Journal of Molecular Liquids 278 (2019) 496–504

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Journal of Molecular Liquids

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

Cr(VI) removal with rapid and superior performance utilizing

cost-efficient waste-polyester-textile-based mesoporous carbon:
Behavior and mechanism
Zhihua Xu, Zhihang Yuan, Daofang Zhang ⁎, Yuanxing Huang, Weifang Chen ⁎, Zhenhua Sun, Yuwei Zhou
School of Environment and Architecture, University of Shanghai for Science and Technology, 516 Jungong Rd, Shanghai 200093, PR China

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

Article history: As a typical heavy metal, Cr(VI) poses a serious threat to the environment and to human health. Here, waste-
Received 1 October 2018 polyester-textile-based highly mesoporous carbon (mPC), synthesized by the pyrolysis method in the presence
Received in revised form 21 December 2018 of MgCl2, was employed to rapidly remove Cr(VI) from water. The resultant product presented a high specific sur-
Accepted 15 January 2019
face area (1289 m2·g−1), total pore volume (3.14 cm3·g−1) and mesoporosity (N95%) owing to the strong dehy-
Available online 17 January 2019
drogenation and cross-linking effects of MgCl2 on polymers, as well as the pore-developing effect of MgO. In
Keywords:
further adsorption trials, mPC exhibited excellent removal performance for Cr(VI). The removal efficiency was
Mesoporous carbon significantly enhanced under appropriate conditions (lower pH and ionic strength). Furthermore, mPC showed
MgCl2 high adsorption rate (0.0029 g·mg−1·min−1) and distinguished adsorption capability (165.93 mg·g−1), and
Waste polyester textiles the uptake procedure was fitted well by the Freundlich isotherm and pseudo-second-order kinetics. Fourier-
Cr(VI) removal transform infrared and X-ray photoelectron spectroscopy confirmed that the electrostatic interaction and reduc-
Adsorption mechanism tion effects were the predominant adsorption mechanisms, the ion exchange reaction also accounted for part of
the Cr(VI) removal. This preparation technique of mPC offers a new means of textile waste re-utilization, and the
resultant carbon material with excellent physicochemical characteristics has practical applications in the removal
of Cr(VI) from wastewater.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
Owing to the development of industry, excessive use of landfills, and
stacking of civil solid wastes, large amounts of heavy metals enter rivers
and lakes through sewage systems and runoff. Most of them exist in
complex forms and possess strong diffusivity in water; thus, they can
easily cause a wide range of pollution [1]. Among these metal ions,
hexavalent chromium (Cr(VI)) is a harmful pollutant in water and can
easily enter and damage the human body via the food chain owing to
its toxicity, liquidity, non-biodegradable nature, and carcinogenic prop-
erties [2]. Therefore, various methods have been investigated for the
treatment of Cr(VI)-containing wastewater, including electro-chemical
precipitation, ion-exchange, and biological treatment [3–5]. However,
some of these techniques are difficult to apply in practice as they have
low removal efficiency and high cost. The adsorption method is gener-
ally considered to be a simple and efficient alternative technique for
the disposal of effluent laden with heavy metal ions [6], and the selec-
tion of adsorbent is a vital step.
⁎ Corresponding authors.
E-mail addresses: dfzhang_usst@163.com (D. Zhang), chenweifang@tsinghua.org.cn
(W. Chen).
At present, frequently used adsorbents for the removal of Cr(VI) in-
clude magnetic nanocomposites [7], nanoscale zerovalent iron [8], and
polymers [9]. Mesoporous carbon is also an efficient adsorbent owing
to its large surface area, rich porous structures, and substantial func-
tional groups [10,11]. However, the expansion of the porous carbon pro-
duction industry is restricted by the increasing cost of raw materials and
activation agents, as well as the issues of secondary contamination and
equipment corrosion. Hence, a variety of agricultural and industrial
wastes, including coconut shells [12], cotton stalk [13], sludge [14],
and coal tar pitch [15], have been employed as carbon precursors to re-
duce the costs of raw materials. Meanwhile, some novel activation
agents such as potassium carbonate [16], potassium tartrate [17], so-
dium hydroxide [18], and ammonium polyphosphate [19] have been
utilized in the production of porous carbon to obtain high-surface-
area materials. Unfortunately, the porous structures generated by
these activation agents are usually microporous, which hinders mass
transfer during the uptake processes [20].
Recently, to solve the issue of large output and improper treatment
and disposal of waste textiles, some researchers have attempted to uti-
lize these textiles for the preparation of carbon materials, obtaining var-
ious products with good performance [21–23]. The limitations of these
studies included the complexity of the carbon structure, which meant
that conventional activation processes could not produce carbon

