Chemical Engineering Journal 427 (2022) 131819

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Chemical Engineering Journal

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Influence of ultrasound on the adsorption of single-walled carbon

nanotubes to phenol: A study by molecular dynamics simulation
and experiment
Yong Han a, b, *, Ningning Wang b, Xiaoqiang Guo b, Tifeng Jiao a, *, Hao Ding b
a
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, Hebei 066004, PR China
b
School of Electrical Engineering, Yanshan University, Qinhuangdao, Hebei 066004, PR China

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

Keywords: In this article, the effect of ultrasound on the adsorption of single-walled carbon nanotubes (SWNTs) to phenol
Ultrasound was investigated by performing an all-atom molecular dynamics (MD) simulation. During the simulation process,
SWNTs a novel convenient method based on segmented simulation was proposed to realize the loading of ultrasonic
Phenol
boundary condition in MD simulation, which was realized by controlling the pressure changing as the positive
Adsorption
MD simulation
and negative square wave. For evaluating the adsorption effect, structural parameters, interaction energies,
hydrogen bond and number density distribution of water molecules were examined, and then an experiment was
performed for verifying the conclusions of MD simulation. The results show that the external ultrasound can
increase the amount of phenol around SWNTs, enhance the interaction energy between SWNTs and phenol
molecules and weaken the hydrogen bond between phenol hydroxyl group and water molecules. These results
indicate that the presence of ultrasound can promote the adsorption of carbon nanotubes to phenol. The
experimental results for verification show that under ultrasound action, the concentration of the phenol solution
is lower after adsorbed by SWNTs, which means that the adsorption of SWNTs to phenol has been promoted. In
addition, the density distribution of water molecules decreases significantly only when the ultrasound generates
negative pressure in the aqueous solution, which proves the correctness of the ultrasonic loading method pro­
posed in this study.

1. Introduction
Phenol is a raw material or intermediate products in papermaking,
oil refining, plastics, pesticides, pharmaceutical synthesis and other in­
dustries. It is widely present in various industrial wastewater[1–2], thus
phenol is also the main detectable substance in various industrial water
pollution accidents in recent years. Phenol is biologically toxic. If
humans drink water contaminated with phenol for a long time, the
central nervous system will be inhibited, and it will also cause liver
damage, kidney damage, digestive tract damage and other diseases.
Therefore, the technology of removing phenol from water has always
been a research hotspot in the field of water treatment. At present, the
commonly used methods to remove small organic molecule from fluid
include adsorption, membrane treatment, chemical oxidation, chemical
precipitation and biodegradation[3–9]. Among them, the adsorption
method has become the most widely used method due to its high
removal efficiency, simple operation, and no secondary pollution. The
material properties of the adsorbent directly determine the adsorption
efficiency.
In recent years, Nanotechnology has developed rapidly[10–13].
Carbon nanotube is considered as a new type of adsorbent with great
potential due to its large specific surface area, large specific surface
energy (because of the topological defects in the pipe wall[14]) and
large number of available active sites, which therefore can be used to
remove and separate organic pollutants in water. According to previous
studies[15,16], the original driving force of nanotube adsorption of
small organic molecules mainly are based on the van der Waals inter­
action between molecules or the complementary π-π Stacking (It de­
pends on the composition of the small molecules). However, the
adsorption characteristics of carbon nanotube are affected by many

* Corresponding authors at: State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, Hebei 066004, PR China (Y.
Han, T. Jiao).
E-mail addresses: hanyong@ysu.edu.cn (Y. Han), tfjiao@ysu.edu.cn (T. Jiao).

https://doi.org/10.1016/j.cej.2021.131819
Received 26 May 2021; Received in revised form 8 August 2021; Accepted 10 August 2021
Available online 15 August 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
Y. Han et al.
factors, such as dispersibility in water, pH value, and ionic strength
[17–19]. Therefore, it is essential to study the technology to enhance the
adsorption efficiency of carbon nanotubes.
Researchers have introduced power ultrasound into the adsorption
process for using the cavitation effect of ultrasound in water to change
the efficiency of adsorption. O. Hamdaoui[20,21] experimentally stud­
ied the adsorption of p-chlorophenol by activated carbon under the
action of ultrasound, and concluded that the saturated adsorption ca­
pacity of activated carbon under the action of ultrasound is lower than
that without ultrasound, and this result also meet with Ruey-Shin
Juang’s research conclusion [22]. S. Bekkouche [23] studied the
adsorption of phenol by TiO2 powder under ultrasonic conditions. The
result showed that the amount of phenol adsorbed on TiO2 increased by
a small amount under the action of ultrasound. They believed that this
was mainly due to the fact that ultrasonic waves can effectively prevent
the agglomeration of TiO2, which increases the specific surface area of
the adsorbent, resulting in a small increase in the amount of adsorption.
According to the above research reports, it can be seen that applying
ultrasound can indeed affect the adsorption efficiency. Inspired by this,
in the present study the ultrasound was attempted to introduce into the
process of single-walled carbon nanotubes adsorbing phenol, then the
effect of ultrasound on the adsorption efficiency and its internal mech­
anism were studied.
At present, most studies analyze the effect of ultrasound on adsorp­
tion efficiency by observing the changes in saturated adsorption ca­
pacity and adsorption isotherms through experiment[24–27], but the
internal micro-mechanism still needs to be further explored. At the
atomic level, the conformational change (caused by ultrasound) occurs
too quickly to be detected by experiments. Molecular dynamics (MD)
method has been proven to be employed to theoretically study the
phenomena at the atomic level[28–30]. Many researchers have used the
MD method to study the properties of carbon nanotubes in different
systems[31–33]. However, there are few literatures on the use of mo­
lecular dynamics to simulate systems with ultrasound. Hisashi Okumura
[34] studied the amyloid fibril disruption by ultrasonic cavitation using
MD method (performed by Generalized-Ensemble Molecular Biophysics
program). They wrote a script for ultrasonic boundary condition during
the modeling process, which described a system pressure that changes
sinusoidally over time. The setting method of this boundary condition is
reasonable, because the effect of ultrasound is essentially the periodic
drastic change of the partial pressure in the solution. However, a more
simple and effective method of ultrasonic environment simulation may
need to be explored. As is well known, the frequency of ultrasound is
generally high (greater than 20 kHz), so the pressure that changes ac­
cording to the sinusoidal waveform is very similar to the pressure that
changes according to the positive and negative square wave. Therefore,
inspired by Hisashi Okumura’s work, a positive and negative square
wave can be used to approximate the sine wave as the waveform of the
pressure change, and according to this approximation, the ultrasonic
boundary condition can be realized by the method of segmented simu­
lation calculation (the system pressure in each segment is different).
In the present study, MD simulation was employed to study the
adsorption characteristics of single-walled carbon nanotubes to phenol
under different frequency of ultrasound, and a novel method of
segmented simulation calculation was put forward to realize ultrasonic
boundary condition. Our research is also expected to propose a new
technology to enhance the adsorption efficiency of carbon nanotubes,
and reveal the mechanism of the effect of ultrasound on the adsorption
of phenol by carbon nanotubes at the atomic level. In addition, our
research results are expected to propose a simple and reliable ultrasonic
loading method in MD simulation, and then promote the development of
molecular dynamics research in the field of sonochemistry.
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Chemical Engineering Journal 427 (2022) 131819
2. Details of MD simulation and experiment verification
2.1. MD simulation
Several equilibrium MD simulations were performed in the present
study by using GROMACS software [35–37]. The simulation box is 6 nm
× 6 nm × 6 nm in size as the periodic boundary condition and contains
80 phenol molecules, 6344 water molecules (according to the solubility
of phenol in water under the temperature of 23.9 ◦ C (solubility is 7.5 g/
100 ml) and 29.6 ◦ C (solubility is 7.8 g/100 ml)), and a single-wall
carbon nanotube. The SPC/E model was used for water molecules
[38]. Phenol molecules were modeled with the rigid model. The single-
walled carbon nanotubes (5, 10) with a length of 5 nm were infinitely
rigid and fixed in the central region of the box modeled by visual mo­
lecular dynamics (VMD). Snapshots of the initial configuration of the
simulation and the all-atom phenol model with atomic name is shown in
Fig. 1.
OPLS/AA all-atom force field was used in the simulation process,
which is widely used in organic systems and has significant advantages
in liquid simulation research [39–43]. Electrostatic interaction was
solved by particle mesh Ewald (PME) method and real space cut-off
value of 1.0 nm, and Lenard-Jones interaction was calculated with
cut-off value of 1 nm. Table 1 exhibits the Lenard-Jones potential pa­
rameters for applied molecules. All the simulations were performed on
the basis of NPT ensemble. Pressure was controlled with Parrinello-
Rahman method. Temperature was controlled with nose-Hoover ther­
mostat at 300 K. Leapfrog algorithm MD was employed in all simulations
with 2 fs time step. The time step for the initial energy minimization was
5000 steps. In this paper, the pressure changing according to positive
and negative square wave was used to load ultrasound boundary con­
dition of MD simulation inspired by Reference [29], which is shown in
Fig. 2. And the frequency of ultrasonic wave was changed by changing
the square wave period. The period in this study was set as T = 1 ns, 2 ns,
3 ns, 4 ns and 5 ns respectively, and the corresponding ultrasonic fre­
quencies were 1000 MHz, 500 MHz, 333 MHz, 250 MHz and 200 MHz
respectively. The first simulation ran with 3 ns for equilibration. In each
condition, the time of running the dynamics simulation was 5 ns.
2.2. Experiment verification
In order to verify the MD simulation conclusion that ultrasound may
affect the adsorption of phenol on SWNTs, a series of effective experi­
ments were carried out. Since the adsorption characteristics between
SWNTs and phenol can be directly characterized by measuring the
amount of phenol remaining in the solution, in the present experiment,
after the SWNTs have fully adsorbed phenol, the concentration of phenol
in the solution with and without the application of ultrasound was
measured and analyzed.
2.2.1. Experimental setup and sample preparation
The setup used in the experiment is shown in Fig. 3. As shown in
Fig. 3, an ultrasonic generator was used to provide the ultrasonic os­
cillations required for the experiment. The output frequency of the ul­
trasonic generator is 40 kHz, and the output power is 500w. A
cylindrical glass container with 50 ml test solution inside was fixed by an
iron stand, and the experimental solution in the test tube was completely
immersed below the water level in the ultrasonic generator. During the
experiment process, the temperature of all solution was controlled at
293 K through a thermostatic water bath.
The water used in this experiment was manufactured by a milli-Q
Millipore System, and the total organic carbon and dissolved oxygen
of the water were below 0.05 mg/L and 5.0 mg/L, respectively.
Analytical pure phenol was used to prepare a phenol solution with a
concentration of 200 mg/L. SWNTs with a purity greater than 95 wt%
were used as the adsorbent in the experiment. This SWNTs was prepared
by a chemical vapor deposition (CVD) method. The inner diameter of the
Y. Han et al. Chemical Engineering Journal 427 (2022) 131819

