Chemosphere 206 (2018) 285e292

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Chemosphere
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An experimental and theoretical study of the adsorption removal of

toluene and chlorobenzene on coconut shell derived carbon
Xiaoyan Zhao a, Xiaolan Zeng a, Yu Qin a, Xiang Li a, *, Tianle Zhu a, **, Xiaolong Tang b
a
School of Space and Environment, Beihang University, Beijing, 100191, PR China
b
School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Coconut shell derived carbon (CDC)

shows better VOCs removal perfor-
mance than commercial activated
carbon (CAC).

Chlorobenzene adsorption on CDC
exhibits greater affinity (Lennard
eJones potential) than toluene.

The electron-withdrawing carbonyl
weakens the interaction between
VOCs and adsorbents.

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption performance of toluene and chlorobenzene on prepared coconut shell derived carbon
Received 16 January 2018 (CDC) is investigated and compared with commercial activated carbon (CAC) by experiment and theory
Received in revised form calculation. Textural properties of prepared adsorbents are characterized by N2 adsorption, infrared
2 April 2018
spectra (FT-IR), Raman spectra and X-ray photoelectron spectra (XPS). Adsorption isotherms of toluene
Accepted 20 April 2018
Available online 26 April 2018
and chlorobenzene are obtained and fitted using structure optimizations, Grand Canonical Monte Carlo
(GCMC) simulation and thermodynamic models. The results indicate that CDC shows better volatile
Handling Editor: Tsair-Fuh organic compounds (VOCs) removal performance than CAC, and chlorobenzene is easily adsorbed than
toluene. On the aspect of textural characteristics, CDC possesses more micropores ratio and narrower
Keywords: pore size distribution than CAC. Furthermore, amounts of electron-withdrawing carbonyl groups on the
Adsorption isotherm CAC surface reduce the electron density of adsorbents, thus weakening the interaction between VOCs
Theory calculation and adsorbents. On the aspect of model fitting, the Yoon and Nelson (Y-N) and DubinineAstakhov (D-A)
Coconut shell derived carbon models can well describe the dynamic adsorption and the adsorption equilibrium of toluene and chlo-
Aromatic VOCs
robenzene on CDC respectively. It is believed that substituent groups of adsorbates, making the charge
D-A model
distribution deviate, lead to adsorption potentials of chlorobenzene larger than toluene. In general, both
the pore structure and the surface property of adsorbents affect the VOCs adsorption behaviors on CDC.
© 2018 Published by Elsevier Ltd.

1. Introduction

Toluene and chlorobenzene are two typical aromatic volatile

organic compounds (VOCs) which are mainly emitted from chem-
* Corresponding author.
** Corresponding author. ical process industries, including painting, coating, rubber, and so
E-mail address: xiangli@buaa.edu.cn (X. Li). denas et al., 2005). Aromatic VOCs are seriously toxic to
on (Lillo-Ro

