Journal of Hazardous Materials 354 (2018) 258–265

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Journal of Hazardous Materials

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

Molecular simulation and experimental validation of resorcinol adsorption T

on Ordered Mesoporous Carbon (OMC)
Zaki Uddin Ahmada,c, Bing Chaoa, Mas Iwan Konggidinatab, Qiyu Liana,c, Mark E. Zappib,c,
⁎
Daniel Dianchen Ganga,c,
a
Department of Civil Engineering, University of Louisiana at Lafayette, P. O. Box 43598, Lafayette, LA, 70504, USA
b
Department of Chemical Engineering, University of Louisiana at Lafayette, P. O. Box 43675, Lafayette, LA, 70504, USA
c
Center for Environmental Technology, The Energy Institute of Louisiana, P. O. Box 43597, Lafayette, LA, 70504, USA

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Numerous research works have been devoted in the adsorption area using experimental approaches. All these
Ordered mesoporous carbon approaches are based on trial and error process and extremely time consuming. Molecular simulation technique
Rhombic OMC model is a new tool that can be used to design and predict the performance of an adsorbent. This research proposed a
Molecular simulation simulation technique that can greatly reduce the time in designing the adsorbent. In this study, a new Rhombic
Adsorption
ordered mesoporous carbon (OMC) model is proposed and constructed with various pore sizes and oxygen
Validation
contents using Materials Visualizer Module to optimize the structure of OMC for resorcinol adsorption. The
specific surface area, pore volume, small angle X-ray diffraction pattern, and resorcinol adsorption capacity were
calculated by Forcite and Sorption module in Materials Studio Package. The simulation results were validated
experimentally through synthesizing OMC with different pore sizes and oxygen contents prepared via hard
template method employing SBA-15 silica scaffold. Boric acid was used as the pore expanding reagent to syn-
thesize OMC with different pore sizes (from 4.6 to 11.3 nm) and varying oxygen contents (from 11.9% to 17.8%).

⁎
Corresponding author at: Department of Civil Engineering, University of Louisiana at Lafayette, P. O. Box 43598, Lafayette, LA, 70504, USA.
E-mail address: Gang@louisiana.edu (D.D. Gang).

