Article

pubs.acs.org/JPCC

Observation and Analysis of Water Transport through Graphene

Oxide Interlamination
Bo Chen, Haifeng Jiang,* Xiang Liu, and Xuejiao Hu*
Key Laboratory of Hydraulic Machinery Transients of Ministry of Education, School of Power and Mechanical Engineering, Wuhan
University, Wuhan, Hubei 430072, China

ABSTRACT: Water transport inside graphene-based materi-

als has drawn much attention nowadays because of its
promising potential in ions filtration applications. Using
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molecular dynamics (MD) simulations, we investigated the

mechanism of water transport inside the interlayer gallery
between graphene oxide layers. The model of slipped-
Poiseuille flow was cited to depict the characteristic transport
of interlayer flow. This significant flow rate was related to slip
velocity of water, which is constrained by hydrogen
interactions between water molecules and hydroxyl groups.
We find that hydrogen-bond networks are correlated with both
functionalization and nanoconfinement. MD simulation results
show that the slip velocity is negatively correlated with oxide concentration while independent of the array of hydroxyl groups,
and the volumetric flux is linearly dependent to the slip velocity. It reveals that graphene oxide layers could get better water
permeability after reduction.

■ INTRODUCTION
Water is the backbone of industry, agriculture, and economy all
over the world.1 With the striking growth of population and
industrial activities, freshwater and energy scarcity are the most
severe challenge in the 21st century.2,3 Thus, water desalination
is expected to play an increasingly crucial role to provide fresh
and sustainable water for many water stressed communities and
industrial sectors. Desalination processes are generally classified
as thermal or membrane based technologies. Membrane
process, such as reverse osmosis (RO), has been more prevalent
in industrial development for several decades mainly due to its
energy efficiency contrast to other desalination methods.4
However, there are some limitations in the use of these
membrane methods, such as self-contamination, huge power
requirements, low water permeability, and so on.5 Nowadays,
many nanostructured materials have been investigated to
improve the process of water purification. In particular,
graphene-based membrane is identified as one of the most
promising material for water desalination because of its
outstanding ions filtration, high water permeability, feasible
fabrication of functional group and so on.4−8
Surwade et al. manufactured nanoporous graphene (NPG)
membrane through bombarding the suspended graphene by
gallium ions and electrons, and they observed that water could
pass through the NPG membrane quickly while the salt
rejection could be 100% by controlling the radius of the
nanopore.9 Using molecular dynamics simulations, Grossman
have investigated that NPG membrane with pores decorated by
hydrogen atoms or hydroxyl could not only effectively enhance
the rejection of ions but also improve the permeation of water.10
Besides, NPG membranes with pores doped specific atoms can
also be utilized for filtration and separation of mixed gases.11−13
Graphene oxide has been found recently as another
membrane suitable for desalination because of its ease of
fabrication, mechanical strength and industrial scale production
compared to ordinary graphene sheets.14−17 Many researches
have proved that the graphene-based membrane have excellent
properties of salt selectivity and water permeability.18,19 In the
work of Nair et al.,12 mass leakage tests have been performed
using spin-coating graphene oxide membranes. These submi-
crometer thick membranes are almost completely impermeable
to gases like helium but allow unimpeded permeation of water
vapor. Sun et al. have investigated a series of solutes in water
through graphene oxide membranes and concluded that the
heavy metal salts got the weakest permeability.15 The theoretical
research related to water flow across multilayer graphene
membranes have been explored by Yoshida via numerical
simulation.20 They showed that results for the permeability
calculated by continuum hydrodynamic model are in agreement
with those obtained by MD simulations. All of researches above
have demonstrated the outstanding transmembrane perme-
ability of water, but it is still obscure in the mechanism of mass
transport interlaminated graphene or graphene oxide sheets.
In this work, we performed pressure-driven flow simulations
to reveal the nature of interlayer flow between the graphene
oxide sheets and to clarify the influence of surface functionaliza-
tion in combination with layer distance on water permeation.
Received: September 27, 2016
Revised: December 30, 2016
Published: January 3, 2017