https://doi.org/10.1016/j.chemosphere.2018.04.126
0045-6535/© 2018 Published by Elsevier Ltd.
286 X. Zhao et al. / Chemosphere 206 (2018) 285e292
human living conditions and healths, and even though at very low
concentrations. They can lead to eye and throat irritation, damage
to liver and central nervous system (Das et al., 2004). In addition, as
important contributors and precursor to air pollution, they can also
contribute to the ozone and secondary organic aerosol (SOA) for-
mation, which makes up photochemical smog (Guenther et al.,
1995; Riipinen et al., 2012). Therefore, removal of aromatic VOCs
like toluene and chlorobenzene is of great significance and
extremely pressing.
Activated carbon adsorption, as a low-cost, facile recycle, easy
operation and efficient technique, has been widely studied and
used for industrial VOCs abatements. The adsorption capacity of
activated carbon mainly relies on adsorbent properties like pore
structure and size, specific surface area and surface functional
group. However, these parameters greatly depend on the raw
material and activation technique used in the production stage.
Besides, traditional coal and wood, some fruit byproducts, such as
cherry, peach stone, grape seeds and coconut shell, are commonly
used as preparation precursors because of high carbon content and
surface area (Giraudet et al., 2006; Bhatia et al., 2009; Lemus et al.,
2012). Among these carbonaceous sources, cheap coconut shell
with low ash contents is considered as an ideal precursor. Some
researchers found that coconut shell derived carbon with a high
BET surface of 800e1500 m2/g showed excellent absorptive ca-
pacity for methane and aquatic phenol than commercial activated
carbon. Recently, there have been several studies on the aromatic
VOCs adsorption over CDC. However, few researches have focused
on the adsorption mechanism comparison of aromatic VOCs. In
fact, those VOCs with similar structures often coexist, carcinogenic
and refractory in industrial flue gas.
As mentioned, the important characteristics of activated carbon
are pore size distribution and surface property in the structure,
which directly determine aromatic VOCs adsorption performance,
storage capacity and separation efficiency. In the perspective of
porosity investigation, Guo et al. studied that the effects of acti-
vated carbon properties on chlorobenzene, concluding that pore
structure of the activated carbon is the main influence factor (Guo
 denaset et al. found that benzene and toluene
et al., 2014). Lillo-Ro
are prefer to be adsorbed in the narrow micropores on activated
carbon (Lillo-Ro denas et al., 2005). In the aspect of surface property,
some researchers considered that some basic carbonyl surface
groups form a bond with the aromatic ring of phenol
(donoreacceptor argument) (Garcıa et al., 2004). However, others
assumed that electron-rich regions locate in graphene layers
interacting with the p electrons of the aromatic ring of phenols
(pep argument) (Haydar et al., 2003). Generally speaking, learning
the in-depth information from the adsorption equilibrium is
essential and significant to understand the adsorption mechanism
and structure-function relationship. However, these works are al-
ways based on the breakthrough curves, surface functional groups
characteristic and thermodynamic predictions but adsorption iso-
therms, due to the difficult and poisonous measurements to
investigate the adsorption equilibrium curves of aromatic VOCs by
conventional experimental methods. In fact, based on the theo-
retical analysis, some researchers have systematically developed
molecular simulation models with random packing of carbon
sheets for disordered activated carbon building to better predict the
adsorption behaviors of small molecules (Kim et al., 2006; Di Biase
and Sarkisov, 2015). Therefore, the way using theoretical calcula-
tion to simulate adsorption isotherms and then explore that
appropriate models of adsorption thermodynamics for aromatic
VOCs on activated carbon is advisable and feasible.
In this study, coconut shell derived activated carbon are pre-
pared, investigated and compared with commercial coal activated
carbon on the toluene and chlorobenzene adsorption performance.
́
The pore structures, surface features and the physicochemical
properties of adsorbents are investigated by N2 adsorption, FTIR,
Raman and XPS. On the basis of geometry optimization and Grand
Canonical Monte Carlo (GCMC) simulation, the adsorption iso-
therms and thermodynamic parameters are well predicted. More-
over, dynamic adsorption behaviors and equilibrium isotherms of
toluene and chlorobenzene are also fitted by multiple theory
models to analyze adsorption mechanism and structure-activity
relationship in this paper.
2. Experimental methods
2.1. Preparation of adsorbents
The preparation of coconut shells derived carbon was similar
with Hu's method except steam activation(Hu and Srinivasan,
1999). Typically, the coconut shells were crushed and sieved to
20e60 mesh, then dried them at 120  C for 8 h in vacuum. The
certain amounts of raw materials were pyrolyzed at 1173 K in a tube
furnace under nitrogen gas flow. Subsequently, N2 was switched to