Fig. 1. Snapshots of the (a) initial configuration of the simulation and (b) phenol model with atomic name.

Table 1
Lenard-Jones parameters used in the MD simulations.
Molecule Atom ε(kcal/mol) σ(Ǻ)
Water OW 0.155 3.166
H1.H2 0.00 0.00
Phenol C01.C02. C03. C04.C05.C06 0.070 3.550
H08.H09.H0A.H0B 0.030 0.240
OP 0.170 3.070
H07 0.00 0.00
SWNT C 0.086 3.40

Fig. 3. Schematic diagram of the experimental setup. 1-CNC thermostat, 2-

Refrigerating tube, 3-Electric heating tube, 4-Temperature sensor, 5-Circulating
pump, 6-Cylindrical glass container, 7-Ultrasonic generator, 8-Constant tem­
perature water bath, 9-Iron stand.

with the peak area as the ordinate and the concentration of the phenol
solution as the abscissa. The standard curve regression equation can be
obtained as:
A = 24.357C − 10.814 (1)

Fig. 2. The waveform of the pressure over time.
tube wall is 0.8–1.6 nm, the outer diameter is 1–2 nm, and the length is
5-20um.
2.2.2. Experimental methods
In this article, the effect of ultrasound on the adsorption of phenol by
SWNTs is studied by measuring the concentration of phenol solution
after the adsorption of SWNTs with and without ultrasound application.
The concentration of the phenol solution is measured by liquid chro­
matography. Thus, it is necessary to prepare a standard curve of the
phenol concentration before the experiment is performed. Prepare 2
mg/L, 4 mg/L, 6 mg/L, 8 mg/L, and 10 mg/L phenol solutions respec­
tively (it can be obtained by diluting the previously prepared 200 mg/L
solution), and use the liquid chromatography system to measure the
solution of each concentration to obtain the peak area (A) for each
concentration. Then, draw the standard curve of the phenol solution
Where A is the peak area, and C is the concentration of the phenol so­
lution (The minimum value that the standard curve can accurately
represent is 2 mg/L).
For comparison, three independent experiments were implemented:
Experiment I: In order to evaluate the effect of ultrasound on phenol
solution without adding carbon nanotubes, a test tube containing 50 ml
of 200 mg/L phenol solution was placed in the ultrasonic generator, and
then turned on the ultrasonic generator. The entire ultrasonic treatment
lasted for 8 h, and during the experiment the concentration of the phenol
solution at different time points was measured.
Experiment II: Put 0.05 g of SWNTs powder into a test tube, then
poured 50 ml of phenol solution with a concentration of 200 mg/L into
the test tube, and made the SWNTs powder evenly distributed in the
solution by shaking and stirring. After this, placed the test tube in the
ultrasonic generator and turned on it. The entire ultrasonic treatment
time was 8 h, and during the experiment the concentration of the phenol
solution at different time points was measured.
Experiment III: In order to compare with the measured data of
Experiment II, put 0.05 g of SWNTs powder into a test tube, then poured
50 ml of phenol solution with a concentration of 200 mg/L into the test
tube, and made the SWNTs powder evenly distributed in the solution by

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Y. Han et al. Chemical Engineering Journal 427 (2022) 131819

shaking and stirring. After this, leave the test tube in a thermostatic
water bath for 8 h, and during the experiment the concentration of the
phenol solution at different time points was measured.
For all experiments, the sampling time points were 0 min, 5 min, 10
min, 15 min, 20 min, 30 min, 40 min, 50 min, 60 min, 80 min, 100 min,
120 min, 150 min, 180 min, 210 min, 240 min, 300 min, 360 min, 420
min and 480 min, respectively. After the collected samples are diluted
20 times, they are measured with a liquid chromatography system. After
that, the measured data is converted into the concentration value of the
solution through the standard curve of the concentration of the phenol
solution.

