Journal of Water Process Engineering 47 (2022) 102678

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Journal of Water Process Engineering

journal homepage: www.elsevier.com/locate/jwpe

Molecular dynamics simulation of Polyacrylonitrile membrane

performance in an aqueous environment for water purification
ZiYing Zhang a, b, JunFang Gou a, XiaoYan Zhang a, ZhuQing Wang a, Ning Xue a,
Gang Wang a, b, *, Roozbeh Sabetvand c, Davood Toghraie d, **
a
Hebei Agricultural University Bohai College, Cangzhou, Hebei 061100, China
b
China Institute of Water Resources and Hydropower Research, Beijing 100038, China
c
Department of Energy Engineering and Physics, Faculty of Condensed Matter Physics, Amirkabir University of Technology, Tehran, Iran
d
Department of Mechanical Engineering, Khomeinishahr Branch, Islamic Azad University, Khomeinishahr, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this computational work, we report the Polyacrylonitrile (PAN) as a polymeric membrane for water purifi­
Polyacrylonitrile cation from Arsenide (As) pollution with molecular dynamics (MD) approach. In our calculation, the PAN
Purification membrane was simulated in an aqueous environment with the TIP3P-CHARMM model. The membrane purifi­
Atomic membrane
cation behaviour is reported with temperature, total energy, filtration value, permeability, and selectivity
Mechanical test
Molecular dynamics
simulated structures. Temperature and total energy convergence show the atomic stability in our simulations.
Water, arsenide Further, the atomic purification process was detected after 1 ns for the PAN membrane. This process is affected
using temperature enhancement from 275 K to 350 K, and permeability value in MD simulations varies from 68
L/cm2/day/MPa to 85 L/cm2/day/MPa. Also, mechanical calculations show that the polymeric membrane was
weakened mechanically after the purification procedure. Numerically, Young's module of the pristine membrane
decreases from 321.27 GPa to 288.50 GPa after As atoms separation from H2O molecules.

1. Introduction stability and mechanical properties of these materials are essential in

Recently, membrane production and utilization technology were
used as an efficient method for water purification [1,2]. The use of this
technology accounts for about 50% of all processes to produce drinking
water. Some advantages of using membranes in water purification are
low cost, ease of use, high removal capacity, reduced chemicals, etc.
Separating membranes are mainly polymeric. Polymer membranes have
more flexibility, a simple cavitation mechanism, lower cost, and smaller
installation space than mineral membranes. Polyacrylonitrile (PAN) is a
synthetic, semi-crystalline polymeric structure by the (C3H3N)n chemi­
cal composition. Though this is a thermoplastic polymeric structure, it
does not melt under standard states. Further, PAN is infusible and
insolvable in common solvents [3]. Structurally, all PAN mixtures are
copolymers composed of monomers with acrylonitrile as the cardinal
atomic part. Technically, the PAN matrix phase change from solid to
liquid at T = 573 K if the temperature change values are 50 K/min [4].
This thermal behaviour, the possibility of recycling, and the high
many homes, industrial and manufacturing applications such as auto­
mobile industries, textile industries, high-temperature industrial plants,
Medicine, Construction, etc. [5]. Today, this polymeric structure is a
versatile compound that generates various productions like ultra-
filtration membranes, fibres for textiles, oxidized PAN fibres, etc.
[6,7]. Past studies show that PAN-based polymers, due to the presence of
a bis-amide group, have a significant capacity to remove various ions
such as manganese, cobalt, copper, chromium, magnesium, etc. and
wastewater treatment [8].
Recently, increasing attention has been given to low-cost membrane
materials such as PAN nanostructures for the water purification process.
For instance, lee et al. [9] examined the water purification process using
a PAN membrane. This study investigates various factors such as
diameter, porosity, and size of membrane pores in the water treatment
process. The results reveal that the use of PAN membrane is effective in
water treatment. Also, other studies such as Jang et al. [10], Chang et al.
[11], Prakash et al. [12], etc. was performed to examine the usage of

* Correspondence to: G. Wang, Hebei Agricultural University Bohai College, Cangzhou, Hebei 061100, China.
** Corresponding author.
E-mail addresses: wgang@hebau.edu.cn (G. Wang), Toghraee@iaukhsh.ac.ir (D. Toghraie).

https://doi.org/10.1016/j.jwpe.2022.102678
Received 7 November 2021; Received in revised form 11 February 2022; Accepted 20 February 2022
Available online 28 February 2022
2214-7144/© 2022 Elsevier Ltd. All rights reserved.
Z. Zhang et al. Journal of Water Process Engineering 47 (2022) 102678

