J Mater Sci

Efficient ethanol/water separation via functionalized

nanoporous graphene membranes: insights
from molecular dynamics study
Qi Shi1,2, Zhongjin He2, Krishna M. Gupta2, Yunhui Wang1,2, and Ruifeng Lu1,*

1
Department of Applied Physics, Nanjing University of Science and Technology, Nanjing 210094, China
2
Department of Chemical and Biomolecular Engineering, National University of Singapore, 117576 Singapore, Singapore

Received: 16 June 2016 ABSTRACT

Accepted: 18 August 2016
Ó Springer Science+Business
Media New York 2016
Systematic molecular dynamics simulations are conducted to study the sepa-
ration of ethanol/water mixture through single-layer graphene with designed
nanoscale pores. The effects of pore size, chemical functionalization, and
applied pressure were investigated. It was found that the diameter of pore plays
a key role for efficient separation of ethanol from water. With appropriate
diameter, water molecules can pass through but flow of ethanol is essentially
blocked. Compared to hydrophobic, hydrophilic functionalization is found to be
more efficient for ethanol/water separation as energy barrier for water molecule
is less than ethanol in case of hydrophilic porous graphene membrane. Overall,
our results indicate that the flux through hydrophilic functionalized (P2_OH)
graphene membrane is nearly four times higher than conventional reverse
osmosis membranes with a good selectivity for ethanol/water separation. This
simulation study provides molecular-level understanding of ethanol/water
separation through functionalized nonporous graphene and reveals the key
governing factors that are essential for designing novel graphene membranes for
bioethanol purification.

Introduction for commercial use, for example, the United States

Bioethanol, as the most promising renewable and
clean energy source, can effectively reduce the
dependence on fossil fuels and inhibit the greenhouse
effect [1–3]. In addition, it can be added to gasoline as
an oxygenate which has been used as a fuel in several
countries [4–6]. Bioethanol has already been applied
and Brazil are the world’s largest producers of bioe-
thanol, accounting for 87 % of global biofuel pro-
duction [7–9]. It is mainly produced by the
fermentation of biomass feedstocks (e.g., starch, cel-
lulose). However, fermentation broths only contain
5–12 wt% ethanol, which need to be further concen-
trated and dehydrated in order to use bioethanol as
fuel (99.5 wt% ethanol) [10]. Azeotropic distillation,