https://doi.org/10.1016/j.jhazmat.2018.04.072
Received 2 February 2018; Received in revised form 25 April 2018; Accepted 26 April 2018
Available online 27 April 2018
0304-3894/ © 2018 Elsevier B.V. All rights reserved.
Z.U. Ahmad et al.
Based on the simulation and experimental validation, the optimal pore size was found to be 6 nm for maximum
adsorption of resorcinol.
1. Introduction
The conventional porous carbon materials used as adsorbents, for
example activated carbon, usually possess relatively wide pore size
distributions in micropore range (pore size less than 2 nm) [1]. Lim-
itations such as slow mass transfer and low specific surface area that
lead to lower adsorption capacity have been reported for these ad-
sorbents [2]. To overcome such limitations, synthetically produced
adsorbent such as Ordered Mesoporous Carbon (OMC) with tunable
pore size (3–10 nm), high specific surface area (1300–2000 m2 g−1) and
large pore volume (1–2 cm3 g−1) was studied [3]. Previous studies have
demonstrated that OMCs with well-controlled pore structure and
narrow pore size distribution have shown good potential for the ad-
sorption of organic and inorganic pollutants. Wang et al. [4] suggested
that OMC is a potential adsorbent for the removal of volatile organic
compounds (VOCs). Good adsorption capacities of OMC were reported
for the removal of resorcinol, BTEX and synthetic azo dyes from aqu-
eous solutions [5,6,7,8,9]. Chen et al. [10] reported the synthesis of
OMC with large accessible pores (22 nm). The obtained OMC was found
to be an effective adsorbent for Cr(VI) removal. In addition, OMC
functionalized with 4-acetophenone oxime reported by Tian et al. [11]
demonstrated promising adsorption capacity for U(VI). Several dif-
ferent approaches have been proposed and experimentally studied to
synthesize OMC and develop the relation between structural char-
acteristics of OMC and its adsorption capacity. Yuan et al. [12] in-
vestigated the effect of pore volume on the adsorption capacity of
Methylene Blue onto OMC. It was concluded that the volume of me-
sopores with the pore size larger than 3.5 nm have large impact and was
found to be important in the effective adsorption of Methylene blue
onto OMC. Kim et al. [13] synthesized OMC at three different pyrolysis
temperatures to understand the effects of acidic function groups and
porosity on adsorption capacity. It was found that the adsorbed amount
of methyl mercaptan onto OMC was strongly influenced by the acidic
functional group. Hence, the pore size and surface chemistry of OMC
are two important factors that can affect the adsorption capacity
[14,15].
Although widespread experimental research works have been un-
dertaken to synthesize OMC with different pore sizes and different
function groups to enhance the adsorption capacity and to investigate
the adsorption mechanism, the interactions between OMC and ad-
sorbates are still not completely understood. An alternative technique
to study the adsorption behavior of mesoporous materials is molecular
simulation on atomistic level. Zhou et al. [16] constructed a hexagonal
Fig. 1. (a) The model of amorphous carbon unit cell (b) Repetitive rhombic unit for OMC modeling.
259
Journal of Hazardous Materials 354 (2018) 258–265
model of MCM-41, and studied the adsorption of CO2, N2 and flue gas
on MCM-41 by the Grand Canonical Monte Carlo (GCMC) simulation.
Chen et al. [17] constructed ZSM-5-MCM-41 model using Materials
Visualizer module to investigate the structural information and toluene
adsorption. The simulated adsorption isotherm followed Langmuir
isotherm and was consistent with the experimental results. Cao et al.
[18] carried out the GCMC simulation to investigate the adsorption of
nitrogen onto MCM-41 by employing Tjatjopoulos–Feke–Mann (TFM)
potential to understand the interaction between fluid molecule and
MCM-41 pore wall. In addition, Jentys et al. [19] studied the type and
concentration of hydroxyl groups present on MCM-41 as a function of
Si/Al ratio and the pore size using infrared spectroscopy. The internal
surface of MCM-41 was found to be partially covered with hydroxyl
groups based on the results from spectroscopy and simulation. Yuan
et al. [20] studied the adsorption equilibrium and kinetics of CO2, CH4
and N2 onto OMC for the separation of CO2 and CH4 from air for the
purpose of controlling greenhouse gas emission. Higher adsorption
capacity was shown by OMC for the separation of binary mixtures and
separation selectivities were estimated based on Ideal Adsorbed Solu-
tion Theory (IAST) model.
Based on literature survey, limited number of research effort has
been dedicated to understand the adsorption of organic compounds
onto OMC utilizing the simulation technique and to explore the re-
lationship between adsorption capacity and physiochemical properties
of OMC. In this paper, a study to explore the relationship between the
structural information of OMC and adsorption capacities is presented in
order to find the optimal pore size and oxygen content for resorcinol
adsorption by simulation and the obtained results were validated ex-
perimentally. In order to investigate the structural information and to
find the optimal structural conditions for adsorption, the Materials
Studio software was used in this study. Materials Studio is an effective
tool for studying the structural details and properties of porous mate-
rials on atomistic level. OMC models with different pore sizes and
oxygen contents were constructed and simulated using ZSM-5 as the
repetitive unit cell. ZSM-5 is the most studied and used zeolite due to its
distinct features such as, unique framework topology, higher hydro-
thermal stability, and easy modification of physicochemical properties
such as acidity and texture [21]. ZSM-5 framework contains two in-
tersecting channel systems, with one straight channel parallel to [0 1 0]
and the other sinusoidal running parallel to [0 0 1] defined by 10-
membered ring openings of 0.53 nm × 0.56 nm and
0.51 nm × 0.55 nm, respectively [22,23]. The typical organic con-
taminant, resorcinol, was selected to evaluate the adsorption capacity.
Z.U. Ahmad et al. Journal of Hazardous Materials 354 (2018) 258–265