3. Results and discussion

3.1. MD simulation

3.1.1. Structure parameters

In this section, the radial distribution functions (RDF) of SWNTs (C)
and phenol molecules (P), the average radii of the first phenol shell of
SWNTs (RC-P) and the first phenol coordination of SWNTs (nc-p) are
calculated to analyze the distribution of phenol molecules around
SWNTs under ultrasound with different frequencies. In addition, the
RDF of the oxygen atoms in phenol molecules (OP) and the oxygen atoms
in water molecules (OW), RDF of SWNTs (C) and water molecules (W),
the average radii of the first water shell of OP (ROp-Ow) and the first water
coordination of OP (nOp-Ow) are calculated to evaluate the structural
changes of the water molecules in the periphery of phenolic hydroxyl
when different frequencies of ultrasound are applied. RC-P and ROp-Ow
can be acquired from the location of the first minimum of RDF curves. [g
(r)] is defined as [44]:

〈ρB (r)〉 1 1 ∑ NA ∑ NB
δ(rij − r)
gAB (r) = = (2)
〈ρB (r)〉local 〈ρB (r)〉local NA i∈NA j∈NB 4πr2

Where <ρB(r)>is the density of B particle at the position of distance r from A particle, and
<ρB(r)>local is the average density of B particle at shells around A particle with radius rmax.
Generally, the half of the minimum box length is the value of rmax. NA is the number of A
particle, NB is the particle of B particle. The value of n can be calculated by[45]:
∫ rs
nBA (rs ) = 4πρ0 gAB (r)r2 dr (3)
0

Where rs is the value of position of the first minimum of gAB(r).

Fig. 4(a–c) shows the RDF curves of C-P (gC-P(r)), OP-OW (gOp-Ow(r)) and C-W (gC-W
(r)) under ultrasound with different frequencies, and the RC-P, ROp-Ow, nC-P, and nOp-Ow
under ultrasound with different frequencies can be found in Table 2.
It can be seen from Fig. 4(a) and Table 2 that when there is no ultrasound, the first peak of
gC-P(r) is about 0.5nm away from SWNTs and this position almost don’t change after the
ultrasound is applied. The first minimums (ROP-OW) are also unchanged under ultrasound
with different frequency. The function value of the first peak is prominent compared to other
positions, which means that most phenol molecules are distributed in the position of first peak.
Compared with the gC-P(r) curve in the absence of ultrasound, the height of the first peak
under applying ultrasound is higher, and with the increase of ultrasonic frequency, the height
of the first peak decreases. It indicates that there are more phenol molecules gathered at the
first peak position under the action of the ultrasound, and this trend is inversely proportional
to the ultrasonic frequency (within the ultrasound frequency range of this article). In order to
investigate the adsorption mode between carbon nanotube and phenol, the potential of mean
force (PMF) was calculated based on the RDF results in Fig. 4(a). which can be calculated
by[46]:

E(r) = − kB TlngC− P (r) (4)

Where kB is the Boltzmann’s constant, T is the system temperature,
gC-P(r) is the RDF of carbon nanotube and phenol. The PMF result is
shown in Fig. 5.
As can be seen from Fig. 5, there are two lowest peaks at 0.49nm and Fig. 4. The RDF of (a) C-P, (b) OP and Ow and (c) C-W under different
1.32nm respectively, This indicates that there are two relatively stable frequencies.

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Y. Han et al. Chemical Engineering Journal 427 (2022) 131819

Table 2
Average radii of the first water shell of phenol, the first water coordination number of phenol, the average radii of the first phenol shell of SWNTs, the first phenol
coordination number of SWNTs under the ultrasound with different frequencies.
Frequency (MHz) 0 200 250 333 500 1000

RC-P (nm) 1.146 1.146 1.146 1.146 1.146 1.146

ROP-OW (nm) 0.342 0.340 0.340 0.340 0.340 0.340
nC-P 124.985 152.667 148.011 144.118 140.162 129.332
nOP-OW 0.033 0.028 0.028 0.028 0.028 0.028

that ultrasound enhances the π – π stacking interaction and van der

Fig. 5. Potential of mean force between carbon nanotube and phenol.
states at these two positions, which is due to two kinds of adsorption
between carbon nanotubes and phenol. According to Song’s study[15],
The lowest peak at 0.49 nm indicates that there is π-π stacking interac­
tion between the surface of carbon nanotubes and the benzene ring of
phenol, while the lowest peak at 1.32 nm indicates that there is van der
Waals interaction between the surface of carbon nanotubes and the tail
group (hydroxyl) of phenol, which means phenol molecules form a
double-layer assembled architecture films on nanotube surface. The
results of Song and present study show that the adsorption of small ar­
omatic molecules on the surface of carbon nanotubes seems to tend to
form a double-layer assembled structure. As shown in Fig. 4, the absolute
values of the two lowest peaks of PMF curve increase when ultrasound is
applied compared with the case without ultrasound, which indicates
Waals interaction between the surface of carbon nanotubes and phenol,
and thus leads to the enhancement of the adsorption of phenol on carbon
nanotubes. The schematic diagram of ultrasound enhanced adsorption
of phenol on carbon nanotubes is shown in Fig. 6.
According to Fig. 4(b), when there is no ultrasound, the positions of
the first peak and the first minimum of gOp-Ow(r) are 0.272 nm and
0.342 nm respectively, which is almost consistent with the Zhang’s MD
simulation result[47] (0.275nm and 0.33nm) and Guedes’s Monte Carlo
simulation result[48] (0.265nm and 0.32nm). The small difference be­
tween the results of the present study and these two references may be
due to the difference of the simulated solution concentration or the
simulation method. In addition, the presence of carbon nanotubes in the
simulation model in this paper may also cause changes in the distribu­
tion of solvents around the solute.
When there is an external ultrasound, the position of the first
maximum and the first minimum of gOp-Ow(r) have no change, but the
height of the first peak of gOp-Ow(r) are lower than that with no ul­
trasound, which means the ultrasound can reduce the density of water
molecules around the phenol molecules. In addition, it can be seen from
Fig. 4(b) that as the ultrasonic frequency increases, the density of water
molecules around the phenol molecules will gradually increase. This
means that the ultrasound with a relatively lower frequency has more
influence on the distribution of water molecules around the phenol
molecules.
The results in Table 2 show that, the presence of ultrasound can not
influence the RC-P value. Compared with no ultrasound, the value of nC-
P increases under the action of ultrasound, and with the increase of
ultrasonic frequency, the value of nC-P decreases. In addition, the ROp-
Ow and nOp-Ow with ultrasound are less than those without ultrasound,
but the increase in ultrasonic frequency does not seem to have an effect
on the values of ROp-Ow and nOp-Ow. This result may be explained as
that the mechanical vibration of ultrasound can destroy the structure of
the water solvent layer around phenol[34], thereby reducing the num­
ber of water molecules around phenol, which reduces the binding of
water molecules to phenol. However, the mechanical vibration of

Fig. 6. Enhancement of the adsorption of phenol on carbon nanotubes caused by applied ultrasound.

