due to the existence of modified
groups. As shown in Figure 4a, they are described as the
oxidized region (d1 = 3.38 Å), the half-oxidized region (d2 =
5.34 Å), and the pristine graphene region (d3 = 7.3 Å),
Figure 4. (a) Schematic of GO channels with three kinds of spacing. (b−d) Three built channels (oxidized, half oxidized, and pristine) resembling
the different regions as shown in (a), respectively.
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respectively. In order to study the transport behavior in these
three regions, we built three channels analogous to these three
regions as shown in Figure 4b−d.
Figure 5 gives the number of gas molecules passed the
channel along with the simulation time. In the oxidized channel
(Figure 4b), there is no gas molecules passed across the
channel. This result could be ascribed to the limited channel
size of 3.38 Å, which is comparable to the sizes of CO2 (3.30 Å)
and N2 (3.64 Å). In the half-oxidized channel, both the CO2
and the N2 exhibit large enough permeability, but the selectivity
is low. In the pristine channel, the CO2 and N2 could equally
pass across the channel without any selectivity. The transport
behavior in these three regions indicates the half-oxidized and
pristine region could offer quick transport channel for either
CO2 or N2, and hence, only the oxidized region could endow
the GO channel with high selectivity. However, the CO2 could
not transport through the oxidized channel derived of the
limited size. Based on these analyses, we propose the selectivity
mechanism as follows. Generally, in the synthesized GO
membrane, the distribution of the three regions is random.
Therefore, when the passing gases meet the oxidized region,
they will bypass it and go ahead through the half-oxidized
region or pristine region. This point can be confirmed by the
transport pathway displayed in Figure S2. As a result, the
existence of oxidized region will decrease the permeability of
the channel. Meanwhile, because of the strong affinity between
the modified groups and the CO2, the existence of the modified
group will strengthen the preferential adsorption of CO2 and
yield an enhanced selectivity. In summary, the pristine and half-
oxidized regions endow the channel with permeability, and the
oxidized region grants the channel selectivity.
Effects of Interlayer Spacing and Oxidation Degree.
From the above discussions, the interlayer configuration is the
crucial factor determining the transport behavior of gas
molecules. Here, two configurational parameters, the interlayer
spacing and oxidation degree, were considered to investigate
the transport behavior of gas molecules. Three interlayer
spacings of 6.3, 7.3, and 8.3 Å and a series of oxidation degrees
of 0%, 10%, 20%, 30%, 40%, 50%, and 60% were adopted. The
permeability and selectivity of these GO membranes were
summarized in Table 1.
The selectivity was defined by following equation47
yCO /yN
2 2
SCO2 /N2 =
xCO2 /x N2
DOI: 10.1021/acs.jpcc.6b06940
J. Phys. Chem. C 2016, 120, 26061−26066
The Journal of Physical Chemistry C Article

Figure 5. Time evolutions of the number of permeated CO2 and N2 for (a) oxidized channel, (b) half-oxidized channel, and (c) pristine channel.

Table 1. Permeability and Selectivity of Channels with Different Interlayer Spacings and Oxidation Degreesa
oxidization degree (%)
interlayer spacing (Å) 0 10 20 30 40 50 60
6.3 μCO2 (106 GPU) 1.83 1.76 1.41 0 0 0 0
μ N2 (106 GPU) 1.62 0.28 0.07 0 0 0 0
SCO2/N2 1.13 6.25 20
7.3 μCO2 (106 GPU) 1.52 1.46 1.28 1.28 1.46 0 0
μ N2 (106 GPU) 1.52 1.28 0.24 0.06 0.06 0 0
SCO2/N2 1 1.14 5.25 21 24
8.3 μCO2 (106 GPU) 1.44 1.39 1.39 1.18 1.12 1.28 1.28
μ N2
6
(10 GPU) 1.34 1.39 1.07 0.96 0.96 0.43 0.11
SCO2/N2 1.08 1 1.30 1.22 1.17 3 12
a
GPU (gas permeation unit), 1 GPU = 3.35 × 10−10 mol· m−2 ·s−1·Pa−1.