steam and activation process was continued for 1 h. After that,
adsorbent materials were washed by HCl-to-carbon mass ratios
0.08 for 2 h and with deionized water to neutral. Finally, dry and
sieve them to 40e60 meshes. The obtained sample was designated
as CDC. In comparison, commercial activated carbon (CAC) was also
used. The brand of CAC was supplied by Kecheng activated Carbon
Co., Ltd. (Beijing, China). CAC used in this study is derived from coal.
2.2. Adsorption performance
The schematic diagram of the experimental setup is provided in
Fig. 1. The tested inlet concentrations of gaseous toluene and
chlorobenzene both are 80 ppm. The adsorption evaluation of VOCs
was carried out in a fixed-bed quartz reactor (i.d. ¼ 10 mm) using
1.2 cm3 of adsorbents. The total gas flow rate was 2 L/min. The
concentrations of VOCs were online monitored by GC-17A (Shi-
madzu) with a flame ionization detector. The breakthrough time
was chosen when the outlet concentration was up to 10% of the
initial value (Wang et al., 2014). Besides, the temperature pro-
grammed desorption (TPD) was performed in the range of
50e400  C at a speed of 5  C/min with Ar flow of 100 mL/min. A
maximal desorption temperature (Tm) was chosen at the position of
desorption peak.
2.3. Characterizations
The N2 adsorption-desorption experiments were performed on
the Micromeretics ASAP 2460 apparatus. The BET method was used
to obtain specific surface area (SSA) at relative pressure between
0.06 and 0.2 and the t-plot method for micropore volume (Vmic)
estimation (Rodriguez-Reinoso et al., 1987; Mestre et al., 2014).
Micropore size distributions (PSDs) were calculated by applying the
density functional theory (DFT). The infrared spectra were recorded
on a FT-IR spectrometer (Bruker E55Xfra106, Germany) in the fre-
quency range of 400e4000 cm1 by the KBr method. Raman
spectra from 500 to 3500 cm1 were collected using Raman spec-
trometer (LabRam HR 800) equipped with a He/Nelaser
(k ¼ 633 nm) at 50  magnification and 30% power. X-ray photo-
electron spectroscopy (XPS) characterization was conducted with
the Thermo Scientific Escalab 250XI electron spectrometer equip-
ped with Al K-Alpha (hn ¼ 1486.6 eV, 150 W power) radiation as a
primary excitation source. The positions of binding energy scale
were calibrated using the C1s at 284.8 eV as the standard peak.
 X. Zhao et al. / Chemosphere 206 (2018) 285e292
Fig. 1. Schematic of the experimental setup.
2.4. Calculation details and isotherms model
Toluene and chlorobenzene isotherms of CDC at 298 K, 303 K
and 313 K were simulated using the energy biased GCMC method.
The structure of coronene was selected as the basic structural units
(BSUs). A cubic simulation box with a side of 33.7 Å in length was
considered and 64 BSUs were randomly packed in it and placed
periodic boundary conditions. GCMC simulation was implemented
using the sorption module of the Material Studio. Further details of
GCMC simulation protocol adopted in this work, including details of
the potential cut-offs, number of Monte Carlo moves per adsorption
point, type and weight of Monte Carlo moves and other parameters,
were provided in the SI file. Adsorption equilibrium isotherms of
toluene and chlorobenzene on the CDC sample were fitted with
Langmuir, Tὸth and DubinineAstakhov (DeA) isotherm models
(Mertens, 2009; Purewal et al., 2012).
3. Results
3.1. Dynamic adsorption and desorption behaviors
The adsorption breakthrough and TPD curves of chlorobenzene
and toluene on CDC and CAC are shown in Fig. 2, and corresponding
parameters are collected in Table 1. It can be seen that the dynamic
adsorption capacity decreases with the order of CSDC > CAC (272
and 252 mg/g for chlorobenzene, respectively). Meanwhile, chlo-
robenzene is adsorbed more easily than toluene for the same
adsorbent due to its shorter breakthrough time but higher capacity.
Adsorption curves fits are carried out by the Yoon and Nelson (Y-N)
and linear driving force (LDF) models to quantitatively elucidate the
kinetic adsorptive and diffused behaviors in micropores (Thomas,
1944; Dou et al., 2011; Wang et al., 2015b). The specific adsorp-
tion rate constant can be calculated by the Y-N model as follow:
1 C
t ¼tþ ln
k0 C0  C
where C0 and C are inlet and outlet concentration of adsorbate (mg/
L), t is the adsorption time (min), k is the rate constant (min1) and
0
t is the time required for 50% adsorbate breakthrough (min). As
shown in Fig. 2(a), the adsorption breakthrough curves of CB and
MB on CDC and CAC were well fitted. Furthermore, from Fig. S2 and
Table S1, there are notably linear relationships between ln (C/C0-C)
and time t, which illustrates that the dynamic adsorption behaviors
of CB and MB can be well described by Y-N model. As listed in
287
0
Table 1, the rate constant (k ) of chlorobenzene adsorption on CDC
(0.0697 min1) is lower than that on CAC (0.1046 min1), which
obeys the same order of toluene adsorption on CDC (0.036 min1)
and CAC (0.0381 min1). Besides, Y-N model can predict break-
through time and adsorption equilibrium time under the operating
conditions of VOC inlet concentration 80 ppm, total flow 2 L/min at
30  C. Take the CDC-MB system as an example, based on the fitting