© 2017 American Chemical Society 1321 DOI: 10.1021/acs.jpcc.6b09753

J. Phys. Chem. C 2017, 121, 1321−1328
The Journal of Physical Chemistry C
Figure 1. Atomic structure of graphene oxide. (a) Initial configuration of simulation. (b) Structure of graphene oxide sheets. Gray, red, white. and pink
spheres represent carbon atoms, hydrogen atoms and oxygen atoms in hydroxyl, and hydrogen atoms and oxygen atoms in water molecules,
respectively.
The model of slipped-viscous flow is cited to elucidated the
dynamics of fast water flow between the pristine graphene
layers, while flow enhancement is reduced by hydrogen bonds
between the surface and water molecules in graphene oxide
sheets.20,21 We find that hydrogen-bond networks are correlated
with both functionalization and nanoconfinement.
■ THEORY
Interlayer water transport between graphene oxide sheets can be
considered as the slipped Poiseuille flow confined between two
flat plates separated by a distance d. Generally, the velocity
profiles of no slip flow is parabolic:
Δp ⎛ D2 ⎞ of hydrogen bonds apply stronger interaction between graphene
V= ⎜ − h2⎟
2ηl ⎝ 4 ⎠ (1)
Here Δp, η, l, D, and h denote the pressure difference, the
viscosity of water, the length of plates, the distance between two
plates, and the location perpendicular to the plate, respectively.
The volumetric flux Q can be estimated by the integral of the
velocity function:
D3W dp
Q no − slip = −
12η dx
Here dp/dx expresses the pressure gradient along the flow
direction and W is the width of the plate. In refs 12−14, the fast
mass transport upon graphite sheet or through carbon nanotube
is often attributed to the low-friction and superlubricity
phenomenon during water flow. Graphene oxide can be
considered as two parts. The pristine graphene region, enhances
the flow like water−graphite/water−carbon nanotube system.
Article
The oxidic region, reduces the enhancement of transport,
because the hydrogen bonds between water molecules and
hydroxyl groups capture the flowing water molecules near the
wall and increase the friction between fluid and boundary.
Therefore, interlayer flow between graphene oxide gallery is the
coupling of superlubricity flow and viscous flow. The flux ratio
of part slippage flow to no slip flow can be estimated as
Q slip ⎛ D 2 dp ⎞
= 1 + vs /⎜ − ⎟
Q no − slip ⎝ 12η dx ⎠ (3)
where vs is the slip velocity, related to the concentration of oxide.
With the growth of oxide concentration, the increasing number
walls and water molecules as well as reduce the effect of slipped-
boundary and the slip velocity.
■
SIMULATION MODEL
The molecular structure of graphene oxide generally consists of
hydroxyl, epoxy, carbonyl groups, defective sites and open edges
on the pristine graphene plane.14,22 The hydroxyl groups are
investigated in this work because they were reported to be able
to remain rich in the long-living quasi-equilibrium state.23,24 The
(2)
initial configuration was water sandwiched between two
graphene oxide sheets, as shown in Figure 1a. The molecular
structure of graphene oxide is presented in Figure 1b. For
oxidized domain of graphene oxide, we constructed hydroxyl
function groups at concentration c = nOH/nC ranged from 0
(pristine graphene) to 25%, where nOH and nC are the number of
hydroxyl groups and carbon atoms, respectively. Different layer
distances of capillary channels at c = 10% were also performed in
1322 DOI: 10.1021/acs.jpcc.6b09753
J. Phys. Chem. C 2017, 121, 1321−1328
The Journal of Physical Chemistry C Article

this study. There were 1200, 1800, 2400, and 3000 water
molecules inserted initially corresponding to interlayer distance
h of 1.1, 1.5, 1.9, and 2.3 nm, respectively. Besides, the influence
of uniform and random distribution of hydroxyl groups was
investigated as well.
Molecular dynamics (MD) simulations were performed using
the LAMMPS package.25 The simulation system dimensions are
15 × 3 × 3 nm in x, y, z, respectively, where period boundary
conditions were used on all dimensions. The all-atom optimized
potentials for liquid simulations (OPLS-AA) were used for
graphene oxide, which are widely used to capture essential
many-body terms in interatomic interactions. The rigid simple
point charge effective pair (SPC/E) model were used for water
molecules. Both of them include van der Waals and electrostatic
terms.23,24,26 The potential parameters of atoms are given in
Table 1. The characteristic length σ and energy parameter ε