https://doi.org/10.1016/j.molliq.2019.01.088
0167-7322/© 2019 Elsevier B.V. All rights reserved.
 Z. Xu et al. / Journal of Molecular Liquids 278 (2019) 496–504
materials with controlled mesoporous structures. Waste polyester tex-
tiles (WPT), which account for N50% of waste textiles, are considered
to be potential carbon precursors because of their high carbon and
fixed carbon content [24]. We have carried out some pertinent studies
and found that the MgO-template method was an efficient way to
form homogeneous mesopores on WPT-based porous carbon [25].
That study showed that utilizing low-cost and widely available magne-
sium chloride (MgCl2) as the precursor of the MgO template could yield
a superior sample compared with other Mg-containing compounds
such as magnesium citrate and magnesium oxide. In our subsequent
studies, the preparation parameters of the WPT-based carbons in the
MgCl2 method were optimized, and the corresponding pore-forming
mechanism was systematically elucidated [26,27]. The results sug-
gested that plentiful surface groups and turbostratic structures were
formed on the carbon surface, potentially enhancing the adsorption per-
formance of the carbons toward different pollutants in water and the at-
mosphere. Owing to the excellent properties of waste-textile-based
activated carbon, it is typically used for storing energy and absorbing
dyes [21,28]. However, there have been few reports on its adsorption
performance for heavy metals, especially for Cr(VI).
Accordingly, MgCl2 was utilized as a pore former to synthesize WPT-
based mesoporous carbon (mPC) based on the optimal preparation pa-
rameters from our previous study, and the synthesized carbons were
used to eliminate Cr(VI)-containing simulated wastewater. This study
aimed to evaluate the removal performance and behavior characteris-
tics of Cr(VI) ions on the interface between adsorbate and mPC. Batch
adsorption tests examining kinetics, isotherms, and thermodynamics
were implemented to acquire the corresponding parameters to describe
the relationship between the adsorption properties and reaction condi-
tions. Furthermore, Fourier transform infrared (FTIR) and X-ray photo-
electron spectroscopy (XPS) analysis of mPC were used to
systematically elucidate the possible adsorption mechanisms.
2. Experimental
2.1. Materials
WPT were obtained from a textile mill (Shuangou textile factory,
Shanghai) in China. Potassium dichromate (K2Cr2O7), magnesium chlo-
ride hexahydrate (MgCl2·6H2O), sodium chloride (NaCl), hydrochloric
acid (HCl), nitric acid (HNO3), and sodium hydroxide (NaOH) were of
analytical grade, bought from Sinopharm Chemical Reagent Co., China.
Ultra-pure water (18.2 MΩ·cm−1, prepared by Milli-Q Advantage
A10) was employed for the production of all solutions. Nitrogen (N2)
with purity of 99.99% was obtained from Shanghai Pujiang Special Gas
Co., Ltd.
2.2. Preparation
WPT was heat-treated in a muffle furnace under ambient air (target
temperature: 265 °C, duration: 1 h) with a heating rate of 10 °C·min−1
[29]. The cooled solid mass was ground into powders (40 meshes) and
mixed with MgCl2·6H2O solution at a mass ratio of 5:1 (MgCl2·6H2O/
powder). The mixture was stirred mechanically for 12 h and then left
to dry in a loft drier at 80 °C overnight. Subsequently, the dried mixture
was heated to 900 °C (heating rate: 10 °C·min−1) under an N2 atmo-
sphere, maintaining constant until 90 min. The mixture was washed
with 300 mL 10 vol% HCl solution to isolate the carbonaceous material
and then rinsed with deionized water until the eluent pH value
approached 7. Finally, the residue was dried at 105 °C for 24 h.
The preparation parameters (mass ratio: 5:1, pyrolysis time: 1.5 h,
pyrolysis temperature: 900 °C) employed in this work were determined
according to the optimum parameters based on the Box-Behnken de-
sign approach described in our previous work [26]. The mesoporous
carbon prepared under optimum conditions and the carbonization
497
sample without MgCl2 (pyrolysis temperature and time: 900 °C, 1.5 h)
were named mPC and CSWM, respectively.
2.3. Characterization
N2 adsorption-desorption isotherms (77 K) of the carbons were ob-
tained using a physical adsorption apparatus (Quantachrome autosorb-
iQ, USA). The specific surface area (SBET) was calculated using the
Brunauer-Emmett-Teller (BET) method, based on data obtained from
0.06 to 0.2 P/P0. The total pore volume (Vt) was calculated from the ad-
sorption isotherm at 0.99 P/P0. The external surface area (Sext), micropo-
rous surface area (Smic), and microporous volume (Vmic) were
determined by the t-plot approach [30]. The external pore volume