5
Y. Han et al.
ultrasound vibration is not enough to destroy the adsorption of phenol
on the SWNTs. Thus, this makes it easier for phenol to approach the
SWNTs and adsorb on it. Therefore, it comes to the conclusion that the
external ultrasound can make more phenol molecules absorbed on
SWNTs and reduce the number of coordination water molecules of
phenol.
As is shown in Fig. 4(c), in the presence of ultrasound, the distribution
density of water molecules around the carbon nanotubes is lower than
that without ultrasound. This indicates that ultrasound can enhance the
surface hydrophobicity of carbon nanotubes. This result may also be due
to the enhancement of the adsorption capacity of carbon nanotubes for
phenol. More phenol occupies the space of surrounding water mole­
cules, which makes the water molecules farther away from the surface of
carbon nanotubes.
3.1.2. System energy
The interaction between adsorbent and adsorbate can be analyzed
and studied by calculating the interaction energy. In this section the
interaction of SWNTs-phenol and phenol-water under ultrasound with
different frequency is studied. The interaction energy mainly includes
van der Waals energy (VLJ) and electrostatic interaction energy (VC),
which can be calculated by [49,50]:
[( ) ( )6 ]
∑∑ σij 12 σij qi qj
Vij = VLJ + VC = 4εij − +f (5)
i j
r ij rij ri rj
Where rij is the distance between atomic pairs, σ ij and εij are the potential
energy that conforms to the coupling rules, which are calculated with
σ ij=(σiiσ jj)1/2 and εij=(εiiεjj)1/2. The f is electrostatic conversion factor
and its value is 138.9KJ⋅mol− 1⋅nm⋅e− 2.
According to Equation (4), the interaction energy of SWNTs-phenol
and phenol-water was calculated. For SWNTs-phenol interaction en­
ergy, since there is no Coulomb interaction between SWNTs and phenol
(SWNTs is electrically neutral), the electrostatic interaction energy is
zero. Thus the SWNTs-phenol interaction energy is mainly determined
by van der Waals energy, the results are shown in Fig. 7. For phenol-
water interaction energy, the results of van der Waals energy and elec­
trostatic interaction energy under ultrasound are shown in Fig. 8.
For SWNTs-phenol interaction energy, the value of Vij of SWNTs-
phenol is equal to the value of VLJ, which indicates that Van der
Waals energy is the major driving force for the adsorption of phenol
Fig. 7. The van der Waals energy of SWNTs and phenol molecules under ul­
trasound with different frequency.
6
Chemical Engineering Journal 427 (2022) 131819
molecules on the SWNTs surface. As shown in Fig. 7, the VLJ value of
SWNTs-phenol is -1123.09 kJ⋅mol-1 without ultrasound. When the ul­
trasound with frequencies of 200MHz, 250MHz, 333MHz, 500MHz and
1000MHz, the values of VLJ are -1587.39 kJ⋅mol-1, -1530.6 kJ⋅mol-1,
-1473.58 kJ⋅mol-1, -1446.23kJ⋅mol-1 and -1268.59kJ⋅mol-1, respec­
tively, the absolute value of which are higher than that under no ul­
trasound. This indicates that the VLJ between SWNTs and phenol is
enhanced under ultrasound. Since all the values in Fig. 3 are negative, it
means that the interaction between the SWNTs and phenol is attraction
[51]. Therefore, the calculation result reveals that the presence of ul­
trasound promotes the adsorption between SWNTs and phenol.
According to Fig. 8(a), compared with the Van der Waals energy of
phenol-water without ultrasound (-1590.31 kJ⋅mol-1), the values of VLJ
under the action of ultrasound are less. When the ultrasound with fre­
quencies of 200MHz, 250MHz, 333MHz, 500MHz and 1000MHz are
applied, the values of VLJ are -754.895 kJ⋅mol-1, -799.547 kJ⋅mol-1,
-843.179 kJ⋅mol-1, -876.580 kJ⋅mol-1 and -1127.330 kJ⋅mol-1,
respectively. From the results of VLJ interaction energy, it can be seen
that ultrasonic can weaken the van der Waals energy between phenol
and water molecules. As shown in Fig. 8(b), compared with the VC value
of no ultrasound (-5314.2 kJ⋅mol-1), the electrostatic interaction energy
between phenol and water molecule is reduced under the action of the
ultrasound. When the ultrasound with frequencies of 200MHz, 250MHz,
333MHz, 500MHz and 1000MHz are applied, the values of VC are
-754.895 kJ⋅mol-1, -799.547 kJ⋅mol-1, -843.179 kJ⋅mol-1, -876.580
kJ⋅mol-1 and -1127.330 kJ⋅mol-1, respectively. The results of the elec­
trostatic interaction energy reveals that the ultrasonic can weaken the
electrostatic attraction between the phenol molecules and water mole­
cule. Unlike the interaction between phenol and SWNTs, there are both
van der Waals and electrostatic interaction between phenol and water
molecule. The water molecule is a polar molecule, and its positive and
negative charge centers do not overlap, thus the water molecule is not
electrically neutral. Due to the presence of hydroxyl, the phenol mole­
cule is also a polar molecule and has a certain degree of hydrophilicity.
Therefore, there is electrostatic attraction between phenol and water
molecule. Comparing Fig. 8(a and b), it can be seen that the van der
Waals interaction between phenol and water molecule is much smaller
than the electrostatic interaction, which means the electrostatic inter­
action between phenol and water is dominant. According to the results
in Fig. 8, it can be concluded that ultrasound can weaken the van der
Waals and electrostatic effects between phenol and water molecule at
the same time, that is, weaken the total interaction energy vij, which
means that the ultrasound effect can weaken the hydrophilicity of
phenol.
In addition, a notable phenomenon can be found in Fig. 7 and Fig. 8
is that as the frequency of ultrasound increases, the effect of ultrasound
on the interaction energy of SWNTs-phenol and phenol-water shows a
downward trend. This makes it possible in theory that when the ultra­
sonic frequency increases to a certain value, the effect of ultrasound may
change from a positive effect to a negative effect. Therefore, it indicates
that excessively high ultrasonic frequencies may not be beneficial for
enhancing the adsorption of phenol on the nanotubes.
3.1.3. Hydrogen bonding analysis
Previous studies [52–55] have shown that the adsorption between
carbon nanotubes and phenol may also due to hydrophobic adsorption,
which means that under other conditions unchanged, the hydropho­
bicity of phenol is directly proportional to the adsorption strength be­
tween phenol and carbon nanotubes. Phenol has both hydrophilic and
hydrophobic properties. Its hydrophilicity comes from phenolic hy­
droxyl group, while its hydrophobicity comes from phenyl group. The
phenolic hydroxyl group can form a hydrogen bond with water mole­
cule, which makes phenol to exhibit hydrophilicity. If the hydrogen
bond structure formed around phenol changes, this will affect the hy­
drophilicity of phenol, and further affect the hydrophobicity of phenol.
Therefore, in this section the number of hydrogen bond formed around
Y. Han et al.