0
liner equation: y ¼ 27:77x þ 617, k and t can be obtained. Then
the Y-N equation can change to the following form:
C 1
¼ (2)
C0 1 þ e½k0 ðttÞ
Assuming that the outlet concentration is equal to 10% inlet
concentration, it is defined as breakthrough point (t1), and the
outlet concentration is equal to 90% inlet concentration (equilib-
rium point t2). The calculating t1 is 556 min and t2 678 min, which is
close to the experimental result (t1 ¼ 544 min, t2 ¼ 695 min).
On the other hand, the microporous diffusion coefficient (D/R2)
from LDF equation has also been used for expressing the uptake
rate of sorbates on the sorbents (Epiepang et al., 2016). The diffu-
sion equation is given by:
vu v2 u
¼D 2 (3)
vr vr
 1 =
Mt 4 Dt 2
¼ pffiffiffiffi (4)
M∞ p R2
where u¼Cr, D is the pore diffusivity, R is the radius of the particle,
while C is the concentration at radial distance, r. t is time and Mt and
M∞ are the total sorbate amounts adsorbed at time t and at equi-
librium, respectively.
The approximate conditions (Zhao et al., 2007) used are:
(1)
Mt =M∞ < 0:3 (5)
r¼R (6)
According to the calculation results in Table 1, the calculated D/
R2 (105 s1) values are in the order of: CDC-chlorobenzene
(1.94) > CAC-chlorobenzene (1.866) > CDC-toluene (1.237) > CAC-
toluene (1.159). Since a high D/R2 yields low resistance and fast
mass transfer, the chlorobenzene adsorption on CDC is prior to
occupying adsorption sites (Stuckert and Yang, 2011). Similarly, the
288 X. Zhao et al. / Chemosphere 206 (2018) 285e292
Fig. 2. Adsorption breakthrough curves fitted by Y-N model (a), desorption profiles (b) and competitive breakthrough adsorption curves on CAC (c) and CDC (d).
uptake rate of CDC for toluene and chlorobenzene adsorption is
greater than that of CAC, which is in accordance with the conclu-
sion from Y-N model. Therefore, CDC originated from saturated
chain fiber structures may generate more developed pore struc-
tures than CAC from unsaturated aromatic rings.
The TPD curves of two adsorbed materials are also shown in
Fig. 2(b). The desorption peaks of two adsorbents display symme-
try, which can be considered as the existence of homogeneity in the
strength of the adsorption sites. Besides, the differences of the Tm
indicate that VOCs adsorption sites on the adsorbents are distinct,
which may be related with different surface chemical functional
groups (Table 1). CDC with desorption peaks at 167  C for toluene
and 196  C for chlorobenzene show the maximum desorption
amounts, implying the higher affinity for two adsorbates. More-
over, competitive adsorption experiment is carried out to explore
the affinity between adsorbates and adsorbents. Fig. 2(c and d)
shows the adsorption breakthrough curves of a mixture of toluene
and chlorobenzene on two adsorbents. For both adsorbents, the
partially adsorbed toluene is gradually displaced by chlorobenzene
when the adsorbent approaches adsorption saturation. As listed in
Table 1, the mono-component breakthrough time of toluene and
chlorobenzene on CDC is in the order: toluene (544min) > chloro-
benzene (205min), while for the binary adsorption: chlorobenzene
(113min) > toluene (97min), whose tendency is similar with CAC.
Hence, the displacement of toluene by chlorobenzene in the
channel may be related with stronger adsorption of chlorobenzene
on the adsorbent surface and lower volatility of chlorobenzene
(Tefera et al., 2014).
3.2. Adsorbent characteristics
Fig. 3(a) illustrates the N2 adsorptionedesorption isotherms at
77 K and the PSDs of CAC and CDC. Both the two types of adsorption
isotherms exhibit a type I profile (Langmuir type isotherm), and a
small hysteresis loop occurs in each adsorbent, implying that it has
few amounts of mesopores (Warhurst et al., 1997; Chiang et al.,
2001). According to the pore structure parameters of adsorbents
provided in Table 1, the SSA, Vt and Vmicro of CDC are significantly
larger than those of CAC. Furthermore, the CDC (Da ¼ 1.9081 nm)
has a high adsorption uptake at low P/P0 (P/P0 < 0.1) and possesses
almost 90% micropores. Because the filling of micropores takes
place sharply at relatively low partial pressures, micropores may be
more imperative than mesopores during adsorbing VOCs (Do and
Do, 2002). To understand how the pore diameter affects the VOCs
adsorption, micropore size distributions were calculated by the
density functional theory (DFT). As shown in Fig. 3(a) inset, both
CDC and CAC display narrow bimodal PSDs of micropores centered
at 0.53 and 0.8 nm. Generally, when the micropore size of adsor-
bents is close to the dynamic diameter of adsorbates, the van der
Waals potential fields produce by the pore walls overlaps, resulting
in a larger adsorption energy for adsorbates (Do and Do, 2002).
Kinetic diameters of toluene and chlorobenzene are 0.67 nm and
0.78 nm, respectively. And the latter approximately equals the
micropore size (0.8 nm). In contrast, the kinetic diameter of toluene
(0.67 nm) does not match with pore size of CAC and CDC. In other
words, activated carbon with specific micropore size may
contribute to better chlorobenzene adsorption performance than
 X. Zhao et al. / Chemosphere 206 (2018) 285e292 289