PAN membranes in the water purification process. The results show that
these PAN matrices are good candidates for removing heavy metal ions
from water.
Today, the use of nanostructures has improved the behaviour of
conventional materials in various fields. Therefore, the study of struc­
tures with low dimensions in different areas of science is routinely done
[13–17]. In addition to experimental methods, computer simulations
like molecular dynamics simulation (MDS) efficiently describe nano­
structures' behaviour in various aims, such as the purification process
[18–20].
Several studies have examined the water treatment process by the
MDS method. For instance Nalaparaju et al. [21], Rizzuto et al. [22], .
Lin et al. [23], Ebro et al. [23], etc., examined the water treatment in the
presence of different nanoparticles using molecular MDS. These papers
show that using the MDS method has many advantages over other
theoretical and experimental methods and can simulate the water
treatment process well. Different values related to system dynamics can
be calculated using time averages in this method. Also, another advan­
tage of this method is its application as an experimental tool to study a
system that has deviated from equilibrium [24,25]. Also, previous
studies show that MDS is an appropriate method for studying polymeric
structures [26–29]. Based on previous research, it can be said that the
water purification process using a PAN-based membrane was not studied
by using the MDS method. Since PAN membranes have excellent me­
chanical properties, these structures are an appropriate candidate for
water purification. For instance, Ala et al. [30] examined the mechanical
properties of PAN membranes at various concentrations (in the range of
0.05–0.3 wt%). The results reveal that increasing the PAN membrane to
[( ) ( )6 ]
( ) σ 12 σ
U rij = 4ε − rij ≤ rc (1)
rij rij
where σ, ε, rc, and rij represent the finite distance, the depth of the po­
tential well, cut-off radius and the distance among the atoms. These
atomic interaction constants for various particles in the MD box are
reported in Table 1.
The bonded interactions can be computed by computing the simple-
bond and angular-bond terms. In our MDS, with an ordinary angular
harmonic oscillator, simple-bond and angular-bond of the bonded in­
teractions in the PAN membrane can be computed [43]:
E = ½ kr (r − r0 )2 (2)
E = ½ kθ (θ − θ0 )2 (3)
where kr, r0, kθ, and θ0 represent the constant of the harmonic oscillator,
the atomic bond length, the constant of the angular oscillator, and the
angle's balance amount. These constants of interaction for different
atoms in the MD box are reported in Table 2.
We used the TIP3P-CHARMM model for an aqueous environment,
appropriately describing H2O molecules' behaviour [42]. In this atomic
pattern, three situates are considered for interactions of electrostatic. A
negative charge is sited on the oxygen atom. This negative charge has
been utilized to equilibrium the hydrogen atoms' partial positive
charges. Numerically, in the TIP3P-CHARMM pattern, the r0 of O–H
interaction is equal to 0.9572 Å, and θ0 of H-O-H interaction is equal to
104.52 [42]. The other atomic interaction parameters for H2O mole­
◦

0.3% improves the tensile strength and mechanical properties. Mataram

cules in the TIP3P-CHARMM model are represented in Table 3 [42].
et al. [31] examined PAN membranes' physical and mechanical attri­
The computational procedure was fulfilled after describing the po­
butes. The results revealed that this membrane shows good resistance at
tential function for simulated samples in the MD box. Equation of
room temperature. Wang et al. [32] examined the mechanical charac­
Newton's second law is solved as the gradient of the potential function to
teristics of the PAN membrane for wastewater treatment. This mem­
describe the particle evolution in terms of time [44],
brane is suitable for water treatment since water-purifying requires
membranes with high mechanical strength, high flux, good durability, ∑ d 2 ri dvi
Fi = Fij = mi 2 = mi (4)
and contaminant repellency. i∕
=j
dt dt
According to the previous studies about waste water and purification
of water [33–36] and the efficiency of the MDS method in simulating the Fij = − grad Vij (5)
water treatment process, in this work, we use the MDS approach to
describe PAN membrane performance in the H2O purification process In the above, mi, ri, dt, and Vij represent the atomic mass, the position
from the H2O-As mixture for the first time. Our MD study on this topic is of atom i, MD time stage, and the potential function, respectively. And
novel and can design water purification applications. Further, this the velocity-Verlet algorithm accomplishes the association of motion
polymeric membrane's mechanical behaviour changes after the water equations [45,46].
purification process are reported. These calculations could be used in
industrial applications for optimized PAN-based membrane design.
2.2. Present simulation