The molecular size of resorcinol is found to be 0.56 nm × 0.47 nm [24]. geometry of the structure until the relative distances between a group
To validate the simulation results, OMCs were synthesized experimen- of atoms are fixed. Smart algorithm was chosen to run the iteration
tally via hard template method with sucrose as the carbon precursor process to adjust both the cell parameters and atomic coordinates.
and SBA-15 as the silica scaffold. OMCs with tunable pore sizes ranging Smart algorithm is a cascade of methods using successively Steepest
from 4.6 to 11.3 nm were obtained experimentally by utilizing boric Descent and Conjugate Gradient Algorithms. The convergence quality
acid as the pore expanding reagent [25]. In addition, a series of char- was set as Medium, in which energy was 0.001 kcal mol−1, maximum
acterization techniques, such as nitrogen adsorption-desorption iso- force was 0.5 kcal mol−1 per Å, and maximum displacement was
therm, pore size distribution (PSD), specific surface area (SSA), small- 0.015 Å. The cell parameters and atomic coordinates were adjusted
angle XRD, transmission electron micrograph (TEM) and resorcinol until the total energy of the structure was minimized [27].
adsorption experiments, were undertaken in the experimental phase to The small-angle X-ray diffraction patterns were also acquired using
validate the simulation results. Forcite module. The physical properties of the OMC models could be
obtained by embedding the models into the Materials Studio
2. Details of simulation Quantitative Structure-Activity Relationships (QSAR) module, in
which, the properties (molecular mass, volume, surface area and crystal
2.1. OMC model construction dimensions) of the model are united and listed. The specific surface
area (SSA) was calculated by the following equation:
Zhao [26] reported a rectangular shaped model using amorphous
A
carbon unit cell (Fig. 1(a)) as the repetitive unit. The rectangular model SSA =
ρ×V (1)
had several limitations in the pore size control and formation of the
hexagonal structure if the ratio of the side length and diagonal is only 2. Where A is the BET surface area obtained from surface area analysis
Additionally, the density of the proposed model was 3.5 g cm−3 which module; ρ is the density of the OMC model which calculated by the
was too dense and there was no channel connectivity. For this reason, Forcite Analysis module; V is the bulk volume of the OMC model cal-
the specific surface area of this rectangular shaped model could only culated by the lattice length.
reach approximately 100 to 200 m2 g−1, which was way off from that of
the OMC prepared in this study. In addition, OMC prepared in this
2.3. Adsorption simulation
study possessed two dimensional hexagonal array (p6mm) pore struc-
ture as shown in Fig. 1(b). Therefore, the rectangular shaped model
The resorcinol molecular model built in material studio is depicted
could not be directly used in this study.
in Fig. 3. A six-membered ring was drawn by Sketch Ring tool. Then
In this study, a new OMC model was proposed using rhombus
two oxygen atoms were added in the symmetrical position in the phenyl
shaped repetitive cell and ZSM-5 as the unit cell as shown in Fig. 2(a).
ring. The hydrogen atoms were filled with the empty valences by Adjust
ZSM-5, imported from the database of Materials Studio, is an alumi-
Hydrogen tool. The small-angle X-ray diffraction pattern and
nosilicate zeolite. It has a density of approximately 1.78 g cm−3 and has
abundant and uniform micropore structure with channel connectivity
as shown in Fig. 2(b). The structure unit of ZSM-5 model was
2.007 × 1.992 × 1.342 nm3 in size. The unit cell was modified by
changing all the other atoms to carbon atoms. The obtained structures
were optimized by Forcite module. The lattice parameter of angle was
set to α = 90°, β = 90° and γ = 120° in order to build a hexagonal array
structure. The OMC model as depicted in Fig. 2(c) was constructed by
carving out straight cylindrical pores in a ZSM-5 silica super cell which
was imported from the database of Materials Studio. The dimension of
the supper cell was determined by the pore size of the OMC model.
Next, two and a half cylindrical pores were created by removing the
atoms inside the pore of the diameter selected. The pores and internal
surface were saturated with hydrogen by Hydrogen Adjust Module.
Variations of oxygen contents were achieved by adding oxygen
atoms to the unsaturated carbon atom sites on the pore surface. All the
oxygen atoms existed in the form of hydroxyl and carboxyl groups.
OMC models with different oxygen contents were generated through
the following procedure: (1) the carbon atoms located inside the pore of
the selected diameter were removed; (2) the vacant bonds on carbon
atoms on the surface of the pore were saturated by oxygen atoms; (3)
saturation of all the carbon and oxygen atoms with hydrogen atoms.
Different pore sizes were obtained by changing the radius of the carving
cylindrical channel.