toluene. Consequently, the more micropores and narrower micro-

0.956
0.999
pore size distribution may play a very significant role in adsorption

MB
performance.
Fig. 3(b) depicts the Raman spectra of CAC and CDC. It is

0.998
0.989
CB
observed that two characteristic peaks for carbonaceous material,

R2
including D (at 1350 cm1) and G (at 1580 cm1) bands are obvious

1.237
1.159
D/R2[105s1]
(Aher et al., 2017). Generally, G band (the E2g mode of sp2 carbon) is

MB
observed for all graphitic structures, whereas D band (symmetric
A1g mode) is from the disorder induced vibrational mode. The short

1.944
1.866
LDF

CB
range order of CDC is further confirmed by the presentation of the
2D-band at 2700 cm1 (Kormann et al., 2009). It is observed that
0.994
0.975
the ID/IG of CDC is lower than that of the CAC, indicating the higher
MB

degree of graphitization possibly promotes the aromatic VOCs

adsorption on CDC because of p-p conjugated effect.
0.999
0.974

Infrared spectroscopy has been also used to analyze the corre-

CB
R2

lation between surface functional groups and adsorption perfor-

617
417
MB

mance. As is shown in Fig. 3(c), a strong and broad peak at about

3435 cm1 for CAC and 3401 cm1 for CDC are assigned to the
t(min)

241
188

stretching vibration of OeH functional groups (Fang and Chen,

CB

2012). The small band at the range of 2800e3000 cm1 denotes

Dynamic models

0.036
0.038

that the presence of aliphatic (-CH3, -CH2, -CH) compounds (El-

MB

Hendawy, 2003). The band at 1626 cm1 attributes to the over-

lapping of the v(C¼C) stretching vibration mode of the aromatic
0.070
0.105
Y-N

ring carbon with the v(C¼O) absorption bands of oxygen-

CB
k'

containing groups (Xu et al., 2014). The bands at ~1051 cm1 and
218
124

below 1000 cm1 denote the phenolic OeH bending vibration and
MB
Tm( C)