Table 1. Potential Parameters of Atom

Figure 2. Velocity profiles along z axis for different pressures ranging
atom σ (Å) ε(kcal/mol) from 10 to 850 MPa.
C (C−C) 3.851 0.105
C (C−OH) 3.550 0.070
O (C−OH) 3.070 0.170
H (C−OH) 0.000 0.000
O (H2O) 3.166 0.1553
H (H2O) 0.000 0.000

between water molecules and carbon atoms were obtained by

the common Lorentz−Berthelot combination rule.27 The van
der Waals interactions are truncated at 1.2 nm, and the long-
range Coulomb interactions are computed by utilizing the
particle−particle particle-mesh (PPPM) algorithm.28
We performed the pressure-driven water flow by directly
adding forces to water molecules in nonequilibrium molecular
dynamics simulations, which was widely used to investigate fluid
flow.24,29 The simulation process lasted for a sufficiently long
time (4 ns) at 298 K to reach equilibrium, and the sample
evolved for 1 ns for data collection. The coordinates and
velocities of all the atoms were recorded every 50 ps to get
converged results. All the MD simulations were performed in Figure 3. Volumetric flux as a function of applied pressure, where the
square scatters represents for the MD simulation results and the dash
constant number of particles, volume, and temperature (NVT) dot line denotes for the fitting plot of relation between flux and driven
ensemble. The postprocessing was made by Visual Molecular pressure. In particular, the circle dot represents for the pressure in the
Dynamics (VMD)30 and The Open Visualization Tool simulation followed.
(OVITO).31

■ RESULTS AND DISCUSSION

We specifically noted that the pressures applied in our works
were significantly greater than the pressures employed in RO
plants (<8 MPa).10 To obtain precise data for water flux in a
finite simulation time, a high simulated pressure on the order of
∼1000 MPa was performed in this simulation. To justify this
approach’s reasonability, we investigated the water flow driven
by different applied pressures ranged from 11.1 to 850 MPa,
which was interlaminated between graphene oxide sheets with
the same interlayer distance and oxide concentration (h = 1.9
nm, c = 10%). The velocity profile at every pressure obviously
presented the characteristic of parabolic distribution as shown in
Figure 2. It reveals that the model of Poiseuille flow is also
suitable for low pressure drop. In Figure 3, the linearity of water
flux scaling with driving pressure ensured that results obtained at
high pressure can be extrapolated to calculate the water flux
from lower net driving pressures in an RO system. In particular,
the circle dot in Figure 3 represents for the pressure we
1323
performed in the simulation of different oxide concentration and
interlayer spacing followed.
We have investigated the effects of oxide concentration and
interlayer spacing in detail. The representative snapshots of
water flow between graphene sheets and graphene oxide layers
are illustrated in Figure 4. It is observed that water flows in the
channel of graphene sheets with the formation of 0.05 nm-thick
vacuum region along the gallery walls. It is mainly due to the
hydrophobic interaction between water and graphene, which
induces fast water transport by low-friction and superlubricity
within the pristine graphene channels. In contrast, water
molecules are easy to attach on the hydrophilic oxidic regions
because of the hydrogen bonds between water molecules and
hydroxyl groups. These arguments were made by assuming that
the reduced capillary driven flow sandwiched between graphene
oxide layers breaks down the expected flow enhancement.
In order to quantify the effect of oxidic regions on pristine
graphene sheets on water transport, variable concentrations of
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Figure 4. Represented snapshots of water flow. (a) Interlayer flow between graphene oxide. (b) Interlayer flow between graphene. Red, white, pink,
blue, and light yellow spheres represent carbon atoms, hydrogen atoms and oxygen atoms in hydroxyl, and hydrogen atoms and oxygen atoms in water
molecules, respectively.