2.2. Structure optimization

The structures of the final models generated were geometrically

optimized by Forcite Module in Materials Studio packages using
Condensed-Phase Optimized Molecular Potentials for Atomistic
Simulation Studies (COMPASS) force field. Therein, Forcite Module is a
tool to perform a wide range of molecular mechanics calculations (such
as single-point energy calculation, geometry optimization and mole-
cular dynamics, etc.) using classical force field based on simulation Fig. 2. (a) The model of ZSM-5 unit cell (b) Channel connectivity of ZSM-5 (c)
techniques. Geometry Optimization task was used to refine the Line model of OMC.

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Z.U. Ahmad et al.
Fig. 3. Resorcinol molecular model built by Materials Studio.
adsorption of resorcinol onto OMC was based on the Grand Canonical
Monte Carlo (GCMC) theory and was simulated using Scattering tool in
Forcite Analysis Module and Sorption Module of Material Studio
packages. The adsorption capacity of resorcinol onto OMC was calcu-
lated by the following equation:
n × Mresorcinol
Adsorption Capacity =
NA × V × ρ
Where n is the number of resorcinol molecules adsorbed per cell;
Mresorcinol is the modular weight of resorcinol; NA is the Avogadro’s
constant, which is 6.02 × 1023; V is the volume of the OMC cell; ρ is the
density of OMC.
3. Details of experiment
3.1. Synthesis of SBA-15
SBA-15 silica template was synthesized under acidic condition using
Pluronic P123 (EO20PO70EO20, BASF) as the surfactant and tetraethyl
orthosilicate (TEOS, 98%) as the silica source. The synthesis procedure
followed the method reported by Zhao et al. [28] with modifications on
the reaction temperature and reaction time. Typically, 100 mL of con-
centrated hydrochloride acid (HCl, 37%) was added into the 525 mL of
distilled water. 20 g of triblock copolymer Pluronic P123 was added
into the aqueous solution. The solution was stirred for approximately
2 h until all P123 was completely dissolved. Next, 46.5 mL of tetraethyl
orthosilicate (TEOS, 98%, Aldrich) was added to the homogenous so-
lution with vigorous stirring for 10 min. The resulting mixture was
placed in a constant temperature water bath (Premiere Thermostatic
water bath HH-4) for 4 h at 40 °C, followed by aging for 24 h at 90 °C.
After the aging was done, the solid product was washed with 80–90 °C
hot distilled water, and dried in an oven at 105 °C overnight. After
drying, the product was calcined in a muffle furnace at 550 °C for 8 h.
The white silica template SBA-15 was obtained and stored in the de-
siccator for the preparation of OMC.
Table 1
Lattice parameters and elemental composition of OMC model and OMC-0 sample.
Sample Pore size (nm) Wall thickness (nm) Oxygen content (%)
OMC model 4.6 7.1 11.2
OMC-0 sample 4.6 7.1 13.3
Journal of Hazardous Materials 354 (2018) 258–265
Fig. 4. Comparison of the XRD patterns between experimental and simulation
(based on Grand Canonical Monte Carlo theory) results.
(2)
Fig. 5. Loading curve of resorcinol onto OMC model by sorption module.
3.2. Fabrication of OMC
Different amounts of boric acid were added as the pore expanding
reagent and sucrose was used as the carbon precursor. The synthesis
procedure followed the methods reported by Lee et al. [1] and Wang
et al. [29]. The obtained OMC samples were denoted as OMC- x . The x
value indicates the molar ratio of boric acid to carbon precursor, which
is varied from 0 to 12. In a typical synthesis of OMC-1, 0.27 g of boric
acid (99.8 wt%), 1.5 g of sucrose and 15 drops of concentrated sulfuric
acid were dissolved in 15.0 ml distilled water. After adding 2.0 g of
SBA-15, the mixture was heated at 100 °C for 6 h and subsequently at
160 °C for another 6 h. The resulting composite was impregnated again
with an aqueous solution of 0.09 g of boric acid, 0.51 g of sucrose and 4
drops of concentrated sulfuric acid. Additional distilled water of
10.0 mL was added in this stage. Following the same heat treatment
method as the previous step, the composite was carbonized at 700 °C for
8 h under the nitrogen atmosphere. Finally the OMC-1 was obtained by
the removal of silica template using 150 mL of 48% HF solution at room
temperature.
3.3. Structural characterization
Small angle X-ray diffraction patterns were obtained using a
PANalytical X-ray diffractometer model Empyream operated at 45 kV
Carbon content (%) Density (g cm−3) Pore volume (cm3 g−1) SSA (m2 g−1)
85.3 1.13 1.36 969.30
83.7 1.12 1.58 1404.2
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Fig. 6. Energy variation in the resorcinol adsorption process.