Address correspondence to E-mail: rflu@njust.edu.cn

DOI 10.1007/s10853-016-0319-4

extractive distillation, vapor permeation separation,
membrane separation, and molecular sieve adsorp-
tion–separation [11–13] have been suggested for
ethanol/water separation [12]. Among these tech-
niques, membrane separation is the most promising
because of easy operation, low energy consumption,
and small carbon footprint [10, 11].
In the past decades, several materials have been
studied as potential membranes for the ethanol/water
separation [14–18]. Polymer or polymer-based hybrid
membranes have also been widely used in ethanol/
water separation owing to their relatively low cost and
ease of processing [19–37]. Nevertheless, plasticization
and swelling significantly decrease the performance of
the polymer membranes and alter their permeability
and selectivity. In this regard, mixed matrix mem-
branes with high-silica zeolite (ZSM-5) dispersed in
polydimethylsiloxane have been found to be effective
in removing ethanol from aqueous mixtures via per-
vaporation [14, 15, 17, 38–41]. Another class of porous
materials named metal–organic frameworks (MOFs)
have also been tested for the separation of alcohol/
water mixtures [42–44], but their performances are not
up to industrial benchmarks. To develop alternate
membrane materials, the key challenges are to achieve
the targets of high flux and selectivity. Ideally, an
efficient ultrafast membrane should be as thin as
possible to maximize the penetration, be robust
enough to withstand the applied pressure, and have a
narrow distribution of pore size for excellent selec-
tivity. Up to date, none of these nanomaterials have
proved efficient ethanol/water separation.
As a mostly studied two-dimensional structure,
graphene has atomic thickness, high mechanical
strength, and chemical inertness. It has been con-
firmed to be an excellent material for developing size-
selective molecular separation membranes [45–50].
Many theoretical studies have demonstrated that the
atomically thick porous graphene (PG) membrane
exhibits superior separation performance for gases
[51–53], water [54–56], and ions [57, 58]. Molecular
dynamics (MD) simulation studies have predicted
that monolayer graphene with sub-nanometer pores
could act as a highly selective and permeable sepa-
ration membrane with much higher efficiencies than
polymeric filtration membranes [59–61]. On the other
hand, experimental studies elucidating this behavior
have thus far been limited because of the challenge of
fabricating leak-free, large area, and single-layer PG
membranes. Transport measurements through
J Mater Sci
graphene have been accomplished merely on micro-
scopic areas with few pores or on multilayered gra-
phene-oxide membranes.
Most recently, Hou et al. [62] presented direct
computational evidence that nanoporous graphene
could be a promising sieving membrane for the
separation of ethanol/water mixtures, with ethanol
permeability several orders of magnitude higher than
current pervaporation membranes. Based on the
nanoporous graphene models designed without any
termination in the pores, they found that interfacial-
affinity sieving is more crucial than pore-size sieving.
It should be noted that the functionalization of
nanoporous graphene sheets with various active
groups and inorganic nanoparticles results in new
class of exciting materials for membrane applications.
Cohen-Tanugi and Grossman made first attempt to
study the role of chemical functionalization on the
edges of graphene pores for water desalination [63].
Using MD simulations, they suggest that the hydro-
xyl groups can double the water flux due to their
hydrophilic character.
To the best of our knowledge, there is no report so
far on the biofuel purification by functionalized
nanoporous graphene sheets. Despite the prevailing
challenges of large-scale application and pressure-
driven separation [64–67], it is necessary and desirable
to further explore the PG nanosheets with well-de-
fined pores as high-efficient membranes for molecular
separation because of their atomic thicknesses.
Therefore, in this study, we have investigated etha-
nol/water separation using single-layer graphene
with various pores and functionalizations that were
mimicked by hydrophilic (–OH) as well as
hydrophobic (–H) terminations. From detailed MD
simulations, we showed how the separation perfor-
mance changes with pore size, pore’s chemical envi-
ronment, and applied hydrostatic pressure. Following
this introduction, the molecular models and simula-
tion methods are described in ‘‘Simulation models and
methods.’’ In ‘‘Results and discussion,’’ result and
detailed discussions are presented. Finally concluding
remarks are summarized in ‘‘Conclusions.’’
Simulation models and methods
Since the kinetic diameters of water and ethanol are
3.0 and 4.3 Å, respectively [68], we drilled three types
of pores in the graphene layer with different pore
J Mater Sci

Figure 1 Functionalized
graphene nanopores: a large
hydrogenated graphene pore
(P1_H), b middle-size
hydrogenated graphene pore
(P2_H), c small hydrogenated
graphene pore (P3_H), d large
hydroxylated graphene pore
(P1_OH), e middle-size
hydroxylated graphene pore
(P2_OH), f small
hydroxylated graphene pore
(P3_OH), g a snapshot of the
simulation system. Colors
cyan (C), red (O), white (H).

size. Then, the pore edges were terminated with
hydroxyl groups (which are hydrophilic in nature)
and hydrogen atoms (hydrophobic) in order to
examine the effect of pore chemistry on ethanol/
water separation, as shown in Fig. 1a–f. These pores
are slightly larger than the kinetic diameter of ethanol
molecule. The graphene was functionalized with 12,
10, 9 number of either –H or –OH groups. The
notations are: 12 –H or –OH, P1_H or P1_OH; 10 –H
or –OH, P2_H or P2_OH; 9 –H or –OH, P3_H or
P3_OH. The atomic charges of the atoms around the
pores are from OPLS-AA force field. For membranes
terminated with –OH group, the charges of O, H, and
C atoms connected with O are -0.585 e, 0.435 e, and
0.15 e, respectively. For membranes with –H group,
the charges of H and C atoms connected with H are
0.115 e and -0.115 e, respectively. Pore diameters
were obtained from the formula d = 2H(A/p) by
plotting atoms as van der Waals spheres in the pore
centers and by calculating the amount of contiguous
area not obstructed by any atomic representation,
which are similar to other works [63].
For each system, our performed simulations
include two parts: (1) an equilibration MD simulation
(EMD) and (2) a non-equilibration MD simulation
(NEMD). First, an initial simulation box of dimension
32 9 32 9 60 Å3 that contains 1 PG layer, 500 etha-
nol, and 500 water molecules was constructed (etha-
nol and water molecules are randomly inserted in the
simulation box to get an equimolar mixture of