(Vext) was calculated as the difference between Vt and Vmic (Vext = Vt
− Vmic). The surface morphologies of all as-prepared carbons were an-
alyzed via scanning electron microscopy (SEM) with an acceleration
voltage of 20 kV (HITACHI S4800, Japan). The prepared samples were
sprayed with gold before measurements were taken. Surface elements
of the samples were analyzed by energy dispersive spectroscopy (EDS,
Genesis, USA), and images of all carbon samples were taken via trans-
mission electron microscopy (TEM, JEM-2200FS JEOL, Japan). Variation
in the functional groups of mesoporous carbon before and after Cr(VI)
adsorption was observed using FTIR (Nicolet iS10, USA) with KBr
(≥99.0%) pellets; the spectra ranged from 4000 to 400 cm−1. The
point of zero charge (pHpzc) was measured as described in the previous
study [31]. Changes in chemical state and surface elements of the adsor-
bent before and after Cr(VI) uptake were detected via XPS (Thermo
ESCALab-250XI, USA) with Al-Kα radiation (hv: 1486.6 eV).
2.4. Adsorption experiment
2.4.1. Effects of pH
To study the effects of pH on the adsorption process of Cr(VI), 50 mg
adsorbents were added to several conical flasks with Cr(VI) solution
(50 mL, 100 mg·L−1). The pH values were adjusted to 2–10. All the slur-
ries were shaken in a rotary shaker for 12 h (temperature: 25 °C, speed:
150 rpm). Once the adsorption reaction was finished, the mixture was
separated using a 0.45-μm filter, then the concentration of filtrate was
analyzed using the method described in the Chinese National Standards
GB/T 7467-87 (two-benzoyl two-hydrazine spectrophotometry).
2.4.2. Effects of ionic strength
The effects of ionic strength on the adsorption of Cr(VI) were inves-
tigated by adding 50 mg adsorbents to several conical flasks with Cr(VI)
solution (50 mL, 100 mg·L−1). The ionic strengths were adjusted to
0.002, 0.020, and 0.200 mol·L−1, and the pH values were adjusted to
2–10 ± 0.1. All slurries were oscillated at a constant temperature on a
shaking table for 12 h (temperature: 25 °C, speed: 150 rpm). The con-
centrations of filtrate were measured using the method described in
Section 2.4.1 (GB/T 7467-87).
2.4.3. Adsorption kinetics
Adsorption kinetics trials were performed by adding 50 mg adsor-
bents to several conical flasks with Cr(VI) solution (50 mL,
50–300 mg·L−1, pH 2.0 ± 0.1). All slurries were oscillated at 150 rpm,
25 °C, and pH 2.0 ± 0.1. After designated time periods, the concentra-
tions of filtrate were determined by the method described in
Section 2.4.1 (GB/T 7467–87).
2.4.4. Adsorption isotherm and thermodynamics
For the adsorption isotherm and thermodynamics analysis, tests
were performed at different dosages of adsorbent (5–100 mg) and at
different temperatures (15, 25, and 35 °C). All slurries were oscillated
at 150 rpm for 12 h. The concentrations of filtrate were determined as
described above.
498 Z. Xu et al. / Journal of Molecular Liquids 278 (2019) 496–504
3. Results and discussion
3.1. Characterization
The N2 adsorption/desorption isotherms and pore size distributions
of mPC and CSWM are displayed in Fig. 1a,b. According to the UIPAC
classification [32], the isotherm for CSWM displayed combined charac-
teristics of type I/IV isotherms with an H4 hysteresis loop, as depicted in
Fig. 1a, indicative of a microporous or mesoporous material. The N2 ad-
sorption capacity was relatively low, indicating lower surface area and
insufficient porous structures. As expected, the N2 uptake capability
(N2000 m3·g−1) of mPC was markedly increased compared with
CSWM (around 110 m3·g−1), demonstrating the formation of abundant
porous structures. Furthermore, mPC showed a type-IV isotherm with a
steep and wide hysteresis loop of type H3 in the medium-and-high
pressure area (0.4–1.0 P/P0), indicating that the sample contained con-
siderable mesoporous structures generated by accumulated flaky car-
bon particles [33]. The pore size distributions of mPC and CSWM are
depicted in Fig. 1b. CSWM contained only tiny amounts of microporous
structures, with sizes ranging from 1.0 to 1.5 nm. After addition of
MgCl2, the porosity of the sample increased significantly, and a large
number of mesopores (10–30 nm) and micropores were found in the
matrix of mPC. The textural properties of mPC and CSWM are provided
in Table S1. Notably, the SBET of mPC reached 1289 m2·g−1, about seven
times of that of CSWM (171 m2·g−1). Moreover, mPC had a larger total
pore volume (3.14 cm3·g−1), N95% of which was composed of
mesopore volume. This indicated that mPC might have potential appli-
cations in environmental functional materials.