Fig. 8. The van der Waals energy (a) and coulomb energy (b) of phenol and water molecules under ultrasound with different frequency.
phenol and the hydrogen bond lifetime are calculated under the action
of ultrasound with different frequency.
Generally, hydrogen bond is defined as an interaction between all
Fig. 9. Schematic diagram of hydrogen bond for phenol − water.
7
Chemical Engineering Journal 427 (2022) 131819
possible donors and acceptors. Geometric criteria is used in the analysis
to determine the presence or absence of hydrogen bond. Geometric
criteria indicates that the distance r between the donor and the acceptor
is less than 0.35 nm and the angle θ of the hydrogen – donor – acceptor is
smaller than 30◦ . In this paper, for defining the hydrogen bond, the O in
phenol (OP) is set as a donor and the O in water (OW) is set as an acceptor
(P-W). A schematic diagram of the hydrogen bond formed by phenol and
water molecules is shown in Fig. 9.
In addition, the average lifetime of hydrogen bond τ [56] is also
investigated to analyze the strength of hydrogen bond, which can be
calculated with Eq (6) [57,58]:
∫∞
τ= C(t)dt (6)
0
Where C(t) represents the probability that a marked hydrogen bond exists at t=0 and remains
intact for a subsequent time t. The definition of C(t) is expressed as Eq. (7):
C(t) = 〈h(0)h(t)/h(0)〉 (7)
Where h(t) is Heaviside unit step function and hi(t)={0,1}. When h(t)=1, it means that
hydrogen bond exists between molecules from time 0 to t, otherwise hi(t)=0.
Table 3 lists the calculated results of the number of hydrogen bond nHB and the lifetime
of hydrogen bond τHB of each phenol molecule at different ultrasonic frequencies.
As can be seen from Table 3, compared with the case of no ultrasound, the number of
hydrogen bond (nHB) between phenol and water molecules is reduced under the action of
ultrasound. However, with the increase of ultrasonic frequency, the number of hydrogen bond
showed an increasing trend. At the same time, compared with the case without ultrasound, the
presence of ultrasound significantly reduces the average lifetime of hydrogen bond (τHB), and
this reduction effect tends to weaken as the ultrasonic frequency increases. These results
indicate that the presence of ultrasound can not only destroy the hydrogen bond structure
around phenol, but also makes the formed hydrogen bond become unstable. This implies that
the interaction between phenol and water is weakened, which means that the hydrophilicity of
phenol is weakened by ultrasound. The weakening of the hydrophilicity of phenol makes its
hydrophobicity more significant, which thus enhances the hydrophobic adsorption between
phenol and carbon nanotube. This phenomenon can be explained by the cavitation caused by
the alternating positive and negative ultrasonic pressure. According to Hisashi Okumura’s
research results [34], when the simulation system is in a half-cycle of ultrasonic when
pressure is negative, the density of water molecule will decrease significantly, and there is a
tendency to form bubbles. When the bubble collapsed after pressure became positive, water
molecules crashed against hydrophilic residues. In the present study, although no bubble is
generated due to the use of periodic boundary conditions and NPT ensemble, the density of
water molecule decreases significantly when the pressure is negative, and when the pressure is
positive the density of water molecule is recovered again. This alternating process of positive
pressure and negative pressure makes the phenolic hydroxyl group of phenol (hydrophilic
residue) be crashed, which breaks the formation of hydrogen bonds between phenol and water.
Y. Han et al.
Table 3
Average Number of Hydrogen Bonds per Phenol Molecule (nHB) and Relaxation Time of Hydrogen Bonds(τHB) at Various ultrasonic frequencies.
Frequency (MHz) 0 200
nHB 1.7238 1.5785
τHB 137.9004 126.6783
3.1.4. The density distribution of water molecules
The density distribution of water molecules around SWNTs directly
affects the adsorption of phenol and SWNTs. Theoretically, the higher
the density of water molecules around SWNTs, the higher the energy
barrier that phenol has to overcome when approaching the SWNTs.
Therefore, in this section the number density distribution of water
molecule around SWNTs (along the × axis) is calculated, and the result
is shown in Fig. 10. According to Fig. 2, it can be seen that positive
pressure and negative pressure alternately occur during the application
of ultrasound. In order to analyze the influence of positive pressure and
negative pressure on the density of water molecules, we exhibit the
density distribution curves of water molecules around SWNTs under
positive pressure and negative pressure in Fig. 10(a and b), respectively.
As can be seen from Fig. 10(a), compared with the case without ul­
trasound, the density distribution of water molecules around SWNTs
does not change significantly under the action of positive pressure, and
Fig. 10. Density distribution of water along the × axis in the negative pressure
and positive pressure of MD simulated ultrasonic waves under different ultra­
sonic frequencies.
Chemical Engineering Journal 427 (2022) 131819
250 333 500 1000
1.5891 1.6050 1.6007 1.6979
127.1325 128.4018 128.6187 135.8332
the change of half-period (related to ultrasound frequency) of positive
pressure has basically no effect on the density distribution of water
molecules. However, Fig. 10(b) shows that negative pressure has a sig­
nificant effect on the density of water molecules around SWNTs.
Compared with the case without ultrasound, the negative pressure
generated by ultrasound of all frequencies significantly reduces the
density of water molecules around SWNTs. But similar to the situation in
Fig. 10(a), the change of half-period of the ultrasonic negative pressure
has no significant effect on the density distribution of water molecules.
The above calculation results show that the density distribution of water
molecules around SWNTs will change significantly only when the ul­
trasound generates negative pressure in the aqueous solution, and this
result is consistent with the results of Mitsuhiro Matsumoto’s research
[59]. Ultrasonic cavitation effect can be employed to explain this phe­
nomenon. When ultrasound acts on liquids, the small bubbles can be
produced. One reason is that partial tensile stress occurs in the liquid to
form a negative pressure, and the strong tensile stress tears the liquid
into a cavity, which is called cavitation. Mitsuhiro Matsumoto’s simu­
lation results showed that cavitation will only appear when there is a
partial negative pressure in the solution. Hisashi Okumura’s research
results also showed that cavitation bubbles will appear around the
protein only when the negative pressure of ultrasound is applied[34].
This indicates that under the negative pressure of ultrasound, the density
of water molecules will decrease locally in the solution, and then bub­