ethanol/water). Then, an energy minimization fol-
lowed by a 2 ns EMD simulation in NPT ensemble at
1 bar were performed to get a precise dimension
along z direction of the simulation box. Finally, a
10 ns NEMD simulation, using the last configuration
of the EMD simulation as initial configuration, was
conducted in NVT ensemble to study the separation
performance of ethanol/water across the PG mem-
brane. The schematic illustration of the simulation
system is shown in Fig. 1g. The functionalized PG
was initially placed in the x–y plane of the orthogonal
unit cell at z = 30 Å and the z-axis is normal to the
PG membrane. Periodic boundary conditions were
considered in all axial directions to mimic a system
with an infinitely large area. For all NEMD and EMD
runs, the carbon atoms at the boundary of the PG
were held fixed to prevent a horizontal displacement
of graphene layer along z direction, while the other
atoms of PG were flexible, and ethanol and water
molecules were allowed to move freely during the
simulations.
All MD simulations were performed using the
GROMACS 4.5.3 package [69]. To represent realistic
water molecules, the intermolecular three-point
potential (TIP3P) model [70] was used. The Ewald
method was taken to handle the electrostatic inter-
actions in the simulations. Van der Waals interactions
were truncated smoothly by means of a 12 Å spher-
ical cutoff in conjunction with a switching function.
The potential energy of intermolecular interactions is
characterized by the sum of Lennard-Jones (LJ) and
Coulomb potentials:
" 
X  6 # X
rij 12 rij qi qj
Unonbonded ¼ 4eij  þ ;
rij rij 4pe0 rij
ð1Þ
where rij refers to the distance between atoms i and j,
eij and rij represent the LJ parameters that are related
to atoms i and j, and qi andqj represent the partial
charge assigned to atoms i and j, respectively. The
OPLS-AA force field was used for ethanol, water, and
PG. The LJ parameters for determining the interac-
tion between different atoms were calculated with
the combination rules: eij = (eiej)1/2, rij = (rirj)1/2.
External forces are applied to both ethanol and
water molecules to create a pressure drop, ranging
from 50 to 200 MPa, across the PG along the ?z
direction (as shown in Fig. 1g). We use high pressure
to accelerate our simulations and obtain well-
J Mater Sci
converged statistics for time scales involved in the
MD calculations. The technique extended by Zhu
et al. [71] was employed in our systems to create a
corresponding pressure gradient between two sides
of the PG layers. The applied force on ethanol/water
molecules is given by
DP ¼ nf=A; ð2Þ
where f is a constant force along the ?z direction of
the system, DP is the chosen pressure, A is the area of
the x–y plane, and n is the number of ethanol or water
molecules in the simulation box. This method has
been used in many studies of pressure-driven flow
[72–78].
The NPT and NVT ensembles were used with a
Nosé–Hoover thermostat [79, 80] at 298 K with an
initial Gaussian velocity distribution consistent with
this temperature. We carried out 10 ns NEMD sim-
ulations with a time step of 1 fs in which first 4 ns
trajectories are for equilibration and other 6 ns are for
production. For each system, three sets of indepen-
dent simulations with different initial seeds were
performed and properties were calculated by aver-
aging over three sets.
Results and discussion
The numbers of ethanol and water molecules trans-
ported across the functionalized pores at 200 MPa as
a function of time are provided in Fig. 2. The profiles
show that the flow rates of both ethanol and water
scale linearly with time. For larger pores P1_H and
P1_OH, the permeations of both water and ethanol
are dependent on the pore size instead of pore
affinity. With large pore size of P1_H (8.2 Å) com-
pared to P1_OH (6.6 Å), the net transfer for both
water and ethanol is higher in P1_H. Again, due to
smaller size of water than ethanol, net transfer of
water is higher than ethanol for all cases. For ethanol,
the flow in P2_OH and P3_OH is relatively lower
than that in P2_H and P3_H (Fig. 2a). With large size
of ethanol (4.3 Å), ethanol flow was restricted by
smaller pores of P2_OH and P3_OH (4.6 and 3.8 Å)
compared to large pores P2_H and P3_H (5.6 and 5.2
Å). Nevertheless, the flow of water in P2_OH and
P3_OH is almost the same with the P2_H and P3_H
(Fig. 2b). This is attributed to the strong interaction of
water molecules with –OH groups at the edge of the
functionalized pores. In contrast, for larger pores
J Mater Sci

Figure 2 Number of net

transferred a ethanol
molecules NETH(t) and
b water molecules
NWAT(t) through the PG layer
at the pressure of 200 MPa.