Fig. 8. Comparison of the simulation results and experimental results: Specific

Surface Area vs. Pore Size.
Fig. 7. Density distribution of resorcinol in the OMC structure (red points de-
note the resorcinol molecules). (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article).

Table 2
Structural parameter and adsorption capacity of the OMC models.
Pore size Density BET Surface Wall Thickness Adsorption
(nm) (g cm−3) Area (m2 g−1) (nm) Capacity (mg g−1)

3 1.060 808.53 8.7 31.5

4 0.955 973.20 7.7 45.6
5 0.857 1132.20 6.7 56.1
6 0.770 1347.60 5.7 68.3
7 0.730 1148.50 4.7 53.3
8 0.666 954.30 3.7 42.8
9 0.613 963.20 2.7 51.2
10 0.579 986.70 1.7 57.3
11 0.543 990.30 0.7 52.2

and 40 mA and using Cu Kα1 radiation (k = 1.5406 Å). Measurements
were carried out to obtain resolved XRD patterns at 2θ angles from 0.5°
to 5°. The step size was 0.0066° and the soller slit was 0.04 rad.
The specific surface area (SSA), pore volume and pore size dis-
tribution were determined using the Micromeritics ASAP 2020 surface
area and porosimetry physisorption system. The nitrogen adsorption
Fig. 9. Comparison of the simulation results and experimental results:
Adsorption Capacity vs. Specific Surface Area.
and desorption isotherm was measured in the relative pressure range of
0 and 0.99.
TEM images were obtained using a Hitachi 7600 Transmission

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Table 3
Results of adsorption simulation for OMC model with different oxygen contents.
Pore Size Oxygen Density SSA (m2 g−1) Adsorption Capacity
(nm) Content (%) (g cm−3) (mg g−1)

4.6 0 0.87 1028.3 41.3

4.6 2.9 0.92 1030.5 43.6
4.6 4.4 1.03 1031.4 45.1
4.6 6.2 1.28 1033.5 45.8
4.6 9.6 1.49 1035.7 46.7
4.6 12.3 1.69 1036.8 47.2

Fig. 10. Pore size distribution curves of synthesized OMC.

Electron Microscopy (Hitachi America Ltd., Tarrytown, New York). The

instrument was operated at the acceleration voltage of 100 kV. The
samples were prepared by dispersing a large number of particles in
ethanol in an ultrasonic water bath for 45 min and a drop of the re-
sulting suspension was placed on a 400 mesh Cu grid.