bles will be generated. Different from the research results of Mitsuhiro
Matsumoto and Hisashi Okumura, in the present study it can be seen
from Fig. 10(b) that the distribution density of water molecule does
decrease under the action of ultrasonic negative pressure, but no cavi­
tation bubbles appear. The reason for this difference may be due to the
periodic boundary conditions and NPT ensemble used in our work. Due
to the use of the NPT ensemble, when the density of water decreases, in
order to keep the pressure constant, the size of the simulated box will
change. Moreover, due to the existence of periodic boundary conditions,
after the water molecules under stress move out from one side of the box,
they enter the box from the other side of the box at the same time.
Therefore, no cavities caused by local negative pressure will appear in
the box.
3.2. Experimental verification
The MD simulation results show that ultrasound can enhance the
interaction between SWNTs and phenol, thus promotes the adsorption of
phenol by SWNTs. In order to verify the simulation results that ultra­
sound can promote the adsorption between SWNTs and phenol, in this
section, a simple but effective experiment is carried out. As is known, if
the adsorption between SWNTs and phenol is enhanced, the phenol
concentration in the solution will inevitably decrease. Therefore, in the
present experimental study, the concentration of phenol solution before
and after the adsorption of SWNTs under ultrasound with different
frequency are measured. The specific experimental details can be found
in Section 2.2. The results of three independent experiments can be
found in Fig. 11. In Fig. 11, the C1 curve represents the result of
Experiment I, the C2 curve represents the result of Experiment III, and
the C3 curve represents the result of Experiment II.
As can be seen in Fig. 11, the C1 curve is the concentration change of
phenol solution under the condition of ultrasound without SWNTs.
When only ultrasound was applied, the concentration of phenol almost
did not change (stabilized at 174 mg/L), which indicates that the ul­
trasound has no significant effect on phenol in the solution. C2 curve is
8
Y. Han et al.
Fig. 11. The concentration changes of phenol solution under three
different conditions.
the concentration change of phenol solution with SWNTs powder added
under no ultrasound. It can be seen from the C2 curve that when there is
no ultrasonic applied, the SWNTs quickly completed the adsorption of
phenol, making the phenol concentration drop from 200 mg/L to
162.17 mg/L, and this concentration had been maintained until the end
of the experiment. This indicates that the adsorption speed of SWNTs to
phenol is very fast, and the saturated adsorption SWNTs are relatively
stable.
C3 curve is the concentration change of phenol solution under the
condition of ultrasound with SWNTs powder added. It can be clearly
seen from the C3 curve that the concentration of the phenol solution has
a change process of first decreasing and then increasing. This process
takes place between 80 min and 210 min of the experimental time, and
the minimum (111.81 mg/L) appears at the time point of 100 min. This
phenomenon shows that after about 80 min of ultrasound treatment, the
adsorption efficiency of SWNTs on phenol began to increase signifi­
cantly, and at 100 min, the adsorption capacity of carbon nanotubes on
phenol reached the maximum. After that, as the ultrasonic effect
continued, the adsorbed phenol began to fall off the carbon nanotubes
and return to the solution. After 210 min, the effect of ultrasound on the
phenol adsorbed on SWNTs was weak. In order to verify that phenol
falling off carbon nanotubes after 100 min is the result of ultrasonic
continuous action, an additional comparative experiment was per­
formed. In this additional experiment, the operation process was
consistent with experiment II in the first 100 min, and after that the
ultrasonic generator was turned off. During the later period, the solution
was placed in a constant temperature water bath and sampled at spec­
ified intervals. The result of additional comparative experiment was
shown as curve C4 in Fig. 11. According to curve C4, it can be seen that
after 100 min of ultrasonic treatment, the concentration of phenol in the
solution remained unchanged, and did not rise as in C3. This indicates
that the concentration rise of C3 after 100 min is due to the continuous
effect of ultrasound.
The above experimental results indicate that ultrasound can indeed
enhance the ability of SWNTs to adsorb phenol. This is consistent with
the results of the MD simulation study, which proves the correctness of
the simulation conclusion. However, the results of the experimental
study also show that the enhancement effect of ultrasound on the
adsorption of phenol by the SWNTs only occurs within a certain period
of time, after which the enhancement will disappear. This may be due to
the mechanical oscillation of ultrasound for saturated adsorbed SWNTs,
which will cause the phenol molecules adsorbed on the nanotubes to fall
off again and return to the solution. Therefore, the treatment time
should not be too long when using ultrasound to enhance the adsorption
of SWNTs to phenol. But from another perspective, compared with the
9
Chemical Engineering Journal 427 (2022) 131819
traditional methods for the recovery and regeneration of carbon based
adsorbents (such as heating regeneration method, biological regenera­
tion method, microwave regeneration method, etc[60–64]), this phe­
nomenon may also provide a new solution for the regeneration of carbon
nanotubes after adsorption of phenol by controlling the ultrasonic action
time.
4. Conclusion
In this article, a novel convenient method based on segmented
simulation was proposed to realize the loading of ultrasonic boundary
condition in MD simulation, and using this method, the effect of ultra­
sound on the adsorption properties of SWNTs to phenol were studied.
The effects of ultrasound with different frequency on the adsorption
properties of SWNTs were studied by comparing the structural param­
eters, interaction energy, hydrogen bond and density distribution of
water molecules, and then a series of experiments were performed to
verify the MD simulation results. Some important conclusions are as
follows:
(1) The ultrasound can not only make more phenol molecules
absorbed on SWNTs, but also reduce the number of coordination
water molecules of phenol according to the RDF study. In addi­
tion, ultrasound enhances the π – π stacking interaction and van
der Waals interaction between the surface of carbon nanotubes
and phenol according to the PMF study.
(2) Compared with the case under no ultrasonic waves, the external
ultrasound can enhance the interaction energy of SWNTs and
phenol.
(3) The ultrasound can weaken the strength of hydrogen bond be­
tween phenolic hydroxyl and water molecules, which means that