Breakthrough time: adsorption capacity of the absorbent when the outlet concentration of VOC is 10% of the inlet concentration.

out-of-plane deformation vibrations of CeH groups in aromatic

Bi-component adsorption data

218
188

structures, respectively (Kyzas et al., 2013). As for the band at

CB

1384 cm1 in CAC, it can be assigned to the C¼O stretching vibra-

MB
Qtotal(mg/

44
32

tion from ketones, aldehydes or carboxyl groups, which does not

appear in CDC (Shen et al., 2008; Wang et al., 2015a). To investigate
144
136
CB

the surface C¼O group difference from CDC and CAC, the C1s XPS
g)

spectra are also performed. As shown in Fig. 3(d), the C1s peak can
MB

97
91

be fitted into three independent sub-bands which can be assigned

tb (min)

to C-C (~284.8 eV), C-O-C (~286.4 eV) and C¼O (~288.4 eV) func-
113
CB

65

tional groups (Aher et al., 2017). According to the results of

deconvolution, the proportion of C¼O in CAC (14.8%) is obviously
The comprehensive data of porosity parameters, adsorption/desorption data and dynamic models.

167
146
MB

larger than that in CDC (13.8%). Therefore, both the XPS and FTIR
Tmb( C)

results imply that the electron-withdrawing carbonyl found in CAC

196
140

may reduce its surface electron density, weakening the p-p con-
CB
Monocomponent adsorption/

jugated effect between VOC and CAC.

255
189
MB
Qtotal(mg/

3.3. Theoretical calculation and model fit

272
252
CB
g)
desorption data

Based on the constructing CDC model from a random packing

544
348
MB

with BSUs in Packmol procedure as shown in Fig. 4(a), isosteric

tba (min)

heats (figure S2) and adsorption isotherms (Fig. 4(b)) were ob-
205
161
CB

tained by the GCMC simulation using the sorption module of Ma-

terial Studio. Isosteric heat (qst) of adsorption is an important
Vmicro(cm3/g)

physiochemical parameter to explore the intermolecular forces

between adsorbent and adsorbate (Madani et al., 2016). As shown
Temperature of maximal peak of TPD profiles.
0.430
0.382

in Fig. S2, the qst of chlorobenzene is generally higher than that of

toluene, which signifies a stronger binding force of chlorobenzene
on CDC.
Vt(cm3/g)

As seen in Fig. 4(b), the adsorption isotherms were fitted by

Porosity parameters

0.480
0.461

CB: Chlorobenzene; MB: Toluene.

Langmuir, Tὸth, and DubinineAstakhov (DeA) isotherm models

(Mertens, 2009; Purewal et al., 2012). The results show that the D-A
SSA(m2/g)

model, based on the potential theory, can well describe the

adsorption equilibrium at different temperatures than another two
1137
1011

models. As for Langmuir equation, it is assumed to be homoge-

neous on the surface of adsorbent, and no interactions between
Adsorbents

adsorbed molecules. Obviously, it is not in accordance with actual

circumstance. In addition, the Tὸth isotherm equation is based on
Table 1

CDC
CAC

the potential theory put forward by Polanyi and is also applicable to

a
b

heterogeneous adsorption. As shown in Fig. 4, the adsorption

290 X. Zhao et al. / Chemosphere 206 (2018) 285e292

Fig. 3. The N2 adsorptionedesorption isotherms and PSDs curves (a) and Raman (b) and FT-IR (c) and C1s XPS spectra of CAC and CDC (d).