3.4. Batch adsorption study

Resorcinol, a typical TOC model compound, was selected to eval-

uate the adsorption capacity of OMC. The adsorption experiments were
Fig. 12. Comparison of simulation results and experiment results: Adsorption
carried out by analyzing 100 mL of 7.5 mg L−1 resorcinol solution using capacity vs. oxygen content.
10 mg of OMC at the pH of 6.1. One sample of the same concentration
solution without the adsorbent (blank) was prepared and treated under
the same conditions as the solutions containing adsorbent. This blank phase initial and final concentration of resorcinol (mg L−1), respec-
was used as a reference to establish the initial concentration of the tively; V is the volume of the solution (L) and M is the mass of ad-
solutions containing the adsorbent. After the addition of adsorbent, sorbent used (g).
these solutions were placed in a mechanical shaker at 250 rpm for 24 h
at 25 °C. The conical flasks were then removed and solutions were fil- 4. Results and discussion
tered using a 0.45 μm filter paper. The equilibrium concentrations of
each solution were measured by Cary 50 UV–vis spectrophotometer 4.1. Verification of OMC model
(Varian) at wavelength of 500 nm in room temperature. The amount of
adsorbed resorcinol at equilibrium, q (mg L−1) was calculated by using In order to investigate the effects of pore size and surface chemistry,
the following equation: the ideal models of OMC with different properties were constructed and
their adsorption capacities were simulated. The OMC model was opti-
(C i−C f ) × V
q= mized with the same unit cell parameter of OMC-0 sample. The pores
M (3)
were arranged hexagonally with pore radius of 4.6 nm and wall thick-
−1
Where q is the adsorption capacity (mg g ); Ci and Cf are the liquid- ness of 7.1 nm.

Fig. 11. TEM images of (a) OMC-0 (b) OMC-12.