2. Theory method
This simulation is performed in the following 2 stages:

2.1. MDS method

Stage A) Atomic purification performance of PAN membrane: Initially,
the pristine PAN membrane was modelled in the MD box with 200 Å
This study investigates the separation of water molecules by the PAN
lengths in x, y, and z- directions. In this simulation, boundary situ­
matrix using the MDS method. The MDS method is a suitable technique
ations in y and z orientations are considered periodically, and those
for describing the different particles' physical behaviour as a time (time
in x are considered fixed ones. The Nose-Hoover thermostat was used
stages) function based on Newton law. In this method, the particles
to set the temperature at T = 300 K (as primary temperature)
interacted for a certain period, giving the complete vision for structural
[47–49]. The canonical ensemble (NVT) was used to examine the
development. In the present study, MDS was performed by LAMMPS
thermal equilibration of atomic structures. After equilibrium phase
package released using Sandia National Laboratories [37–40]. Gener­
detection, As atoms, separation from H2O molecules was done with
ally, many parameters can affect the accuracy of the outputs of an MDS.
the PAN matrix. In this step, the grand canonical ensemble (NPT) is
Since the interaction between particles is the most important part of any
simulation, the potential function's choice is significant. Generally, the
Table 1
interactions of particles are defined by the potential function [41]. In
The ε LJ potential function constant in PAN matrix simulations [43].
this MDS, the interaction between N, H, O, As, and C-based particles
were studied using DREIDING force-field [42], a subset of the Lennard- Element σ(Å) ε(kJ/mol) rc(Å)

Jones (LJ) potential function. This force-field potential was utilized to C 4.180 1.27612 12
calculate the interaction of different atoms in PAN membrane [42], H 3.200 0.96485 12
N 3.995 1.73636 12

2
Z. Zhang et al. Journal of Water Process Engineering 47 (2022) 102678

Table 2 3. Results and discussion

The kr/kθ and r0/θ0 constants for PAN matrix simulations' simple/angular
bonded interaction [43]. 3.1. Atomic purification performance of PAN membrane
Physical Parameter (Bond/Angle) kr/kθ(kJ/mol) r0 (Å)/θ0(degree)

C− C 2929 1.530
In the first stage of current research, the atomic evolution of the PAN
Bonds C-H 2929 1.090 membrane and H2O-As mixture was studied. The atomic arrangement of
N− C 2929 1.462 these structures for the water purification process simulation is depicted
C-C-C 418 109.471 in Fig. 1. The geometry of these atomic mixtures was optimized by the
C− C− H 418 109.471
Angles Conjugate Gradient (CG) method before the equilibration phase [50,51].
H-C-H 418 109.471
N− C− C 418 109.471 This procedure is frequently applied as an iterative algorithm, appli­
cable to sparse systems that are too large to be handled using a direct
implementation or other direct procedures like the Cholesky decompo­
sition. After geometry optimization, the balance procedure is accom­
Table 3
plished in the MD box. Computationally, for the balance phase
The LJ potential function constant in the TIP3-CHARMM model [42].
implemented in the simulated membrane, this structure temperature
Element σ(Å) ε(kJ/mol) rc(Å)
increases from 275 K to 500 K for 5 ns. Next, the atomic compound
O 3.1507 0.63638 12 temperature decreases to 300 K for t = 5 ns. These simulations show that
H 0.4000 0.19246 12 the glass transition temperature of the PAN sample is 370 K, which is
consistent with previous reports [47]. Finally, MDS continued for 10 ns
used. The simulation time is 20 ns (10 ns for the equilibration process later to converge the total system temperature to T = 300 K as initial
and 10 ns for the separation process). This atomic process reports temperature (see Fig. 1).
calculated physical parameters such as filtration value, permeability, Fig. 2 shows the total energy of the PAN membrane and liquid
and polymeric matrix selectivity. mixture as an MD time. This atomic parameter equals the summation of
Stage B) Mechanical behaviour of PAN membrane: Next, the process of simulated structures' potential energy and kinetic energy. Fig. 2 shows
mechanical deforming was applied to pristine and after filtration that the total energy converged to − 1,028,440 kJ/mol in the final step.
PAN matrix for 10,000,000-time steps (10 ns). After the tensile test, Physically, this balance situation stems from atomic oscillation reducing
physical factors like stress-strain curve, Young's modulus (YM), and over MD time, which displays the correctness of the primary atomic
ultimate strength (US) were stated to describe the atomic behaviour arrangement and suitability of the utilized interatomic potentials in our
of pristine and final (after purification) polymeric membranes. computational work.
Next, to validate our computational procedure in the current simu­
lations, we calculate the Radial distribution function (RDF) and density
of water in the MD box. The RDF of simulated samples can define their
atomic arrangement of them. Computationally, RDF indicated in Eq. (6)
by g(r), defines the probability of finding particle (atom) at r distance

Fig. 1. The atomic representation of PAN membrane in the aqueous environment via LAMMPS package.

