Multilayer Graphene Oxide Membrane in Forward

Osmosis: Molecular Insights

Abhijit Gogoi,† K. Anki Reddy,∗,‡ and Pranab Mondal†

†Department of Mechanical Engineering, Indian Institute of Technology Guwahati, Assam,

India.
‡Department of Chemical Engineering, Indian Institute of Technology Guwahati, Assam,
India.

E-mail: anki.reddy@iitg.ernet.in

1 OPLS-AA Force Field

In OPLS-AA force field 1 the following bonded interactions are considered.

• Bond Stretching

Vb (rij ) = kijb (rij − b0 )2 (1)

The bond stretching interaction between atoms i, j is given by Vb (rij ) which is modeled
through Eq. 1. Here b0 is the equilibrium bond distance between atoms i,j and rij is the
instantaneous bond distance between them. kijb is the spring constant of the bond between
i and j.

• Bond-angle bending

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  2
θ 0
Va (θijk ) = ki,j,k θijk − θijk (2)

The bond-angle bending interaction Va (θijk ) between the three atoms i, j and k which
are bonded through two bonds is given by Eq. 2. θijk is the instantaneous bond angle
0 θ
between i, j, k with j being the central atom. θijk is the equilibrium bond angle and ki,j,k is
the corresponding force constant.

• Torsional Interaction

V1
Vd (φijkl ) = [1 + cos(φ + f1 )] +
2
V2
[1 − cos(2φ + f2 )] +
2
V3
[1 + cos(3φ + f3 )] (3)
2

The torsional interaction Vd (φijkl ) due to the torsional angle φijkl between the planes
containing the atoms with indices i, j, k and j, k, l is given by Eq. 3 where Vi , (i = i, 2, 3...)
is the corresponding Fourier coefficients for torsional energy functions.
The non-bonded interactions in the present simulation are van der Waals interaction and
Coulomb interaction.

• van der Waals interaction

(12) (6)
Cij Cij
VLJ (rij ) = (12)
− (6)
(4)
rij rij

In this present work the van der Waals interaction is modeled through Lennard-Jones
(12) (12) (6) (6)
(LJ) potential given by Eq. 4. The parameters Cij = 4ij σij and Cij = 4ij σij depend

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on the pair of atom types. For the interactions with different atom types the following
combination rules are applied

 1 /2
(6) (6) (6)
Cij = Cii Cjj (5)
 1 /2
(12) (12) (12)
Cij = Cii Cjj (6)

1/
2
ij = (ii jj ) (7)
1/
2
σij = (σii σjj ) (8)

In the above expression ij is the potential well depth and σij is the distance where potential
equals zero.

• Coulomb interaction

1 q i qj
VC (rij ) = (9)
4π0 r rij

Here 0 and r are the vacuum and relative dielectric permittivities, respectively.

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2 Graphene Oxide (GO) Nanosheets and Layered GO

Membranes

Figure S1a shows a single layer GO nanosheet of size 50.0 × 49.0 Å2 . The distribution of
oxygen containing groups in a GO nanosheet is depicted in Figure S1b. The three membrane
configurations used in this study are shown in Figure S2.

(a)

(b)

Figure S1: (a) GO nanosheet of size 50.0 × 49.0 Å2 and (b) The distribution of functional
groups on GO nanosheet. The green color is for hydrogen atoms, the red color is for oxygen
atoms and the cyan color is for carbon atoms.

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 (a)

(b)

(c)

Figure S2: The three membrane configurations (a) Configuration-1 (b) Configuration-2 (c)
Configuration-3. The green color is for hydrogen atoms, the red color is for oxygen atoms
and the cyan color is for carbon atoms.

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3 Supporting Results

Figure S3: Variation of number of water molecules in the feed solution box (Nf ) with time.

We computed the variation of number of water molecules in the feed solution box Nf
with time (Figure S3). As the water molecules from the feed solution permeate towards the
draw solution through the membranes the number of water molecules in the feed solution
gradually decreases and it decreases more for configuration-3 followed by configuration-2 and
configuration-1.

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 Figure S4 and S5 show the trajectory of a representative water molecule inside the layered
GO membrane of configuration-2 and configuration-3 respectively.

Figure S4: (a)Trajectory of the water molecule inside the layered GO membrane of
configuration-2. (b) The number of water molecules in the hydration shell of water at
various positions while permeating through the membrane. The permeated water molecule
is shown in violet color. Red color is for oxygen atoms, green color is for hydrogen atoms
and cyan color is for carbon atoms.

Figure S5: (a) Trajectory of the water molecule inside the layered GO membrane of
configuration-3. (b) The number of water molecules in the hydration shell of water at
various positions while permeating through the membrane. The permeated water molecule
is shown in violet color. Red color is for oxygen atoms, green color is for hydrogen atoms
and cyan color is for carbon atoms.

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Figure S6: Distribution of number of hydrogen bonds among water molecules along the Z
direction. (a) Configuration-1 (b) Configuration-2 (c) Configuration-3. The positions of the
two membranes are shown by two pair of dotted green lines.