where x is the molar fraction of the gas component in the left

chamber at the initial simulation and y is the molar fraction of
the gas component in the right chamber after the simulation.
The permeability could be characterized by the following
equation
n
μ=
APt
where n is the amount of substance of gas molecules passed
across the channel, A is the cross section area of channel, P is
the applied pressure, and t is the corresponding simulation
time.
Table 1 shows that, on one side, with the increase of
oxidization degree, the overall permeability decreases, while the
selectivity increases. This result could be ascribed to the fact
that the increased oxidization degree reduces the transport Figure 6. Schematic of the channels with the increase of oxidation
space and reinforces the affinity of the channel to CO2, which levels (from a to c) of GO. The black solid lines denote graphene. The
leads to a high selectivity. This point can be readily understood red balls and white hollow circles represent the oxygen and hydrogen
by the schematic in Figure 6. On the other side, when a atoms of oxidative functional groups.
narrower channel (6.3 Å) is adopted, the transport space is
compressed. Correspondingly, the gas molecules can only pass the optimal selectivity of channels with different interlayer
through these channels with low oxidization degree, and the spacing emerges at different oxidization degrees. The larger of
maximum selectivity is limited to a value of 20, which is smaller the distance is, the higher of oxidization degree is needed. This
than the maximum value of 24 in channel with interlayer result could be reasonably understood by the changes of the
spacing of 7.3 Å. When a wider channel (8.3 Å) is adopted, the permeability of N2, which is affected by the adsorption quantity
gas molecules have large permeability in every channel, and the of CO2 determined by the oxidization degree.
high oxidization degree endows the channel with high Influence of Channel Length. The influence of the
selectivity. However, the selectivity is also largely smaller than channel length on the gas-transport behavior was further
that obtained in the channel with an interlayer spacing of 7.3 Å. studied. As demonstrated in Figure 7, with the increase of
It is worthy noted that the oxidization degree of the channel channel length, the permeability decreases and the selectivity
has insignificant influence on the permeability of CO2 when the enhances. The results can be explained by the fact that the
channel is permeable. So, the selectivity becomes the point that prolonged channel increases the transporting distance of gas
should be focused on in industrial application. Table 1 indicates molecules, resulting in a lower permeability; meanwhile, the
26064 DOI: 10.1021/acs.jpcc.6b06940
J. Phys. Chem. C 2016, 120, 26061−26066
The Journal of Physical Chemistry C
Figure 7. Number of permeated CO2 and N2 under three different
channel lengths (8.75, 17.5, and 35 Å).
extended channel provides a long selectivity region and yields a
higher selectivity.
■ CONCLUSIONS
In this study, MD simulations were conducted to investigate
the permeability and selectivity of CO2/N2 passing through an
interlayer channel of GO membrane. The preferential
adsorption of CO2 because of the modified groups was found
to be responsible for the high selectivity and large permeability
of CO2 over N2. The effects of oxidization degree and interlayer
spacing were also investigated, and the high oxidization degree
endows the channel with high selectivity and low permeability;
meanwhile, the large interlayer spacing allows the channel to
have large permeability and low selectivity. Furthermore, the
channel length was found to be another factor influencing the
gas transport performance, and the elongated channel decreases
the permeability and enhances the selectivity. This work is
expected to trigger further studies on the design of GO
membrane structure to improve its separation performance in
multiple applications.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b06940.
Force field parameters used in this work; migration
trajectory of CO2 molecule in channel; final config-
uration of N2 molecules alone used as separated gas
source (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: yyg@upc.edu.cn. Tel: 86-0532-86983415.
*E-mail: zhangjun.upc@gmail.com. Tel: 86-0532-86983366.