3
Z. Zhang et al.
Fig. 2. a) Temperature and b) total energy variation of PAN membrane in an
aqueous environment in terms of MD time.
from other atoms [48],
1 dnr
g(r) = (6)
4πρ dr
here ρ and dnr represent the atomic density and a function that computes
the number of atoms within a shell of thickness dr. Fig. 3a displays the
RDF of O atoms in H2O molecules, which is consistent with previous
reports [49]. Further, the density of H2O molecules in defined regions
converged to the density of this fluid in standard conditions as depicted
in Fig. 3b (997.15 kg/m3) [50]. So, these calculations show the validity
of our MD simulation settings in the current computational work.
After equilibrium phase detection, atomic structure evolution was
done to study H2O molecule purification from the H2O-As mixture. Fig. 4
displays the development of atomic structures after 1,000,000-time
stages (Δt = 1 fs). Also, the number of filtered water molecules varia­
tion in terms of MDS time at T = 300 K is reported in Fig. 5. From this
figure, it can be concluded the MD simulation time is long enough for the
atomic purification process detection in the MD box. After this atomic
phase, the number of As atoms that passed from the PAN membrane was
reported (see Fig. 6). Numerically, the number of filtered H2O molecules
reaches 614 molecules, which this calculated value shows the appro­
priate behaviour of the PAN membrane in the water purification pro­
cess. Also computed value of As atoms, which passed from the pristine
4
Journal of Water Process Engineering 47 (2022) 102678
Fig. 3. a) The O–O radial distribution function (RDF) and b) density of
aqueous environment under initial condition of MD simulations (T = 300 K).
membrane, is 5 atoms. Physically, by H2O-As mixture diffusion into PAN
membrane, the attraction force implemented to As atoms cause trapping
of them. By this phenomenon occurs, the water purification process is
fulfilled.
Temperature is an essential parameter in various atomic evolutions,
such as the atomic purification process. We describe this physical pa­
rameter's effect in the water purification process via PAN membrane.
Our results show the atomic interaction between membrane and As
atoms decreases as temperature enlarges, so the efficiency of PAN
membrane in the water purification process decreases. So, the temper­
ature enlarging in the current atomic procedure is a disruptive param­
eter. Physically, this atomic behaviour stems from As mobility increases
in the MD box.
Further, our simulations affect the permeability of atomic structures
by temperature changes. Permeability in fluid mechanics and the atomic
purification process measure a porous material's ability to allow fluids to
pass through it. Computationally, this physical parameter is represented
as below:
Z. Zhang et al. Journal of Water Process Engineering 47 (2022) 102678

Fig. 4. Time evolution of water purification process (As atoms separation process) with PAN membrane at a) initial and b) final time step.

700

600 T=275 (K )
T=300 (K )
T=325 (K )
Number of Water Molecules

500 T=350 (K )

400

300

200

100

0
0 .2 0 .4 0 .6 0 .8 1
Tim e(ns)

Fig. 5. The number of water molecules passed from the PAN membrane in
MD time.
P = KD/h
here D represents the membrane's diffusion constant, K represents the
solubilities ratio, and h represents the thickness of the atomic mem­
brane. From Fig. 7, we can say the maximum amount of this physical
factor reaches 68 and 85 L/cm2/day/MPa using temperature enhance­
ment from 275 K to 350 K, respectively. From these computed results,
we can conclude that increasing temperature disrupts the accuracy of
the atomic purification process and increases this procedure's speed (see
Table 4).
Finally, the atomic interaction between the membrane and H2O
molecules is reported. By temperature increasing in MD box, interatomic
interaction changes from − 26,150 kJ/mol.Å to − 30,680 kJ/mol.Å. This
Fig. 6. The number of As molecules passed from the PAN membrane as a
function of MD time.
(7)
parameter increase shows the atomic absorption enlarging in simulated
systems. With H2O molecules' absorption increasing, the purification
process occurs effectively. Further, the atomic interaction force between
the atomic membrane and As atoms doesn't change effectively by
increasing temperature in the MD box, as reported in Table 5. Therefore,
we conclude that the PAN polymer can be used as an atoms separation
process from H2O molecules in industrial applications [52,53].
3.2. Mechanical behaviour of PAN membrane
The pristine PAN matrix was simulated for the mechanical investi­
gation in this step. After the equilibration process, the density variation

5
Z. Zhang et al. Journal of Water Process Engineering 47 (2022) 102678

100
Permeability(L/cm /Day/MPa)

90
2

80

70

60
280 300 320 340 360
Temperature (K)

Fig. 7. Permeability of PAN-based membrane in terms of the MD simulation

temperature.