Fig. 4. Schematic of the model construction (a) and isotherm curves fitting (b).

isotherm was not well fitted at low pressure (P/P0 < 0.2). Because
the Tὸth equation is a semi-empirical equation, it may not describe
the specific adsorption behaviors accurately. However, in the D-A
equation, the parameter n0 reflects micropore saturated adsorption
capacity. It is seen from Table 2 that the n0 of CB is lager than that of
MB, which also certifies stronger interactions for CB on CDC than
MB. In addition, the parameter c in D-A equation is directly related
to the interactions between adsorbent and adsorbate. Because
c¼(RT/E)m, and E ¼ bE0 , which stands for characteristic adsorption
energy. A lower c represents better adsorption performance
(Epiepang et al., 2016). For instance, the value of c (c ¼ 0.0567) in
the toluene adsorption on CDC at ambient temperature is higher
 X. Zhao et al. / Chemosphere 206 (2018) 285e292
Table 2
Model parameters fitted from adsorption data at 298 K
Tὸth DubinineAstakhov
A[mmol/g] D[atmk] K n0[mmol/g]
MB 298.21 0.039 1.33 286.66
CB 390.65 0.005 2.14 387.81
than the value (c ¼ 0.00926) for chlorobenzene adsorption on CDC,
which embodies as a stronger interaction for chlorobenzene
adsorption, compared to toluene adsorption on CDC.
The adsorbateeadsorbent interaction can also be quantified by
calculating the Henry constant (KH/mol$g1$Pa1) based on the
Virial equation (Cole et al., 1974) as follow:
 