Author Contributions
†
W.L. and X.Z. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work is financially supported by National Basic Research
Program of China (2015CB250904), National Natural Science
Foundation of China (51302321), Shandong Provincial Natural
Science Foundation, China (2014ZRE28048), and Fundamen-
tal Research Funds for the Central Universities (14CX0222A,
15CX05049A, 15CX06073A).
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Article
■ REFERENCES
(1) Rochelle, G. T. Amine Scrubbing for CO2 Capture. Science 2009,
325, 1652−1654.
(2) Olajire, A. A. CO2 Capture and Separation Technologies for End-
of-Pipe Applications-A Review. Energy 2010, 35, 2610−2628.
(3) Team, C. W.; Pachauri, R.; Reisinger, A. Contribution of Working
Groups I, II and III to the Fourth Assessment Report of the
Intergovernmental Panel on Climate Change; IPCC: Geneva, 2007.
(4) Karl, T. R.; Trenberth, K. E. Modern Global Climate Change.
Science 2003, 302, 1719−1723.
(5) Halmann, M. M.; Steinberg, M. Greenhouse Gas Carbon Dioxide
Mitigation: Science and Technology; CRC Press: Boca Raton, 1998
(6) Forte, E.; Galindo, A.; Trusler, J. P. M. Experimental and
Molecular Modeling Study of the Three-Phase Behavior of (n-Decane
+ Carbon Dioxide + Water) at Reservoir Conditions. J. Phys. Chem. B
2011, 115, 14591−14609.
(7) Purtill, R.; Rothman, L.; Eldridge, B.; Chess, C. Precision Parts
Cleaning Using Supercritical Fluids. J. Vac. Sci. Technol., A 1993, 11,
1696−1701.
(8) Kamali, H.; Golmakani, E.; Golshan, A.; Mohammadi, A.; Sani, T.
A. Optimization of Ethanol Modified Supercritical Carbon Dioxide on
the Extract Yield and Antioxidant Activity from Biebersteinia Multifida
DC. J. Supercrit. Fluids 2014, 91, 46−52.
(9) Yang, Q.; Ma, L.; Zhong, C.; An, X.; Liu, D. Enhancement of
CO2/N2 Mixture Separation Using the Thermodynamic Stepped
Behavior of Adsorption in Metal−Organic Frameworks. J. Phys. Chem.
C 2011, 115, 2790−2797.
(10) Bae, Y.-S.; Farha, O. K.; Hupp, J. T.; Snurr, R. Q. Enhancement
of CO2/N2 Selectivity in A Metal-Organic Framework by Cavity
Modification. J. Mater. Chem. 2009, 19, 2131−2134.
(11) Williams, J. J.; Wiersum, A. D.; Seaton, N. A.; Düren, T. Effect
of Surface Group Functionalization on the CO2/N2 Separation
Properties of MCM-41: A Grand-Canonical Monte Carlo Simulation
Study. J. Phys. Chem. C 2010, 114, 18538−18547.
(12) Powell, C. E.; Qiao, G. G. Polymeric CO2/N2 Gas Separation
Membranes for the Capture of Carbon Dioxide from Power Plant Flue
Gases. J. Membr. Sci. 2006, 279, 1−49.
(13) Ritter, J. A.; Ebner, A. D. State-of-the-Art Adsorption and
Membrane Separation Processes for Hydrogen Production in the
Chemical and Petrochemical Industries. Sep. Sci. Technol. 2007, 42,
1123−1193.
(14) Freemantle, M. Membranes for Gas Separation. Chem. Eng.
News 2005, 83, 3.
(15) Bernardo, P.; Drioli, E.; Golemme, G. Membrane Gas
Separation: A Review/State of the Art. Ind. Eng. Chem. Res. 2009,
48, 4638−4663.
(16) Celebi, K.; Buchheim, J.; Wyss, R. M.; Droudian, A.; Gasser, P.;
Shorubalko, I.; Kye, J.-I.; Lee, C.; Park, H. G. Ultimate Permeation
Across Atomically Thin Porous Graphene. Science 2014, 344, 289−
292.