Table 4
The number of water molecules and As atoms passed from the PAN membrane
and membrane permeability in MDS temperature.
Temperature Number of Number of Passed Permeability(L/
(K) Passed As Atoms H2O Molecules cm2/day/MPa)

275 3 588 68
300 5 614 73
325 6 625 81
350 8 643 85

Table 5
The atomic interaction between membrane and water molecules/As atoms in
MDS temperature.
Temperature Atomic Interaction Between
(K) Membrane and H2O Molecules
(kJ/mol.Å)
275 − 26150
300 − 27790
325 − 29040
350 − 30680
in NPT simulation (T = 300 K and P = 1 bar) time is reported in Fig. 8.
We derive that the MDS time is long sufficient for the atomic sample to
reach the balance phase from the mass density variation curve. Next, the
tensile test was applied to the pristine polymeric structure (see Fig. 9).
The stress-strain curve is utilized to study the mechanical attributes of
structures like the YM and the US. As the force increases, the structures'
deformation values are measured, and finally, the stress-strain curve is
obtained using these values. The deformation of a sample will depend on
its elastic modulus and geometry (length and cross-section). Thus the
load values are converted to stress and the deformation values to strain.
Computationally, stress value calculated with “compute/p” command of
LAMMPS package and strain value calculated from Eq. (11) [34]:
L − L0
Strain =
L0
where L and L0 are the primary and final lengths of simulated structure
in the deformation test. The stress-strain curves of the mechanical test
are shown in Fig. 10. Theoretically, the constants of mechanical like the
YM and the PAN matrix's US can be computed from this curve. From our
MD outcomes, Young's pristine PAN membrane's modulus is obtained
Fig. 8. a) The mass density variations and b) the pristine PAN matrix
arrangement after equilibration process with NPT ensemble.
Atomic Interaction Between
Membrane and As Atoms(kJ/
mol.Å) 321.27 GPa up to 2.5% strain. This computed amount is comparable to
prior theoretical and experimental studies. Also calculated amount for
− 9842
− 10030
this polymeric matrix's US is 98.68 MPa, which agrees with previous
− 10320 reports (the previous study reported the US around 118 MPa [54] and in
− 10610 the range of 90 to 150 MPa [55]).
In the final step of the current computational study, the PAN matrix's
mechanical behaviour after the purification process is described by an
external deformation force implemented to the polymeric membrane.
The mechanical test results of this atomic structure are depicted in
Fig. 11.
After the atomic equilibration procedure (t = 20 ns), the polymeric
membrane was expanded to estimate its mechanical properties. The
stress-strain curve of the PAN membrane's tensile test in the z-direction
is presented in Fig. 12. These mechanical constants were computed
using least-square approximation, implemented to reduce information
oscillations. Numerically, by H2O-As mixture diffusion to pristine PAN
membrane, the mechanical properties (YM and US) of the final mem­
brane reduced and reached 288.50 GPa and 91.78 MPa, respectively
(see Table 6). This is due to the swelling of the membrane after the
purification process and the reduction of the mechanical properties, and
(11)
thus the reduction of permeability [56]. These results show that
diffusing H2O molecules to the PAN membrane weakens the pristine
membrane's mechanical properties. The atomic interaction between the
polymer chains and H2O/As mixture in the common zone significantly
influences structural integrity. The H2O-As mixture diffusing to the
pristine membrane reduces the atomic structure's mechanical strength
by the repulsive force (with van der Waals type). In practical cases, the

6
Z. Zhang et al. Journal of Water Process Engineering 47 (2022) 102678

Fig. 9. The time evolution of pristine polymeric matrix under atomic defor­
mation process.
Fig. 11. The time evolution of pristine polymeric matrix under atomic defor­
mation process.

120

100

80
stress(MPa)

60

40

20

0
0 0.002 0.004 0.006 0.008
Temperature (K)
Fig. 10. The stress-strain curve of the pristine PAN matrix after mechanical
tensile test. Fig. 12. The stress-strain curves of the PAN membrane after the water purifi­
cation process.

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Z. Zhang et al. Journal of Water Process Engineering 47 (2022) 102678

Table 6 its anti-fouling properties, Environ. Res. 206 (2022), https://doi.org/10.1016/j.