Figure 5. Velocity profiles along z axis for different oxide concentration: (a) c = 0−0.1; (b) c = 0.1−0.25.

hydroxyl groups are monitored during the simulation, and the
well-characterized velocity profiles are exhibited in Figure 5. It is
clearly shown that the velocity profile for flow changes from low
curvature (c < 10%) to parabolic one at high c values, and the
parabolic viscous flow characteristics covered all the concen-
trations with some fluctuations when it is greater than 10%. The
parabolicity of velocity profile implies that the viscous flow
between parallel plates in continuum hydrodynamics, which can
be calculated by the Poiseuille solution of the Navier−Stokes
equations. Specially, at c = 0, namely water flow between
graphene sheets, the velocity profile is nearly planus, showing
the unimpeded water transport in basal graphene nanochannels.
1324
In contrast, the hydroxyl groups would reduce the enhancement
of water flow.
To obtain the flux of water through the graphene oxide layers
with slipped-boundary, we get the function of velocity profiles
by parabolic fitting, and the volumetric flux Q can be estimated
by integral of velocity function as shown in Figure 6a−d. The
slip velocity as a function of c values is exhibited in Figure 6e. It
is obvious that the flux and slip velocity are negatively correlated
with oxide concentration while they get little fluctuation at high
values, in consistent with Poiseuille flow. The flux ratio as a
function of slip velocity is presented in Figure 6f, and the profile
is linear as predicted in eq 3. It follows that water transport
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The Journal of Physical Chemistry C Article

Figure 6. (a−d) Velocity function at low concentration. (e) Relationship between concentration and slip velocity. (f) Relationship between flux ratio
and slip velocity.