the hydrophilicity of phenol is weakened. However, the hydrogen
bond strength can be enhanced by the increasing ultrasonic fre­
quency within a certain simulated frequency.
(4) The density distribution of water molecules around SWNTs will
change significantly only when the ultrasound generates negative
pressure in the aqueous solution, which proves the effectiveness
of the method of segmented simulation of ultrasonic boundary
condition proposed in this study.
(5) The experimental results showed that the concentration of phenol
solution was significantly reduced under the action of ultrasound,
which can be used to prove the MD simulation results that ul­
trasound can enhance the adsorption effect of SWNTs on phenol.
The research results in this article are expected to provide a theo­
retical basis for carbon nanotube adsorption enhancement technology
based on physical field effects, and to further promote the application of
nanomaterial adsorbent in water treatment technology. In addition,
although power ultrasound has been widely used in many chemical
engineering fields, the microscopic changes caused by the ultrasonic
action occur too fast to be measured by experimental methods. There­
fore, the method of loading ultrasonic boundary condition proposed in
this study can provide a simple and effective way for other researchers to
explore the internal mechanisms related to sonochemistry through MD
simulation method.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (grant no. 51408525 and 61903321), University
Y. Han et al.
Science and Technology Research Projects of Hebei Province (grant no.
ZD2020324) and The Central Guidance on Local Science and Technol­
ogy Development Fund of Hebei Province (grant no. 216Z3601G).
References
[1] K. Coutinho, B.J.C. Cabral, S. Canuto, Can larger dipoles solvate less?
solute− solvent hydrogen bond and the differential solvation of phenol and
phenoxy, Chem. Phys. Lett. 399 (2004) 534–538.
[2] S.G. Estacio, B.J.C. Cabral, Born− Oppenheimer molecular dynamics of phenol in a
water cluster, Chem. Phys. Lett. 456 (2008) 170–175.
[3] J.A. Zazo, J.A. Casas, A.F. Mohedano, J.J. Rodríguez, Catalytic wet peroxide
oxidation of phenol with a Fe/active carbon catalyst, Appl. Catal. B 65 (3-4) (2006)
261–268.
[4] Z. Zeng, H. Zou, X. Li, M. Arowo, B. Sun, J. Chen, G. Chu, L. Shao, Degradation of
phenol by ozone in the presence of Fenton reagent in a rotating packed bed, Chem.
Eng. J. 229 (2013) 404–411.
[5] M. Ahmaruzzaman, D.K. Sharma, Adsorption of phenols from wastewater,
J. Colloid Interface Sci. 287 (1) (2005) 14–24.
[6] D. Yuan, C. Zhang, S. Tang, Z. Wang, Q. Sun, X. Zhang, T. Jiao, Q. Zhang, Ferric
ion-ascorbic acid complex catalyzed calcium peroxide for organic wastewater
treatment: Optimized by response surface method, Chin. Chem. Lett. (2021),
https://doi.org/10.1016/j.cclet.2021.04.050.
[7] F.-F. Mao, Y. Zhou, W. Zhu, X.-Y. Sang, Z.-M. Li, D.-J. Tao, Synthesis of
Guanidinium-Based Poly(ionic liquids) with Nonporosity for Highly Efficient SO2
Capture from Flue Gas, Ind. Eng. Chem. Res. 60 (16) (2021) 5984–5991.
[8] X. Liu, Y. Zhou, C.h. Wang, Y. Liu, D. Tao, Solvent-free self-assembly synthesis of N-
doped ordered mesoporous carbons as effective and bifunctional materials for CO2
capture and oxygen reduction reaction, Chem. Eng. J. 427 (2022), 130878.
[9] D. Tao, F. Qu, Z. Li, Y. Zhou, Promoted absorption of CO at high temperature by
cuprous-based ternary deep eutectic solvents, AIChE J. 62 (2021), e17106.
[10] D. Aditya, P. Rohan, G. Suresh, Nano-adsorbents for Wastewater Treatment: A
Review, Res. J. Chem. Environ. 15 (2011) 1033–1040.
[11] G. Pulido-Reyes, F. Leganes, F. Fernández-Piñas, R. Rosal, Bio-nano interface and
environment: A critical review, Environ. Toxicol. Chem. 36 (12) (2017)
3181–3193.
[12] L. Guo, H. Cao, L. Cao, N.a. Li, A. Zhang, Z. Shang, T. Jiao, H.L. Liu, M. Wang,
Improve optical properties by modifying Ag nanoparticles on a razor clam SERS
substrate, Opt. Express. 29 (4) (2021) 5152, https://doi.org/10.1364/OE.418551.
[13] Y. Xu, R. Wang, J. Wang, et al., Facile fabrication of molybdenum compounds
(Mo2C, MoP and MoS2) nanoclusters supported on N-doped reduced graphene
oxide for highly efficient hydrogen evolution reaction over broad pH range, Chem.
Eng. J. 417 (2021), 129233.
[14] A. Peigney, C.h. Laurent, E. Flahaut, R.R. Bacsa, A. Rousset, Specific surface area of
carbon nanotubes and bundles of carbon nanotubes, Carbon 4 (2001) 507–514.
[15] X. Song, H. Guo, J. Tao, S. Zhao, X. Han, H. Liu, Encapsulation of single-walled
carbon nanotubes with asymmetric pyrenyl-gemini surfactants, Chem. Eng. Sci.
187 (2018) 406–414.
[16] J. Comer, R. Chen, H. Poblete, A. Vergara-Jaque, J.E. Riviere, Predicting
adsorption affinities of small molecules on carbon nanotubes using molecular
dynamics simulation, ACS Nano 9 (12) (2015) 11761–11774.
[17] V. Trovato, E. Teblum, Y. Kostikov, A. Pedrana, V. Re, G.D. Nessim, G. Rosace,
Electrically conductive cotton fabric coatings developed by silica sol-gel precursors
doped with surfactant-aided dispersion of vertically aligned carbon nanotubes
fillers in organic solvent-free aqueous solution, J. Colloid. Inter. SCI. 586 (2021)
120–134.
[18] C. Lu, C. Yao, C.K.F. Lei, Adsorption of trihalomethanes from water with carbon
nanotubes, Water. Res. 39 (2005) 1183–1189.
[19] X.J. Peng, J.J. Jia, X.M. Gong, et al., Aqueous stability of oxidized carbon
nanotubes and the precipitation by salts, J. Hazard. Mater. 165 (2009) 1239–1242.
[20] O. Hamdaoui, E. Naffrechoux, L. Tifouti, et al., Effects of ultrasound on adsorption-
desorption of p-chlorophenol on granular activated carbon, Ultrason. Sonochem.
10 (2003) 109–114.
[21] O. Hamdaoui, E. Naffrechoux, J. Suptil, et al., Ultrasonic desorption of p-
chlorophenol from granular activated carbon, Chem. Eng. J. 106 (2005) 153–161.
[22] R.S. Juang, S.H. Lin, C.H. Cheng, Liquid-phase adsorption and desorption of phenol
onto activated carbons with ultrasound, Ultrason. Sonochem. 13 (2006) 251–260.
[23] S. Bekkouche, M. Bouhelassa, N.H. Salah, et al., Study of adsorption of phenol on
titanium oxide (TiO2), Desalination 166 (2004) 355–362.
[24] B.S. Schueller, R.T. Yang, et al., Ultrasound Enhanced Adsorption and Desorption
of Phenol on Activated Carbon and Polymeric Resin, Ind. Eng. Chem. Res. 40
(2001) 4912–4918.
[25] Z. Li, X.B. Li, H.X. Xi, et al., Effects of ultrasound on adsorption equilibrium of
phenol on polymeric adsorption resin, Chem. Eng. J. 86 (2002) 375–379.
[26] W. Qin, Y.H. Yuan, Y.Y. Dai, Effect of ultrasound on desorption equilibrium, Chin.
J. Chem. Eng. 9 (2001) 427–430.
[27] M. Dastkhoon, M. Ghaedi, A. Asfaram, et al., Ultrasound assisted adsorption of
malachite green dye onto ZnS:Cu-NP-AC: Equilibrium isotherms and kinetic studies
– Response surface optimization, Sep. Purif. Technol. 156 (2015) 780–788.
[28] H. Ding, X. Li, J. Wang, et al., Adsorption of chlorophenols from aqueous solutions