The mechanical properties of various PAN membranes in the current MD study envres.2021.112629.
[3] F. Hans, and H. Claus, "Production of polymerization products," Google Patents,
and the Error of these parameters calculation. 1938.
Atomic structure Young's Ultimate Young's Ultimate [4] A.R. Bunsell, Handbook of Properties of Textile And Technical Fibres, Woodhead
Module Strength module Strength Publishing, 2018.
(GPa) (MPa) Error(%) Error(%) [5] T. Adegbola, O. Agboola, O. Fayomi, Review of polyacrylonitrile blends and
application in manufacturing technology: recycling and environmental impact,
Pristine PAN 321.27 98.68 2.33 2.05 ResultsEng. 7 (2020), 100144.
membrane [6] T. G. Finzel, "Method of preparing polymeric solutions," Google Patents, 1946.
PAN membrane 288.50 91.78 – – [7] A. Serkov, M. Radishevskii, Status and prospects for production of carbon fibres
after the water based on polyacrylonitrile, Fibre Chem. 40 (1) (2008) 24–31.
purification [8] T. Jamil, S. Munir, Q. Wali, G.J. Shah, M.E. Khan, R. Jose, Water purification
process through a novel electrospun carbon nanofiber membrane, ACS Omega 6 (50)
(2021) 34744–34751.
[9] J. Lee, J. Yoon, J.H. Kim, T. Lee, H. Byun, Electrospun PAN–GO composite
nanofibers as water purification membranes, J. Appl. Polym. Sci. 135 (7) (2018)
results obtained in this section of our MD simulations should be 45858.
considered in PAN-based membranes' design. [10] W. Jang, J. Yun, Y. Park, I.K. Park, H. Byun, C.H. Lee, Polyacrylonitrile nanofiber
membrane modified with Ag/GO composite for water purification system,
Polymers 12 (11) (2020) 2441.
4. Conclusion [11] J. Chang, J. Wang, J. Qu, Y.V. Li, L. Ma, L. Wang, X. Wang, K. Pan, Preparation of
α-Fe 2 O 3/polyacrylonitrile nanofiber mat as an effective lead adsorbent, Environ.
In this work, we utilize a computational approach to explain the Sci.: Nano 3 (4) (2016) 894–901.
[12] H.P. Karki, L. Kafle, H.J. Kim, Modification of 3D polyacrylonitrile composite fiber
purification performance of Polyacrylonitrile (PAN) membrane in an for potential oil-water mixture separation, Sep. Purif. Technol. 229 (2019),
aqueous environment in the presence of Arsenide (As) atoms for the first 115840.
time. This purification phenomenon is described by molecular dynamics [13] G. Li, S. Huang, N. Zhu, H. Yuan, D. Ge, Near-infrared responsive upconversion
glass-ceramic@BiOBr heterojunction for enhanced photodegradation
(MD) in atomic systems. MDS outcomes are as follows: performances of norfloxacin, J. Hazard. Mater. 403 (2021) 123981.
[14] S. Yang, X. Yu, M. Ding, L. He, G. Cao, L. Zhao, et al., Simulating a combined lysis-
• DREIDING and TIP3P-CHARMM model are suitable functions to cryptic and biological nitrogen removal system treating domestic wastewater at
low C/N ratios using artificial neural network. Water research (Oxford) 189 (2021)
MDS of PAN-based membrane and H2O-As mixture. 116576.
• MD simulations predicted that the number of H2O molecules and [15] L. He, C. Yang, J. Ding, M. Lu, C. Chen, G. Wang, et al., Appl. Catal. B 303 (2022)
atoms passed from the PAN membrane was 643 and 8 after 1 ns. 120880.
[16] L. He, M. Li, F. Chen, S. Yang, J. Ding, L. Ding, et al., Novel coagulation waste-
• Numerically, the PAN membrane's permeability reaches 85 L/cm2/
based Fe-containing carbonaceous catalyst as peroxymonosulfate activator for
day/MPa at T = 300 K after 1 ns. pollutants degradation: Role of ROS and electron transfer pathway, J. Hazard.
• Increasing temperature parameters in PAN membrane cause the ac­ Mater. 417 (2021) 126113.
[17] J. Guo, J. Gao, C. Xiao, L. Chen, L. Qian, Mechanochemical reactions of GaN-Al2O3
curacy decrease and performance speed increase in the purification
interface at the nanoasperity contact: Roles of crystallographic polarity and
process. ambient humidity, Friction (2021), https://doi.org/10.1007/s40544-021-0501-9.
• PAN membrane was weakened mechanically after the purification [18] D. Toghraie, A.R. Azimian, Molecular dynamics simulation of nonodroplets with