263
Z.U. Ahmad et al.
The optimized structural parameter and elemental composition of
the OMC model and OMC-0 sample are listed in Table 1. The specific
surface area of the OMC model was estimated using the atom volumes
and surface tools in Materials Studio package. The specific surface area
of the OMC model was found to be 969.3 m2 g−1, which was less than
the BET surface area of OMC-0. The decrease in surface area compared
to BET surface area of OMC-0 may be caused by the ideally ordered
structure assumed in the OMC model. In addition, some complications
such as the coarseness of the surface and the extent of crystallization
were ignored in order to simplify the model. In a study carried out by
Chen et al. [17], lower surface area and lower total pore volume were
also observed for the MCM-41 model based on ZSM-5 zeolite structure.
However, there was no significant effect on the description of the pore
structure of the samples, with all the other parameters similar to the
parameters observed for the OMC produced experimentally.
Based on the experimental XRD analysis, the same analysis condi-
tions such as the wavelength (k = 1.5406 Å) and scan angle range (from
0.5° to 5°) were selected. The simulated XRD pattern and experimen-
tally obtained XRD pattern are compared in Fig. 4. The small-angle XRD
estimated by simulation shows three peaks at (100), (110) and (200)
reflection which is a typical pattern for hexagonally ordered array
structure. The (100) diffraction peak of the experimental pattern bi-
furcates to two small peaks, while the (110) and (200) diffraction peaks
are indiscernible. The results indicate that the OMC obtained experi-
mentally has less ordered hexagonal mesopore structures. The model in
the simulation represented an ideal material that was constructed with
an ordered configuration and uniform orientation. Therefore, the model
could only describe the pore structure and crystal reflection up to a
certain extent.
The adsorption process was simulated by Sorption Module which
can be used to predict fundamental properties, such as sorption iso-
therms and Henry’s constants. During the course of simulation, sorbates
are randomly created, deleted, translated and rotated until a stage is
accepted or rejected according to the selection rules of the Monte Carlo
method. The adsorption isotherm was carried out in a pressure range
from 20 kPa to 101 kPa and temperature at 298 K. The COMPASS force
field was used and the system was equilibrated at 298 K to obtain
minimum energy configuration. The isotherm is shown in Fig. 5. The
initial configuration was generated by loading fifty resorcinol mole-
cules randomly in the pore structure. The OMC model rapidly took up
resorcinol molecules in the first stage, followed by a slow continuous
uptake for adsorption. The system was then equilibrated for 60,000
GCMC steps and the average amount of adsorption was reported.
The energy variation during the adsorption process is shown in
Fig. 6. The energy variation results demonstrate that the system is
equilibrated and in a stable condition for each step. The slight increase
of the intermolecular energy and decrease of the Van der Waals energy
and electrostatic energy indicate that the interaction of the adsorbate
and OMC model is not strong. So, the adsorption of resorcinol on OMC
model was more likely a physical adsorption process.
The density distribution of the adsorbate is depicted in Fig. 7. The
channels were found to be fully saturated with the adsorbate molecules.
The loading of resorcinol at equilibrium was found to be 157 adsorbed
resorcinol per cell. The simulated adsorption capacity of OMC model
was found to be 41 mg g−1. The simulated adsorption capacity was
close to the experimentally obtained adsorption capacity of
36.5 mg g−1. Therefore, the OMC model developed using ZSM-5 as the
basic template was a reliable model for adsorption simulation.
4.2. Simulation of resorcinol adsorption
4.2.1. Effect of pore size
In order to investigate the effect of pore size on the adsorption
performance, a series of OMC models with different pore sizes (from
3 nm to 11 nm) were built using Materials Studio. The unit cell para-
meter was maintained at 11.7 nm (calculated from the XRD pattern),
264
Journal of Hazardous Materials 354 (2018) 258–265
which was the same as the experimental OMC. The simulation results
are shown in Table 2.
The relationships between the specific surface area and pore size are
plotted and compared with the experimental data as shown in Fig. 8.
The simulation results and experimental data show a similar trend with
an average relative error of 0.1938. This indicates that the simulation
results are well fitted with the experimental results. The highest ad-
sorption capacity could be obtained at the diameter of 6 nm. At 6 nm,
largest specific surface area was also obtained. The larger pore size did
not indicate a better adsorption capacity. From the simulation results, it
was observed that the specific surface area was the main factor affecting
the adsorption capacity. The result was in line with the conclusion
drawn by You et al. [30], where the specific surface areas were more
closely related to the immobilization capacity of porous materials
compared to the pore sizes.
In order to explore the effect of the specific surface area, the re-
lationship between adsorption capacity and specific surface area is
plotted in Fig. 9. The adsorption capacity obtained from simulation
results increase linearly with the increase in the specific surface area.
The larger surface area provides more interaction sites for the ad-
sorbates. Based on the simulation results, the specific surface area
varied with the pore diameter, OMC with pore diameter of 6 nm yielded
larger surface area. However, when the pore size was increased to