by pristine and surface functionalized single-walled carbon nanotubes, Acta.
Scientiae. Circumstantiae. 43 (2016) 187–198.
10
Chemical Engineering Journal 427 (2022) 131819
[29] A. Striolo, A.A. Chialvo, K.E. Gubbins, et al., Water in carbon nanotubes:
adsorption isotherms and thermodynamic properties from molecular simulation,
J. Chem. Phys. 122 (2005) 56.
[30] L. Liu, D. Nicholson, S.K. Bhatia, Adsorption of CH4 and CH4/CO2 mixtures in
carbon nanotubes and disordered carbons: A molecular simulation study, Chem.
Eng. SCI. 121 (2015) 268–278.
[31] A. Rahman, P. Deshpande, M.S. Radue, et al., A machine learning framework for
predicting the shear strength of carbon nanotube-polymer interfaces based on
molecular dynamics simulation data, Compos. Sci. Technol 207 (2021), 108627.
[32] J.Y. Lee, C. Lee, E. Osawa, et al., Snapshots of the Fragmentation for C-70@Single-
Walled Carbon Nanotube: Tight-Binding Molecular Dynamics Simulations, Int. J.
Mol. Sci. 8 (2021) 3929.
[33] F. Wu, Y.S. Zhao, Y.F. Zhao, et al., Impact-resistant carbon nanotube woven films: a
molecular dynamics study, Nanoscale. 9 (2021) 5006–5013.
[34] H. Okumura, S.G. Itoh, Amyloid Fibril Disruption by Ultrasonic Cavitation:
Nonequilibrium Molecular Dynamics Simulations, J. Am. Chem. Soc. 136 (30)
(2014) 10549–10552.
[35] M. Nedyalkova, S. Madurga, S. Pisov, I. Pastor, Molecular dynamics simulation of
the spherical electrical double layer of a soft nanoparticle: Effect of the surface
charge and counterion valence, J. Chem. Phys. 137 (2012), 174701.
[36] D. Van der Spoel, E. Lindahl, B. Hess, G. Groenhof, A.E. Mark, H.J.C. Berendsen,
GROMACS: Fast, flexible and free, J. Comput. Chem. 26 (2005) 1701–1718.
[37] S. Páll, M.J. Abraham, C. Kutzner, B. Hess, E. Lindahl, Tackling exascale software
challenges in molecular dynamics simulations with GROMACS, J. Chem. Phys. 70
(2015) 139.
[38] H.J.C. Berendsen, J.R. Grigera, T.P. Straatsma, The missing term in effective pair
potentials, J. Phys. Chem. 91 (24) (1987) 6269–6271.
[39] G.A. Kaminski, R.A. Friesner, J. Tirado-Rives, W.L. Jorgensen, Evaluation and
reparametrization of the OPLS-AA force field for proteins via comparison with
accurate quantum chemical calculations on peptides, J. Phys. Chem. B. 105 (28)
(2001) 6474–6487.
[40] W.D. Cornell, P. Cieplak, C.I. Bayly, I.R. Gould, K.M. Merz, D.M. Ferguson Jr., D.
C. Spellmeyer, T. Fox, J.W. Caldwell, P.A. Kollman, J. Am. Chem. Soc. 117 (1995)
5179–5197.
[41] W.L. Jorgensen, D.S. Maxwell, J. Tirado-Rives, Development and testing of the
OPLS all-atom force field on conformational energetics and properties of
organicliquids, J. Am. Chem. Soc. 118 (45) (1996) 11225–11236.
[42] K.F. Rinne, S. Gekle, D.J. Bonthuis, et al., Nanoscale pumping of water by AC
electric fields, Nano. Lett. 12 (2012) 1780.
[43] L. Liu, D. Nicholson, S.K. Bhatia, Impact of H2O on CO2 Separation from Natural
Gas: Comparison of Carbon Nanotubes and Disordered Carbon, J. Phys. Chem. C
119 (2015) 407–419.
[44] Y. Han, L. Zhu, Y. Zhang, Molecular dynamics simulation for the impact of external
electric fields on CaCl2 aqueous solution, Chem. Res. Chinese. U. 32 (4) (2016)
641–646.
[45] A.A. Chialvo, J.M. Simonson, The structure of CaCl2 aqueous solutions over a wide
range of concentration. Interpretation of diffraction experiments via molecular
simulation, J. Chem. Phys. 119 (15) (2003) 8052–8061.
[46] S.S. Liu, H. Zhang, H. Wang, S.L. Yuan, S.F. Hou, Molecular dynamics simulations
of EDTA-modified graphene oxide for Pb (II) and Na (I) removal, Chem. J. Chinese.
U 38 (2017) 67–71.
[47] N. Zhang, X.H. Ruan, Y.C. Song, Z. Liu, G.H. He, Molecular dynamics simulation of
the hydration structure and hydrogen bonding behavior of phenol in aqueous
solution, J. Mol. Liq. 221 (2016) 942–948.
[48] R.C. Guedes, K. Coutinho, B.J. Costa Cabral, S. Canuto, Differential hydration of
phenol and phenoxy radical and the energetics of the phenol O-H bond in solution,
J. Phys. Chem. B 107 (18) (2003) 4304–4310.
[49] W.Q. Lin, L. Xu, L. Chen, et al., Molecular dynamics simulations of the adsorption
of bisphenol A on graphene oxide, Acta. Phys. Sin. 65 (2016) 80–86.
[50] Y. Han, S.R. Ma, J. Ma, et al., In-situ desorption of acetaminophen from the surface
of graphene oxide driven by an electric field: A study by molecular dynamics
simulation, Chem. E.J. 418 (2021) 129–391.
[51] S.S. Liu, H. Zhang, H. Wang, S.L. Yuan, S.F. Hou, Molecular Dynamics Simulations
of EDTA modified Graphene Oxide for Pb (II) and Na (I) Removal, Chem. J.
Chinese. U. 38 (2017) 67–71.
[52] Q.R. Zhang, Y. Han, L.C. Wu, Influence of electrostatic field on the adsorption of
phenol on single-walled carbon nanotubes: A study by molecular dynamics
simulation, Chem. Eng. J. 363 (2019) 278–284.
[53] X.Y. Chen, X.G. Sun, Y.Y. Nie, Z.P. Pang, Absorption of pentachlorophenol on
multiwalled carbon nanotubes in methanol system, New. Chem. Mater. 44 (2016)
73–75.
[54] K. Wang, J.B. Pang, L.W. Li, S.Z. Zhou, Y.H. Li, T.Z. Zhang, Synthesis of
hydrophobic carbon nanotubes/reduced graphene oxide composite films by flash
light irradiation, Front. Chem. Sci. Eng. 12 (2018) 376–382.
[55] M.L. Sun, R.M. Cheng, X.C. Xu, et al., Studies on adsorption of phenol and
substituted phenols on carbon nanotubes, Chem. Res. Appl. 18 (2006) 13–18.
[56] W.F.V. Gunsteren, Biomolecular Simulation: the GROMOS96 Manual and User
Guide, Groningen, Zurich, 1996.
[57] A. Luzar, D. Chandler, Hydrogen-bond kinetics in liquid water, Nature 379 (1996)
55–57.
[58] R. Reale, N.J. English, P. Marracino, M. Liberti, F. Apollonio, Dipolar response and
hydrogen-bond kinetics in liquid water in square-wave time-varying electric fields,
Mol. Phys. 112 (2014) 1870–1878.
[59] M. Matsumoto, How Can Molecular Simulations Contribute to Thermal
Engineering? – Topics from Microbubbles and Microscale Heat Conduction,
J. Therm. Sci. Tech. 2 (2008) 309–318.
Y. Han et al.
[60] J.-H. Kim, S.-J. Lee, M.-B. Kim, J.-J. Lee, C.-H. Lee, Sorption equilibrium and
thermal regeneration of acetone and toluene vapors on an activated carbon, Ind.
Eng. Chem. Res. 46 (13) (2007) 4584–4594.
[61] F. Salvador, C.S. Jiḿ enez, A new method for regenerating activated carbon by
thermal desorption with liquid water under subcritical conditions, Carbon 34 (4)
(1996) 511–516.
[62] Kai Wang, Liwei Li, Tiezhu Zhang, Zaifei Liu, Nitrogen-doped graphene for
supercapacitor with long-term electrochemical stability, Energy 70 (2014)
612–617.
11
Chemical Engineering Journal 427 (2022) 131819
[63] H. Zhao, R. Wang, H. Deng, L. Zhang, L. Gao, L. Zhang, T. Jiao, Facile preparation
of self-assembled chitosan-based POSS-CNTs-CS composite as high-efficient dye
absorbent for wastewater treatment, ACS Omega 6 (2021) 294–300.
[64] C. Coelho, A. Oliveira, M. Pereira, O. Nunes, The influence of activated carbon
surface properties on the adsorption of the herbicide molinate and the
bioregeneration of the adsorbent, J. Hazard. Mater. 138 (2) (2006) 343–349.