process. Numerically, the ultimate strength of the pristine membrane the modified Lennard-Jones potential function, Heat Mass Transf 47 (5) (2011)
579–588.
decreases from 98.68 MPa to 91.78 MPa after H2O-As mixture [19] N.A. Jolfaei, N.A. Jolfaei, M. Hekmatifar, A. Piranfar, D. Toghraie, R. Sabetvand,
diffusion into the polymeric membrane. S. Rostami, Investigation of thermal properties of DNA structure with precise
• The young's module of the pristine membrane decreases from atomic arrangement via equilibrium and non-equilibrium molecular dynamics
approaches, Comput. Methods Prog. Biomed. 185 (2020), 105169.
321.27 GPa to 288.50 GPa after the atomic purification process. [20] M. Tohidi, D. Toghraie, The effect of geometrical parameters, roughness and the
number of nanoparticles on the self-diffusion coefficient in Couette flow in a
The atomic porosity ratio of the simulated membrane is an important nanochannel by using of molecular dynamics simulation, Physica B 518 (2017)
20–23.
parameter for the atomic purification process. Analyzing this atomic [21] A. Nalaparaju, J. Jiang, Ion exchange in metal–organic framework for water
parameter can improve our computational results for using designed purification: insight from molecular simulation, J. Phys. Chem. C 116 (12) (2012)
membranes for actual applications in future works. Finally, we expected 6925–6931.
[22] C. Rizzuto, G. Pugliese, M.A. Bahattab, S.A. Aljlil, E. Drioli, E. Tocci, Multiwalled
the MD simulation results obtained in our study to effectively optimize
carbon nanotube membranes for water purification, Sep. Purif. Technol. 193
polymeric membranes' performance for the water purification process. (2018) 378–385.
[23] S. Lin, M.J. Buehler, Mechanics and molecular filtration performance of graphyne
nanoweb membranes for selective water purification, Nanoscale 5 (23) (2013)
Declaration of competing interest 11801–11807.
[24] H.C. Andersen, Molecular dynamics simulations at constant pressure and/or
The authors declare that they have no known competing financial temperature, J. Chem. Phys. 72 (4) (1980) 2384–2393.
[25] M.P. Allen, Introduction to molecular dynamics simulation, in: Computational Soft
interests or personal relationships that could have appeared to influence
Matter: From Synthetic Polymers to Proteins 23, 2004, pp. 1–28, no.1.
the work reported in this paper. [26] B.J. Alder, T.E. Wainwright, Studies in molecular dynamics. I. General method,
J. Chem. Phys. 31 (2) (1959) 459–466.
Acknowledgements [27] A. Rahman, Correlations in the motion of atoms in liquid argon, Phys. Rev. 136
(2A) (1964) A405.
[28] S. Rafiaee, M.R. Samani, D. Toghraie, Removal of hexavalent chromium from
The Key National Science & Technology Major Project aqueous media using pomegranate peels modified by polymeric coatings: effects of
(No.2018ZX07101-005). various composite synthesis parameters, Synth. Met. 265 (2020), 116416.
[29] M. Hadipeykani, F. Aghadavoudi, D. Toghraie, Thermomechanical properties of
Specific Foundation for Doctor in the Hebei Agriculture University of the polymeric nanocomposite predicted by molecular dynamics, ADMT J. 12 (4)
China (No. YJ201909). (2019) 25–32.
Water conservancy research and promotion project of Hebei Prov­ [30] A. Mohamed, S. Yousef, M.A. Abdelnaby, T. Osman, B. Hamawandi, M.S. Toprak,
M. Muhammed, A. Uheida, Photocatalytic degradation of organic dyes and
ince in 2018 (2018-039). enhanced mechanical properties of PAN/CNTs composite nanofibers, Sep. Purif.
Technol. 182 (2017) 219–223.
References [31] A. Mataram, S. Nasution, M. L. Wijaya, and G. D. Septano, "Physical and
mechanical properties of membrane Polyacrylonitrile." p. 01010.
[32] K. Wang, A.A. Abdalla, M.A. Khaleel, N. Hilal, M.K. Khraisheh, Mechanical
[1] J.G. Cook, Handbook of Textile Fibres: Man-made Fibres, Elsevier, 1984.
properties of water desalination and wastewater treatment membranes,
[2] L. Zhang, l. Wang, Y. Zhang, D. Wang, J. Guo, M. Zhang, et al., The performance of
Desalination 401 (2017) 190–205.
electrode ultrafiltration membrane bioreactor in treating cosmetics wastewater and