Figure 3 Number of net

transferred a ethanol
molecules NETH(t) and
b water molecules
NWAT(t) across the P1_H
membrane as a function of
time. c NETH(t) and
d NWAT(t) across the P1_OH
membrane.

(such as P1_H and P1_OH), both ethanol and water
molecules pass very fast where effect of pore affinity
is insignificant. For P3_OH where the pore size is
almost equal to the kinetic diameter of ethanol
molecule, the ethanol molecules are fully blocked
without permeation. From Fig. 2, we can see that the
pore size of P3_H and P3_OH is so small for ethanol
and water passing through. The separation perfor-
mance of the two pores is not so good. In general for
both ethanol and water molecules passing through
the PG layer, the larger the pore size, the more the net
transferred molecules. When the pore size becomes
more close to the kinetic diameter of water molecule,
the chemical nature of the functional group plays a
dominate role in water permeation.
In Fig. 3, we show plots of ethanol and water flows
across P1_H and P1_OH pores as a function of time at
different applied pressures. We observed that the
flow rates of ethanol/water are almost constant in
time and increase with applied pressure substantially
(Fig. 3a–d). Comparatively, for relatively small func-
tionalized pores P2_H and P2_OH (Fig. S1a–d), the
flow profiles are no more linearly increasing in time
at low pressure of 50 MPa, especially for larger
ethanol molecules passing through the functionalized
pores (Fig. S1a, c), which means that each ethanol
 J Mater Sci

Figure 4 Flux as a function

of applied pressure across
a P1_H, b P1_OH, c P2_H,
and d P2_OH membranes.

Table 1 Comparison of
performance between PG and Membrane Flux (g m-2 h-1 bar-1) Separation factor Reference
bacterial cellulose/alginate
P1_H 10200.0 ± 293.2 3.5 ± 0.2 This work
(BCA) nanocomposite
P1_OH 5991.7 ± 149.5 3.8 ± 0.2 This work
membrane for equimolar
P2_H 2500.6 ± 155.3 3.0 ± 0.4 This work
ethanol/water mixtures at
P2_OH 1656.2 ± 399.4 13.2 ± 3.8 This work
room temperature
BCA 453.7 ± 3.5 16.1 ± 0.2 Ref. [11]