11 nm, the wall thickness was too thin to retain the ordered structure.
Therefore, the optimal pore size of OMC made from SBA-15 is 6 nm for
resorcinol removal.
Boric acid was used as an effective pore expanding reagent to syn-
thesize OMCs with tailored pore size. With the increment of pore size,
the specific surface area increases upto a certain point and then de-
creases (Fig. 8). The adsorption capacity increases with the increment
of specific surface area. So, the increment of pore size cannot be
translated into better adsorption capacity. Based on the simulation re-
sults, the optimal pore sizes are found to be 6 nm and 10 nm with the
corresponding adsorption capacity of 68.3 and 57.3 mg g−1, respec-
tively. However, OMCs modified with boric acid have greater tendency
to structural collapse compared to OMC without boric acid. Considering
the stability of the OMC framework, the pore size of 10 nm was ex-
cluded because of the susceptible structural collapse.
The differences between the simulated and experimental data were
observed. This divergence is mainly caused by the assumption that the
structure in the model is ideally ordered. Additionally, the extent of
crystallization, the coarseness of the surface, and the absence of ideal
pore system in the actual OMC can be the reasons for the reduction of
resorcinol adsorption capacity under experimental conditions.
The increase in the pore size with the increase in boron content was
confirmed by pore size distributions as depicted in Fig. 10. The OMC-4,
OMC-8 and OMC-12 had flatter peaks indicating wider ranges of pore
size and less ordered structure. In addition, the largest pore size of
11.3 nm was obtained by OMC-12. The pore size was close to the unit
cell length. For these three samples, the wall thickness was too thin to
support the rigid carbon structure and therefore, less ordered carbon
structure was obtained as shown in Fig. 11. The same observation was
reported by Ryoo et al. [31]. In general, the OMC made with different
ratio of boric acid to sucrose have tailored pore sizes ranging from
4.6 nm to 11.3 nm.
4.2.2. Effect of oxygen content
The effects of oxygen content on the surface of the OMC model were
evaluated by constructing the OMC model doped with different amount
of oxygen atoms. OMC model with pore size of 4.6 nm was selected as
the basic structure. Oxygen content was the only variable in this
iteration of simulation. The oxygen atoms existed in the form of hy-
droxyl and carboxyl groups and were distributed on the surface of the
pore structure. The simulation results are shown in Table 3.
The plot of oxygen content as a function of adsorption capacity is
presented together with the experimental result as depicted in the
Z.U. Ahmad et al.
Fig. 12. It was observed that the adsorption capacity of resorcinol in-
creased with the increase in oxygen atoms present on the pore surface.
With the increase in oxygen content from 0% to 12%, the adsorption
capacities increased from 41.3 mg g−1 to 47.2 mg g−1. The difference in
the adsorption capacity of OMC model and OMC prepared experimen-
tally may be attributed to the ideal ordered structure assumed in the
OMC model. Comparing the influence of specific surface area with the
influence of oxygen-containing functional groups, the specific surface
area increased the adsorption capacity up to approximate 116% while
the influence of oxygen-containing functional group for the adsorption
of resorcinol was nearly negligible. Many researchers have proved that
the hydroxyl functional group has the ability to enhance the affinity
with the acid adsorbates while the carboxylic functional groups are
more beneficial for the basic adsorbates [32]. However, based on the
simulation results obtained, the oxygen-containing functional groups
show no significant improvement on the adsorption capacity on re-
sorcinol removal. Therefore, the adsorption process of resorcinol is
more of a physical process rather than a chemical interaction. It can
also be confirmed by the energy variation diagram as shown in Fig. 6.
The main attractive force between the adsorbates and carbon is Van der
Waals force.
5. Conclusion
A new rhombic OMC model was proposed and constructed using
Materials Visualizer module to optimize the structure of OMC for re-
sorcinol removal. OMC model was constructed with varying pore sizes
and oxygen contents using Materials Studio Package. To validate the
simulation results, OMCs were synthesized via hard template method
using SBA-15 as the silica scaffold and sucrose as the carbon precursor.
To obtain OMCs with varying pore size and oxygen content, boric acid
was used as the pore expanding reagent for the synthesis. The results
obtained from the experiments were used to validate the simulation
results. Comparison of the simulation results with the experimental
values revealed that optimal pore size was 6 nm which corresponds to
an adsorption capacity of 68.3 mg g−1. Larger pore size do not provide
higher adsorption capacity as the increase in the pore size results in the
decrease of wall thickness and subsequent pore collapse. Simulation
results also revealed that the increment of oxygen content from 0 to
12.3% caused an improvement of adsorption capacity of 14%. The
improvement in adsorption capacity through the increase in oxygen
content is not significant compared to the effects of specific surface
area. In conclusion, molecular simulation technique can be used to
optimize the structure of an adsorbent for adsorption process.
Acknowledgements
This work was supported by the University of Louisiana at Lafayette
and Louisiana Board of Regents (LEQSF(2015–16)-ENH-TR-32 and
LEQSF(2016–17)-RD-C-15). Assistance and support provided by all the
staff of the Energy Institute of Louisiana is also acknowledged in this
research study.
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