Further analysis of SEM and TEM images was performed for mPC and
CSWM in order to observe the microtopography and clarify the role of
MgCl2 in the pore-developing process. As can be seen in the SEM images
(Fig. 2a), CSWM exhibited a smooth surface with sporadic porous struc-
tures. As shown in Fig. 2b, obvious distinctions were found in the surface
structure of mPC; it was heterogeneous and rough, with abundant slit-
shaped holes generated by the accumulation of carbon sheets, consis-
tent with the conclusions from the N2 adsorption/desorption isotherms.
TEM images of mPC before and after the pickling process are presented
in Fig. 2c–d. As shown in Fig. 2c, MgO grains with good dispersibility and
homogeneous size were evenly distributed, and their grain size was
mainly concentrated within the 20–50 nm range. As shown in Fig. 2d,
abundant pores with comparable MgO grain sizes were produced after
pickling, consistent with the pore size distributions. In our previous
work, the interesting findings above were attributed to the strong dehy-
drogenation, decarboxylic and cross-linking effects of MgCl2 on poly-
mers during the pyrolysis process, as well as the formation of porous
walls after the removal of MgO [27]. A schematic illustration of pore de-
velopment in the synthesis process of mPC is shown in Fig. 3. During py-
rolysis, the WPT gradually melted, carbonized, and formed thin films on
the surface of the MgO. After the pickling process, mesopores with
Fig. 1. (a) N2 adsorption/desorption isotherms and (b) pore size distributions (DFT method) for mPC and CSWM.
similar size to MgO particles were formed in the carbon matrix. Remark-
ably, in the middle temperature stage (300–500 °C), WPT could form
cyclic carbon chain structures by cross-linking and dehydrogenation re-
actions under the catalysis of MgCl2, which was beneficial to the forma-
tion of carbon materials.
3.2. Adsorption experiments
3.2.1. Effects of the initial pH
The effects of initial pH on the adsorption of Cr(VI) onto mPC and
CSWM are illustrated in Fig. 4. The removal efficiency of Cr(VI) was
strongly dependent on the initial pH of the solution. The adsorption
properties of mPC and CSWM declined significantly with increasing
pH, in a range from 2 to 10. In particular, for CSWM, the removal effi-
ciency dropped to nearly 0% when the pH was 10.0. In aqueous solu-
tions, the predominant Cr(VI) forms are chromate (CrO42−), chromic
acid (H2CrO4), hydrogen chromate (HCrO4−), and dichromate
(Cr2O72−), the formation of different ions depends mainly on the pH of
the solution [34]. At the pH of solution ranged from 2 to 6, Cr2O72− and
HCrO4− were the predominant Cr(VI) species. When the pH value
exceeded 8, the CrO42− form of Cr(VI) was dominant. In the case of
mPC, plentiful H+ could easily coordinate with the surface groups at
lower pH levels, since the pHpzc of mPC is around 4.4, which made the
sample surface positively charged. Therefore, higher removal efficiency
under lower pH could be attributed to the strong electrostatic interac-
tion between the negatively charged Cr(VI) and the positively charged
mPC. With increasing pH, the protonation degree decreased and the
surface of the carbon gradually converted to negatively charged, thus
the adsorption capacities of mPC decreased markedly owing to electro-
static repulsion between mPC and CrO42−. The lower removal efficiency
of Cr(VI) at high pH might also be the result of competitive adsorption
between CrO42− and OH– [35].
3.2.2. Effect of ionic strength
The effects of ionic strength on the adsorption of Cr(VI) onto mPC are
illustrated in Fig. 5. The ionic strength influenced the interface potential
and the thickness of double electrode-layer, thereby affecting binding of
the adsorbed species [36]. The removal efficiency of Cr(VI) decreased to
a certain extent as the concentration of NaCl increased from 0.002 to
0.200 mol·L−1. These interesting behaviors could be explained as fol-
lows. (1) The formation of electrical double-layer complexes between
Cr(VI) and mPC was favorable to heavy metal sorption, while the con-
centration of competing ions declined [37]. (2) The ionic strength af-
fected the activity coefficient of Cr(VI), thereby limiting the transfer of
metal ions from aqueous solution to the surface of adsorbents when
the ionic strength increased [36]. (3) Under higher ionic strengths, the
electrostatic repulsion between adsorbents decreased sharply, poten-
tially precipitating aggregation among particles and causing a decline
in the number of active sites on the mPC surface [38].
 Z. Xu et al. / Journal of Molecular Liquids 278 (2019) 496–504 499