(17) Li, D.; Hu, W.; Zhang, J.; Shi, H.; Chen, Q.; Sun, T.; Liang, L.;
Wang, Q. Separation of Hydrogen Gas from Coal Gas by Graphene
Nanopores. J. Phys. Chem. C 2015, 119, 25559−25565.
(18) Tao, Y.; Xue, Q.; Liu, Z.; Shan, M.; Ling, C.; Wu, T.; Li, X.
Tunable Hydrogen Separation in Porous Graphene Membrane: First-
Principle and Molecular Dynamic Simulation. ACS Appl. Mater.
Interfaces 2014, 6, 8048−8058.
(19) Blankenburg, S.; Bieri, M.; Fasel, R.; Müllen, K.; Pignedoli, C.
A.; Passerone, D. Porous Graphene as An Atmospheric Nanofilter.
Small 2010, 6, 2266−2271.
(20) Huang, L.; Zhang, M.; Li, C.; Shi, G. Graphene-Based
Membranes for Molecular Separation. J. Phys. Chem. Lett. 2015, 6,
2806−2815.
(21) O’Hern, S. C.; Boutilier, M. S. H.; Idrobo, J.-C.; Song, Y.; Kong,
J.; Laoui, T.; Atieh, M.; Karnik, R. Selective Ionic Transport through
Tunable Subnanometer Pores in Single-Layer Graphene Membranes.
Nano Lett. 2014, 14, 1234−1241.
(22) Surwade, S. P.; Smirnov, S. N.; Vlassiouk, I. V.; Unocic, R. R.;
Veith, G. M.; Dai, S.; Mahurin, S. M. Water Desalination Using
DOI: 10.1021/acs.jpcc.6b06940
J. Phys. Chem. C 2016, 120, 26061−26066
The Journal of Physical Chemistry C Article

Nanoporous Single-Layer Graphene. Nat. Nanotechnol. 2015, 10, 459− (45) Potoff, J. J.; Siepmann, J. I. Vapor−Liquid Equilibria of Mixtures
464. Containing Alkanes, Carbon Dioxide, and Nitrogen. AIChE J. 2001,
(23) Perreault, F.; Fonseca de Faria, A.; Elimelech, M. Environmental 47, 1676−1682.
Applications of Graphene-based Nanomaterials. Chem. Soc. Rev. 2015, (46) Chae, K.; Violi, A. Mutual Diffusion Coefficients of Heptane
44, 5861−5896. Isomers in Nitrogen: A Molecular Dynamics Study. J. Chem. Phys.
(24) Liu, G.; Jin, W.; Xu, N. Graphene-based Membranes. Chem. Soc. 2011, 134, 044537.
Rev. 2015, 44, 5016−5030. (47) Wall, Y.; Braun, G.; Kaltenborn, N.; Voigt, I.; Brunner, G.
(25) Gadipelli, S.; Guo, Z. X. Graphene-based Materials: Synthesis Separation of CO2/N2 by Means of a Carbon Membrane. Chem. Eng.
and Gas Sorption, Storage and Separation. Prog. Mater. Sci. 2015, 69, Technol. 2012, 35, 508−512.
1−60.
(26) Joshi, R. K.; Alwarappan, S.; Yoshimura, M.; Sahajwalla, V.;
Nishina, Y. Graphene Oxide: the New Membrane Material. Appl.
Mater. Today 2015, 1, 1−12.
(27) Smith, Z. P.; Freeman, B. D. Graphene Oxide: A New Platform
for High-Performance Gas- and Liquid-Separation Membranes. Angew.
Chem., Int. Ed. 2014, 53, 10286−10288.
(28) Huang, H.; Ying, Y.; Peng, X. Graphene Oxide Nanosheet: An
Emerging Star Material for Novel Separation Membranes. J. Mater.
Chem. A 2014, 2, 13772−13782.
(29) Kim, H. W.; et al. Selective Gas Transport Through Few-
Layered Graphene and Graphene Oxide Membranes. Science 2013,
342, 91−95.