between graphene oxide layers has great relationship with
hydroxyl groups on basal plane. Besides, the velocity profiles of
uniform and random array of hydroxyl groups at the same oxide
1325
concentration of 5% (c = 0.05) on graphene-derived sheets have
been monitored as shown in Figure 7. There are little differences
in distribution of velocity along z axis, and thus it reveals that
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J. Phys. Chem. C 2017, 121, 1321−1328
The Journal of Physical Chemistry C
Figure 7. Velocity profiles along the z axis for different arrays of
hydroxyl groups, where the red and black curve denote random and
uniform arrays, respectively, and the inserted pictures are molecular
structures of two kinds of graphene oxide sheets (c = 0.05).
water diffusion is independent of the arrangement of functional
groups at the same oxide concentration.
In addition to the oxide concentration, the interlayer spacing
also has a great influence on the water transport. The interlayer
diffusion was performed through a range of layer distances from
1.1 to 2.3 nm. For all of layer distances, H2O molecules behave
as the same of those in bulk water and continuum flow.
Figure 8 shows the velocity profiles of water flow sandwiched
between different layer distances. The average value of velocity
Figure 8. Velocity profiles distributed along the z axis through different
layer distances.
increases along with expanding the interlayer spacing because
the flow velocity is cubic relation with distance between layers
according to eq 1. In order to estimate the permeability of
variable interlayer spacing, a characteristic permeation param-
eter Lp was defined as Lp = Q/(WΔP), where Q is the volumetric
flux, W is the width of plates and ΔP is the driven pressure.
Volumetric flux is calculated by integral of velocity function in
Figure 8 and the width of plates and the driven pressure are set
at the initial configuration. As presented in Figure 9, these
scatters are obtained by MD simulation and the solid line
represents for theoretical calculation of viscous flow. The value
of Lp in large layer spacing is greater than theoretical prediction
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Figure 9. Permeation parameters as a function of interlayer distance,
where the scatters denote the MD simulation results and the line
represents theoretical calculation of viscous flow.
because there are more hydrogen interactions in small interlayer
distance and it can enhance the resistance of water flow near wall
between two sheets.
More evidence about interactions between water molecules
and graphene oxide sheets are exhibited in number density
profiles and pair correlation functions. The distribution of
number density of water molecules in the z direction through
variable layer distances is presented in Figure 10. More
Figure 10. Number density profiles of water through different
interlayer distances.
molecules lie near the interlamination interface than the center
of interlayer because the hydrogen interactions make water
molecules bound to hydroxyl groups during flow and it is also
the reason why flow velocity is almost 0 near the boundary.
Water molecules at the center of interlayer can be considered as
free flow with low friction in the study of Devanathan’s group.21
The number density of free molecules increases with the
expanding layer distance, which means the impeditive
interactions from hydroxyl groups to water transport are less
at larger interlayer spacing. Figure 11 exhibits the pair
correlation functions between hydroxyl groups oxygen atoms
(Og) and water oxygen atoms (Ow) and that between hydroxyl
group hydrogen atoms (Hg) and water oxygen atoms (Ow) for
different layer distances. The Ow−Og distribution has a first peak
at 0.27 nm indicating strong interactions between water
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Figure 11. Pair correlation functions between (a) oxygen atoms in hydroxyl groups and water molecules and (b) hydrogen atoms in hydroxyl groups
and oxygen atoms in water molecules for the different interlayer distances.
Figure 12. Performance chart for interlayer flow between GO as well as RGO versus functionalized nanoporous graphene and existing technologies.
molecules and hydroxyl groups. With expansion of the interlayer
spacing, the height of this peak decreases, which shows fewer
molecules binding to hydroxyl groups. A similar trend is seen in
the Hg−Ow pair correlation function and the longer range
structure as well as the second and subsequent peaks starts to
disappear, indicating that water molecules move away from
hydroxyl groups and perform free flow. Therefore, the hydrogen
interactions will be reduced and the water flow rate will be
enhanced through large-distance gallery. That is the reason why
permeation parameter function deviated from theoretical cubic-
relation calculation of viscous flow.
Overall, our results indicated that graphene oxide could act as
a high-permeability membrane for water filtration. For
illustrative purposes, the theoretical performance of interlayer
flow between graphene oxide (GO) (c = 0.15) as well as reduced
graphene oxide (RGO) (c = 0.05) in our simulations is plotted
in Figure 12, by contrast with the experimental performance of
commercial reverse osmosis (RO) membranes from Pendergast
et al.32 and nanoporous graphene (NPG) from Grossman et
al.10 The water permeability of five kinds of RO membranes
(MFI Zeolite, seawater RO, brackish RO, nanofiltration and
high-flux RO) is not exceeding 1 L/cm2/day/MPa and that of
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NPG ranged from 39 to 66 L/cm2/day/MPa. The interlayer
flow examined in this work could reach 3−4 orders of
magnitude higher than commercial RO.
■ CONCLUSIONS
This article has performed slipped-viscous flow interlaminated
between graphene oxide sheets using molecular dynamics
simulations. Water transport can be enhanced through the
graphene oxide gallery at low oxide concentration, while the
flow velocity and volumetric flux in this flow regime are greater
than that in classical Poiseuille flow. It is the hybrid flow of two
characteristic transport mechanism. In one way, water
contacting on hydrophobic graphene surface will form a 0.05-
nm-thick vacuum layer, which greatly eliminates the friction
between water and boundary while enhances the flow rate
through the interlamination. In another way, the hydrogen
interactions between water molecules and hydroxyl groups
hinder the molecules flow near graphene oxide surface, and thus
make velocity of water flow tend to parabolic distribution.
The simulation results reveals that the enhanced flow rate is
negatively correlated with the oxide concentration as well as
hydrogen interactions below an oxide concentration of 10%,
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while is consistent at variable concentration of high values. It is
mainly because of the limited contact area between water and
boundary surface, and thus it reaches the saturation of hydrogen
bonds at high concentration. We find that hydrogen-bond
networks are correlated with both functionalization and
nanoconfinement. They tend to yield more hydrogen bonds
at high oxide concentration and in narrow interlayer space, but
they are independent of the arrangement of hydroxyl groups.
These results presented will be useful in understanding the
nature of water transport through graphene oxide inter-
lamination and can be utilized to predict and design innovative
reverse-osmosis membrane for desalination.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: hfjiang@whu.edu.cn (H.J.).
*E-mail: xjhu@whu.edu.cn (X.H.).
ORCID
Haifeng Jiang: 0000-0002-1531-0787
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge the support of the National Natural
Science Foundation of China (No. 50906064) and the
Fundamental Research Funds for the Central Universities
(No. 2042016kf0023).
■
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