8
Z. Zhang et al.
[33] M. Sakthivadivel, A. Nirmala, J. Sakthivadivel, R.R. Mukhilan, S. Tennyson,
Physicochemical and biological parameters of water at industrial sites of
metropolitan city of Chennai, Tamil Nadu, India, Water Conservation Manag. 4 (2)
(2021) 90–98.
[34] H. Zarepourfard, A. Aryafar, H. Zia, The investigation of groundwater
hydrochemistry of khezri plain, south khorasan province, iran. Water Conservation
Manag. 1 (2) (2017) 13–16.
[35] G. Li, S. Huang, N. Zhu, H. Yuan, D. Ge, Y. Wei, Defect-rich heterojunction
photocatalyst originated from the removal of chloride ions and its degradation
mechanism of norfloxacin, Chem. Eng. J. 421 (2021) 127852.
[36] X. Wang, X. Lyu, Experimental study on vertical water entry of twin spheres side-
by-side, Ocean Eng. 221 (2021) 108508.
[37] S. Plimpton, Fast parallel algorithms for short-range molecular dynamics,
J. Comput. Phys. 117 (1) (1995) 1–19.
[38] S.J. Plimpton, A.P. Thompson, Computational aspects of many-body potentials,
MRS Bull. 37 (5) (2012) 513.
[39] W.M. Brown, P. Wang, S.J. Plimpton, A.N. Tharrington, Implementing molecular
dynamics on hybrid high performance computers–short range forces, Comput.
Phys. Commun. 182 (4) (2011) 898–911.
[40] A. Stukowski, Visualization and analysis of atomistic simulation data with
OVITO–the open visualization tool, Model. Simul. Mater. Sci. Eng. 18 (1) (2009),
015012.
[41] T. Schlick, Pursuing Laplace's vision on modern computers, in: Mathematical
Approaches to Biomolecular Structure And Dynamics, Springer, 1996,
pp. 219–247.
[42] W.L. Jorgensen, J. Chandrasekhar, J.D. Madura, R.W. Impey, M.L. Klein,
Comparison of simple potential functions for simulating liquid water, J. Chem.
Phys. 79 (2) (1983) 926–935.
[43] S.L. Mayo, B.D. Olafson, W.A. Goddard, DREIDING: a generic force field for
molecular simulations, J. Phys. Chem. 94 (26) (1990) 8897–8909.
Journal of Water Process Engineering 47 (2022) 102678
[44] R. Skyner, J. McDonagh, C. Groom, T. Van Mourik, J. Mitchell, A review of
methods for the calculation of solution free energies and the modelling of systems
in solution, Phys. Chem. Chem. Phys. 17 (9) (2015) 6174–6191.
[45] E. Hairer, C. Lubich, G. Wanner, Geometric numerical integration illustrated by the
Stormer-Verlet method, Acta Numer. 12 (12) (2003) 399–450.
[46] W.H. Press, S.A. Teukolsky, W.T. Vetterling, B.P. Flannery, Numerical Recipes 3rd
Edition: The Art of Scientific Computing, Cambridge University Press, 2007.
[47] P. Patra, B. Bhattacharya, A deterministic thermostat for controlling temperature
using all degrees of freedom, J. Chem. Phys. 140 (6) (2014), 064106.
[48] S. Nosé, A unified formulation of the constant temperature molecular dynamics
methods, J. Chem. Phys. 81 (1) (1984) 511–519.
[49] W.G. Hoover, Canonical dynamics: equilibrium phase-space distributions, Phys.
Rev. A 31 (3) (1985) 1695.
[50] M.R. Hestenes, E. Stiefel, Methods of conjugate gradients for solving linear systems,
J. Res. Natl. Bur. Stand. 49 (6) (1952) 409–436.
[51] T.A. Straeter, On the extension of the davidon-broyden class of rank one, quasi-
newton minimization methods to an infinite dimensional Hilbert space with
applications to optimal control problems, 1971.
[52] L. Wang, N. Wang, J. Li, J. Li, W. Bian, S. Ji, Layer-by-layer self-assembly of
polycation/GO nanofiltration membrane with enhanced stability and fouling
resistance, Sep. Purif. Technol. 160 (2016) 123–131.
[53] Y. Peng, F. Guo, Q. Wen, F. Yang, Z. Guo, A novel polyacrylonitrile membrane with
a high flux for emulsified oil/water separation, Sep. Purif. Technol. 184 (2017)
72–78.
[54] R. Zhao, M. Tian, L. Qu, Y. Zhao, S. Chen, S. Zhu, G. Han, Wet-spinning assembly of
continuous and macroscopic graphene oxide/polyacrylonitrile reinforced
composite fibers with enhanced mechanical properties and thermal stability,
J. Appl. Polym. Sci. 136 (3) (2019) 46950.
[55] G. Duan, S. Liu, H. Hou, Synthesis of polyacrylonitrile and mechanical properties of
its electrospun nanofibers, e-Polymers 18 (6) (2018) 569–573.
[56] S. Robinson, P.R. Berube, Membrane ageing in full-scale water treatment plants,
Water Res. 169 (2020), 115212.