(30) Shen, J.; Liu, G.; Huang, K.; Jin, W.; Lee, K.-R.; Xu, N.
Membranes with Fast and Selective Gas-Transport Channels of
Laminar Graphene Oxide for Efficient CO2 Capture. Angew. Chem.
2015, 127, 588−592.
(31) Sun, C.; Boutilier, M. S. H.; Au, H.; Poesio, P.; Bai, B.; Karnik,
R.; Hadjiconstantinou, N. G. Mechanisms of Molecular Permeation
through Nanoporous Graphene Membranes. Langmuir 2014, 30,
675−682.
(32) Cohen-Tanugi, D.; Grossman, J. C. Water Desalination across
Nanoporous Graphene. Nano Lett. 2012, 12, 3602−3608.
(33) Jiang, D.-e.; Cooper, V. R.; Dai, S. Porous Graphene as the
Ultimate Membrane for Gas Separation. Nano Lett. 2009, 9, 4019−
4024.
(34) Ban, S.; Xie, J.; Wang, Y.; Jing, B.; Liu, B.; Zhou, H. Insight into
the Nanoscale Mechanism of Rapid H2O Transport within a Graphene
Oxide Membrane: Impact of Oxygen Functional Group Clustering.
ACS Appl. Mater. Interfaces 2016, 8, 321−332.
(35) Wei, N.; Peng, X.; Xu, Z. Understanding Water Permeation in
Graphene Oxide Membranes. ACS Appl. Mater. Interfaces 2014, 6,
5877−5883.
(36) Wu, H.; Chen, J.; Liu, H. Molecular Dynamics Simulations
about Adsorption and Displacement of Methane in Carbon Nano-
channels. J. Phys. Chem. C 2015, 119, 13652−13657.
(37) Jiao, S.; Xu, Z. Selective Gas Diffusion in Graphene Oxides
Membranes: A Molecular Dynamics Simulations Study. ACS Appl.
Mater. Interfaces 2015, 7, 9052−9059.
(38) Medhekar, N. V.; Ramasubramaniam, A.; Ruoff, R. S.; Shenoy,
V. B. Hydrogen Bond Networks in Graphene Oxide Composite Paper:
Structure and Mechanical Properties. ACS Nano 2010, 4, 2300−2306.
(39) Kim, D.; Kim, D. W.; Lim, H.-K.; Jeon, J.; Kim, H.; Jung, H.-T.;
Lee, H. Intercalation of Gas Molecules in Graphene Oxide Interlayer:
the Role of Water. J. Phys. Chem. C 2014, 118, 11142−11148.
(40) Gao, W.; Alemany, L. B.; Ci, L.; Ajayan, P. M. New Insights into
the Structure and Reduction of Graphite Oxide. Nat. Chem. 2009, 1,
403−408.
(41) Lerf, A.; He, H.; Forster, M.; Klinowski, J. Structure of Graphite
Oxide Revisited. J. Phys. Chem. B 1998, 102, 4477−4482.
(42) Plimpton, S. Fast Parallel Algorithms for Short-Range Molecular
Dynamics. J. Comput. Phys. 1995, 117, 1−19.
(43) Shih, C.-J.; Lin, S.; Sharma, R.; Strano, M. S.; Blankschtein, D.
Understanding the pH-Dependent Behavior of Graphene Oxide
Aqueous Solutions: A Comparative Experimental and Molecular
Dynamics Simulation Study. Langmuir 2012, 28, 235−241.
(44) Jorgensen, W. L.; Maxwell, D. S.; Tirado-Rives, J. Development
and Testing of the OPLS All-Atom Force Field on Conformational
Energetics and Properties of Organic Liquids. J. Am. Chem. Soc. 1996,
118, 11225−11236.

26066 DOI: 10.1021/acs.jpcc.6b06940

J. Phys. Chem. C 2016, 120, 26061−26066