The distribution of number of hydrogen bonds (Figure S6) also shows the same trend as
density (Figure 5). When the distance between oxygen atom of a water molecule and the
hydrogen atom of an another water molecule is less than 3.0 Å and the angle between oxy-
gen atom of one water molecules and hydrogen and oxygen atoms of another water molecule
(O-H-O) is less than 200 then a hydrogen bond between them is assumed. The number of
hydrogen bonds among the water molecules is less inside the membrane as compared to the
bulk solution. However, it drops to a lower value for configuration-1 and configuration-2
as compared to configuration-3, which can be attributed to the lower water permeability of
configuration-1 and configuration-2 as compared to configuration-3. Similarly, the fluctua-
tions in number of hydrogen bonds among the water molecules is more for configuration-1
and configuration-2 than in configuration-3. As in the density distribution, here also the two
key factors for these fluctuations are, distribution of oxygen containing functional groups
inside the membrane and the movements of the GO nanosheets which at times block the
water (and ions) pathways inside the membrane during permeation. The oxygen contain-
ing functional groups located in the GO nanosheets have different interaction intensity with
water molecules which typically follows the trend carboxyl > hydroxyl > epoxy (Figure 4).
Since these functional groups are randomly oriented inside a GO membrane, it leads to fluc-

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tuations in the density and number of hydrogen bonds between the water molecules inside
the GO membrane.

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Figure S7: Distribution of distance traversed (a) Configuration-1 (b) Configuration-2 (c)
Configuration-3, residence time (d) Configuration-1 (e) Configuration-2 (f) Configuration-
3 and velocity (g) Configuration-1 (h) Configuration-2 (i) Configuration-3, of the water
molecules while permeating through the layered GO membranes.

Figure S7a, Figure S7b, Figure S7c shows the distribution of path traversed by the water
molecules while permeating through the GO membranes, for configuration-1, configuration-2
and configuration-3 respectively. As can be seen for configuration-1 the water molecules have
to traversed a longer path through the membrane while permeating and the corresponding
number of water permeation events is also less. Figure S7d, Figure S7e and Figure S7f
shows the distribution of time taken by the water molecules to permeate through the GO
membranes, for configuration-1, configuration-2 and configuration-3 respectively. As can be
seen in a shorter amount of time a relatively larger amount of water molecules permeated

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through the membrane of configuration-3 as compared to configuration-2 and configuration-
1. The distribution of velocity of the water molecules while permeating through the lay-
ered GO membranes are shown in Figure S7g, Figure S7h, Figure S7i for configuration-1,
configuration-2 and configuration-3 respectively.

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 Figure S8 and S9 show the trajectory of a representative Na+ ion and Cl− ion while
permeating through layered GO membrane of configuration-3.

Figure S8: (a) Trajectory of Na+ ion inside the layered GO membrane of configuration-
3. (b) Number of water molecules in the hydration shell of Na+ ion at various locations
while permeating through the membrane. Red color is for oxygen atoms, green color is for
hydrogen atoms, cyan color is for carbon atoms and yellow color is for Na+ ion.

Figure S9: (a) Trajectory of Cl− ion inside the layered GO membrane of configuration-3.
(b) Number of water molecules in the hydration shell of Cl− ion at various locations while
permeating through the membrane. Red color is for oxygen atoms, green color is for hydrogen
atoms, cyan color is for carbon atoms and blue color is for Cl− ion.

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Figure S10: Number of water molecules in the hydration shell of the ions. (a) Mg2+ ion (b)
Na+ ion (c) Cl− ion.

Figure S10 shows the variation of number of water molecules in the hydration shell of
the ions with simulation time, for all the 3 types of ions (Mg2+ , Na+ and Cl− ) that are
permeating through the layered GO membrane of configuration-3. The Mg2+ ion enters the
membrane at around 22 ns and comes out of the membrane at around 42 ns (Figure S10a).
The Na+ ion enters the membrane at around 42 ns and comes out of the membrane at
around 58 ns (Figure S10b). Similarly, Cl− ion enters the membrane at around 18 ns and
comes out of the membrane at around 24 ns (Figure S10c). For all the 3 types of ions, the
number of water molecules in their hydration shell is less inside the membrane as compared
to its value outside the membrane.

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Figure S11: Trajectory of unpermeated ions: Column 1 (Al3+ ), Column 2 (Cl− ), Column 3
(Mg2+ ), Column 4 (Na+ ) and Column 5 (SO4 2− ). Here (a)-(e) represents configuration-1,
(f)-(j) represents configuration-2 and (k)-(o) represents configuration-3.

We also presented the trajectories of ions which have not permeated through the mem-
brane in Figure S11.

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Figure S12: Internal structure of the membranes during simulations. The blockage of the
water and salt passages are shown in black circles. (a) Configuration-1 (b) Configuration-2
(c) Configuration-3. Red color is for oxygen atoms, green color is for hydrogen atoms and
cyan color is for carbon atoms.

Figure S12 shows the internal structure of the membrane during the simulations. Due
the movement of the GO nanosheets in the Z direction (permeate direction) blockage of
the permeate pathways through the layered GO membrane are observed for configuration-1
(Figure S12a) and configuration-2 (Figure S12b). These blockage are shown in black circles
in Figure S12.

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References

(1) Jorgensen, W. L.; Maxwell, D. S.; Rives, J. T. 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.

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