molecule needs an averagely longer time than water
molecule to travel across the smaller pores. Because
the ethanol/water permeation is a random event, if
the net transferred number of ethanol or water
molecule is too small, the flow will not change lin-
early with time.
On the basis of the number of net transferred
ethanol and water molecules as a function of time,
ethanol and water fluxes permeating the PG layer
were estimated and plotted in Fig. 4. For all pores,
the flux of ethanol or water changes somehow non-
linearly with the applied pressure. Unlike desalina-
tion system, in which the number of water molecules
is much larger than Na? and Cl-, our simulation
system, as an equimolar binary mixture liquid solu-
tion, has much more complex interactions between
ethanol and water molecules, which cause the
nonlinear flux to increase under the external pres-
sure. In Fig. 4c and d, the pore functional effect is
obvious for water at an external pressure of 100 MPa.
For P2_H pore, the –H group inhibits the water per-
meation (Fig. 4c) at 100 MPa, while for P2_OH pore,
the –OH group enhances the water permeation
(Fig. 4d) at 100 MPa. This phenomenon can only be
observed in smaller pores and at 100 MPa, because
for larger pores or high pressure, water molecules
can penetrate the PG layer quickly that the time of the
interaction between water molecules and functional
groups is very short. For lower pressure difference,
the net transferred number of water molecules is too
less to observe the phenomenon.
To judge the performance of ethanol/water sepa-
ration, pressure-normalized flux and separation per-
formance of the PG membranes are listed in Table 1
J Mater Sci
Figure 5 The density profiles
of a ethanol and b water
across the P1_H pore,
c ethanol and d water across
the P1_OH pore, at different
pressures in z direction of the
system.
and compared with the bacterial cellulose/alginate
(BCA) nanocomposite membrane. The PG mem-
branes with pores P1_H, P1_OH, and P2_H have
much higher fluxes compared to BCA but the sepa-
ration factor is very poor. Nevertheless, P2_OH has
nearly four times higher flux than BCA with sepa-
ration factor almost similar. Therefore, P2_OH could
be a better choice for ethanol/water separation.
To deeply understand the distribution of ethanol
and water molecules, we present the density profiles
of ethanol and water for P1_H and P1_OH mem-
branes at different applied pressure as shown in
Fig. 5. The density of ethanol at the left interfacial
layer adjacent to PG is a little lower than in the right
interfacial layer (Fig. 5a, c). On the contrary, for water
(Fig. 5b, d), the density at the left interfacial layer is
much higher than in the right one. This is attributed
to the smaller size and lighter weight of water
molecules, in other words, water molecules are easier
to be pushed to the region in front of the PG. For
P2_H and P2_OH pores, similar density profiles are
plotted in Fig. S2.
In order to further understand the underlying
mechanism of separation process, the free energy
profiles are plotted in Fig. 6. The energetic barrier for
ethanol and water molecules at different positions
along z direction were calculated by
FðrÞ ¼ RTln½qðrÞ; ð3Þ
where R is the gas constant, T is the temperature,
and q(r) is the density at position r. The method is
a quick way to calculate the free energy profiles
and frequently used in other works [81–84]. The
peaks in the middle of each simulation cell (z = 3.0
Å) for both ethanol and water molecules demon-
strate that ethanol and water need to overcome a
specific free energy barrier to pass through the PG
layer. For ethanol, two obvious potential wells are
observed at both sides of the PG at a distance of
0.3 nm from PG, implying that two layers of etha-
nol molecules exist around the PG layer. For water,
a deep potential well and a shallow potential well,
respectively exist on the front side and the back
side of the PG. Therefore, the water molecules are
easier to stay in the front of the PG under the
influence of external pressure. For P2_H and
P2_OH pores, free energy profiles are shown in
Fig. S3, and similar results can be found. In
Table S1, we list the energy barriers of ethanol and
water across the PG. Generally, the trend is
 J Mater Sci

Figure 6 The free energy

profiles for ethanol/water
passing through the P1_H (left
panels) and P1_OH (right
panels) membranes.

consistent with the flux profiles. Particularly for PG Conclusions

membrane with P2_OH pore, due to the
hydrophobic functional group, the energy barrier Separation of ethanol/water mixture through single-
for ethanol permeation is smaller by *3 kJ/mol layer graphene with designed nanoscale pores is
than that for water permeation. investigated. It was observed that graphene
J Mater Sci
nanosheets with suitable nanopores are able to reject
ethanol molecules while allow a fast water flux. The
diameter of the pore and chemical functionalization
are found to govern ethanol/water separation, par-
ticularly performance is more sensitive to the pore
size than pore’s chemistry. Due to lower potential
barrier in the pore vicinity of hydrophilic compared
to hydrophobic PG membrane, water flux is higher.
More specifically, water flux through hydrophilic
functionalized (P2_OH) graphene membrane is
nearly 4 times higher than conventional reverse
osmosis membranes with reasonably good separation
factor for ethanol/water mixture. This simulation
unveils the key governing factors that are important
to design potential graphene membranes for high
performance purification. This work also highlights
the promise of atomically thin and periodic nanos-
tructures like graphene for ethanol/water separation
if nanopores exist, and we expect that PG will be
useful for other organic solution separation and more
monolayer membrane will be developed for ethanol/
water separation in the nearby future.
Acknowledgements
This work was supported by NSF of China (Grant
Nos. 21373113, 21506178), Fundamental Research
Funds for the Central Universities (Grant No.
30920140111008), and the National University of
Singapore (R 279 000 437 112). Q. Shi also acknowl-
edges the support from the program of China
Scholarship Council (CSC).
Electronic supplementary material: The online
version of this article (doi:10.1007/s10853-016-0319-
4) contains supplementary material, which is avail-
able to authorized users.
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