n layers reduce so that the adsorption on CAC has difficulty in binding
ln ¼ A0 þ A1 n þ A2 n2 þ / (7)
p with the aromatic ring of adsorbates. Consequently, CDC is a better
where n (mol g1) is the adsorption amount when the partial
pressure is p (Pa). Ai (i ¼ 0, 1, 2 …) is the Virial constant.
KH ¼ expðA0 Þ and A1 is a function of adsorbate/adsorbate in-
teractions. It is known that the virial constants (A2, A3, etc.) can be
ignored under conditions of low surface coverage, and linear sec-
tion of the Virial graph (~0.01 < p/p0 < ~0.2) can be fitted accurately
(Zhao et al., 2005). From table S1, the values of KH for toluene and
chlorobenzene at 298 K are in the order of chloroben-
zene > toluene. It is obvious that the KH for chlorobenzene is much
greater than that for toluene.
In general, the adsorption potential includes dispersive energy,
repulsive energy, the field-dipole interaction and field gradient-
quadripole interaction, among which dispersive and repulsive en-
ergies are the contributor of adsorption potential. The potentials
are affected by the intermolecular distance (r) and polarization (a),
and the latter is the decisive parameter. In this study, both adsorbed
molecules contain benzene ring, and the difference is the substi-
tutional group. The larger polarization of Cl (2.18) leads to stronger
interaction potential between chlorobenzene and adsorbent than C
(1.76), thereby making chlorobenzene more easily adsorbed by
CDC.
4. Discussion
4.1. Comparison of adsorbents
It is meaningful to construct the structure-activity relationships
between the physicochemical properties of the typical adsorbents
and the VOCs. By comparing the adsorption performance between
CDC and CAC, CDC is more suitable for the VOCs adsorption. The
characterizations of BET and Raman show that the better perfor-
mance for CDC attributes to the developed microporosity and
suitable PSD, which usually play important roles in the adsorption
process as suggested by previous researchers (Bhatia et al., 2009;
Lemus et al., 2012). Besides, according to the surface oxygen-
containing groups detection by FT-IR and XPS, it is reasonably
considered that the existence of carbonyl inhibits VOCs adsorption
on CAC. However, CDC with higher degree of graphitization en-
hances the interaction with toluene and chlorobenzene by p-p
conjugated effect. According to Garcia T's view, it was observed that
electron withdrawal from the graphene layers (pep argument),
and consequently decreases the specific interaction between
phenanthrene and the carbon surface (Garcıa et al., 2004). In the
light of pep argument, the carbonyl, as electron withdrawing
group, reduces the surface electron density of CAC and weakens the
interactions between VOCs and adsorbents. Besides, due to the
291
Langmuir
C m am[mmol/g] b R2
0.057 2.42 306.75 4.870 0.995
0.009 3.89 413.23 17.286 0.997
withdrawing electron effects follow the substituent order: Cl > CH3,
the electron density in the p-system of the aromatic ring in toluene
decreases more than that in chlorobenzene. Haydar S et al. also
assumes that electron-rich regions locate in graphene layers
interacting with the p electrons of the aromatic ring of phenols
(pep argument) (Haydar et al., 2003). For the reason of the
electron-withdrawing carbonyl, the electron densities of graphene
adsorbent than CAC for the removal of aromatic VOCs.
In the perspective of raw materials, coal as CAC precursor,
consists of aromatic and thickening rings with aliphatic chains on
the sides, while the coconut shell as CDC precursor is mainly made
up of natural plant fibers (Gryglewicz et al., 2005; Foo and Hameed,
2012). Unlike the graphite structure of coal, woodiness material in
coconut shell, which is very difficult to form collapse structure
during the solid phase carbonization process. Hence, the smaller
graphitic crystallite size with less disordered structure contributes
to a better adsorption performance (CDC). Due to the unstable
structure, abundant of carbonyl groups formed in the oxidation
pathway on CAC(Gong et al., 1998). In addition, based on the fitting
result from LDF and Y-N models, the diffusion resistance in CDC is
significantly less than that of CAC.
4.2. Comparison of adsorbates
Aiming at comparing chlorobenzene and toluene adsorption
process on CDC, the adsorption isotherm was compared and
investigated. The relevant variables such as KH and qst are obtained
by theory calculation and models fits, which reveal that the chlo-
robenzene adsorption on CDC is much easier than toluene
adsorption. Because of Henry's law which CDC adsorption obeys at
low pressure, the deviation of the Tὸth and Langmuir model occurs.
In contrast, the D-A model, based on the potential theory, can well
describe the adsorption equilibrium for different adsorbates. As is
proposed before, field-dipole and field gradientequadrupole in-
teractions, deriving from an electrical field in the region of the
adsorbent surface, can be negligible for the system of non-polar
activated carbon adsorption (Giraudet et al., 2006). Therefore, the
contributors of adsorption potential are mainly the non-specific
dispersive forces (London) and short-range repulsive energies,
which are known as Lennard-Jones (L-J) potential (Giraudet et al.,
2006). For a specific adsorbent, the L-J potential depends on the
nature of adsorbates, among which polarizability (a) of the adsor-
bate plays a decisive part. The value of a increases with the relative
molecular/atomic mass due to the participation of more polarized
electrons. It is obvious that the relative mass of chlorobenzene is
larger resulting in a greater adsorption potential. Therefore, the
adsorption for chlorobenzene on CDC embodies better adsorption
performance.
5. Conclusion
The adsorption capacity of toluene and chlorobenzene on co-
conut shell derived carbon has been investigated, analyzed and
compared with commercial activated carbon. It is found that raw
292 X. Zhao et al. / Chemosphere 206 (2018) 285e292
materials of coconut shell contribute to developed micropore
structure, narrow pore size distribution and less carbonyl group on
CDC, which is better for toluene and chlorobenzene removal. There
are two major reasons as follows:
(1) Suitable pore size (size < 0.8 nm) leads to larger interaction
on adsorbents for aromatic VOCs adsorption based on the
micropore filling theory. However, the electron-withdrawing
carbonyl found in CAC may reduce the surface electron
density weakening the interactions between adsorbents and
adsorbates.
(2) According to the results of isotherms fits, it can be deduced
that chlorobenzene adsorption on CDC exhibits greater af-
finity (LennardeJones potential) than toluene. Furthermore,
the more polarized electrons of chlorobenzene enhance the
adsorbateeadsorbent interaction, which makes chloroben-
zene more easily adsorbed on the adsorbent.
Acknowledgements
This work was financially supported by the National Key R&D
Program of China (2016TFC0209200) and the American Energy
Foundation (No. 6326012).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.chemosphere.2018.04.126.
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