Fig. 2. SEM micrographs of (a) CSWM and (b) mPC after HCl pickling; and TEM micrographs of mPC (c) before and (d) after HCl pickling.

3.2.3. Adsorption kinetics where qe and qt (mg·g−1) are the adsorptive capabilities at equilibrium
The adsorption kinetics of Cr(VI) sorption on mPC at different initial and time t; and k1 (min−1) and k2 (g·mg−1·min−1) are the rate con-
concentrations were fitted by the following equations. stants of the two models, respectively.
Pseudo-first-order model: The pseudo-first-order and pseudo-second-order reaction kinetics
of Cr(VI) sorption on mPC at different initial concentrations are depicted
  in Fig. S1. Fast adsorption and a slow equilibrium process were ob-
qt ¼ qe 1−e−k1 t ð1Þ
served, and the adsorption capability of Cr(VI) rose sharply in the initial
time of 30 min, as there were many readily accessible sites that en-
Pseudo-second-order model: hanced the adsorption rate. The adsorption process was completed by
720 min, the removal rates of Cr(VI) at initial concentrations of 50,

−1
150, and 300 mg·L−1 were 91.73%, 56.44%, and 40.12%, while the ad-
qt ¼ k2 qe 2 t  ð1 þ k2 qe t Þ ð2Þ sorption capacities reached 45.87, 84.05, and 120.30 mg·g−1,

Fig. 3. Schematic illustration of the synthesis of mesoporous carbon.

500 Z. Xu et al. / Journal of Molecular Liquids 278 (2019) 496–504

Table 1
Adsorption kinetics model parameters for activated carbons.

Concentration Pseudo-first-order Pseudo-second-order

(mg·L−1)
qe k1 R2 qe k2 R2
(mg·g−1) (min−1) (mg·g−1) (g·mg−1·min−1)

50 41.47 0.0581 0.93 44.43 0.0020 0.98

150 74.82 0.1207 0.92 78.89 0.0027 0.97
300 110.69 0.1618 0.96 115.25 0.0029 0.99

rising temperature, and the maximum adsorption capability of around

Fig. 4. Effects of initial pH on Cr(VI) adsorption onto mPC and CSMW (V = 50 mL; C0 =
100 mg·L−1; m = 50 mg; t = 720 min; T = 25 °C).
respectively. According to R2 in Table 1, the adsorption kinetics of mPC
were of the pseudo-second-order type. Furthermore, the adsorption
rate of mPC increased with the increment of the initial concentration,
based on the adsorption rate constant k2. This was due to the existence
of a greater driving force provided by the higher initial concentration,
which helped to reduce the mass transfer resistance between Cr(VI)
and mPC and thus increased the probability of collisions between Cr
(VI) and the surface adsorption sites [34].
165.93 mg·g−1 was reached when the temperature was 35 °C. Based
on the values of R2, the isotherms were better fitted by the Freundlich
equation than via the Langmuir equation, indicating that Cr(VI) adsorp-
tion onto mPC involved multilayer coverage [37]. The values of n at 15,
25, and 35 °C were 2.91, 3.12, and 3.57, respectively; the fact that these
values were N1 suggests that Cr(VI) was readily adsorbed onto mPC. Be-
sides, based on the values of KF (28.36–29.38), it was clear that mPC pos-
sessed a high adsorption capacity and that Cr(VI) could be easily
adsorbed onto it. As shown in Table 3, compared with the maximum ad-
sorption capability of some other porous carbon materials from various
precursors, mPC had excellent adsorption capacity, and thus could be
regarded as a desirable adsorbent for Cr(VI) removal from wastewater.
The adsorption thermodynamics parameter values, including the
standard free energy change (△G0), the standard entropy change
(△S0), and the standard enthalpy change (△H0) were determined
using the following equations:

3.2.4. Adsorption isotherm and thermodynamics △G0 ¼ −RTlnK 0 ð5Þ

The isotherms of Cr(VI) adsorption onto mPC at different tempera-
tures were fitted by the following equations.
Langmuir: ln K 0 ¼ −△H 0  ðRT Þ−1 þ △S0  R−1 ð6Þ

qe ¼ ðqm K L ce Þ  ð1 þ K L ce Þ−1 ð3Þ where T (K) is the absolute temperature in Kelvin, R

Freundlich:
−1
qe ¼ K F ce 1n
where qm (mg·g−1) is the maximum adsorptive capability, Ce (mg·g−1)
is the equilibrium solute concentration, KL (L·mg−1) is the Langmuir af-
finity constant, and n and KF ((mg·g−1)(L·mg−1)1/n) are the Freundlich
constants corresponding to adsorption intensity and capability,
respectively.
The Langmuir and Freundlich isotherms under different tempera-
ture conditions and the relevant model parameter values are presented
in Fig. S2 and Table 2. The removal performance increased with the
(8.314 J·mol−1·K−1) is the universal gas constant, and K0 is the adsorp-
tion equilibrium constant, which can be calculated by plotting lnK
(qe·C−1
e ) vs Ce and extrapolating Ce to 0.
Linear plots of ln(qe·Ce−1) versus Ce at different temperatures are
ð4Þ
shown in Fig. S3(a). As the temperature increased, the linear plot shifted
toward higher ln(qe·Ce−1) values, demonstrating that the adsorption
equilibrium constant K0 increased with increasing temperature. The
specific values of K0 were calculated to be 1.48 for K015°C, 1.64 for
K025°C, and 1.75 for K035°C, respectively. Linear plots of lnK0 versus 1/T
are shown in Fig. S3(b). The thermodynamic parameters (ΔH0 and
ΔS0) were calculated from this plot using Eqs. (5) and (6), and their
values are listed in Table 4. The value of ΔH0 was 6.45 kJ·mol−1,
which is N0, implying that Cr(VI) adsorption on mPC was an endother-
mic reaction. The explanation for the endothermicity was that Cr(VI)
had to have their hydration sheath denuded to a certain degree during
adsorption, and these dehydration reactions needed energy. The posi-
tive value of ΔS0 (25.67 J·(K·mol)−1) demonstrated that the degree of
disorder increased at the contact surface between adsorbents and ad-
sorbents during adsorption. The values of ΔG0 (−0.941, −1.229, and
−1.428 kJ·mol−1) were negative, demonstrating that these adsorption
reactions were spontaneous processes. The absolute values of ΔG0

Table 2
Isotherm model parameter values for Cr(VI) adsorption onto mPC.

Langmuir Freundlich

Temperature qm KL R2 n KF ((mg·g−1) R2
(K) (mg·g−1) (L·mg−1) (L·mg
−1 1/n
) )

288.15 122.26 0.064 0.88 3.57 29.38 0.97

298.15 143.73 0.057 0.86 3.12 28.36 0.97
Fig. 5. Effects of ionic strength on the Cr(VI) adsorption on mPC (V = 50 mL; C0 =
308.15 165.93 0.051 0.93 2.91 28.87 0.99
100 mg·L−1; m = 50 mg; t = 720 min; T = 25 °C).
 Z. Xu et al. / Journal of Molecular Liquids 278 (2019) 496–504
Table 3
Comparisons of qm of Cr(VI) among various adsorbents.
Adsorbents qm (mg·g−1)
Fox nutshell porous carbon 43.45
N-doped porous carbon 30.96
Arundo donax Linn activated carbon 33.74
Corn cob based magnetized porous carbon 57.19
Bamboo bark activated carbon 19.53
Chestnut oak shells activated carbon 85.47
Peganum harmala seed activated carbon 74.67
Longan seed based activated carbon 169.49
mPC 165.93
increased with increasing temperature, illustrated the better adsorption
performance of mPC toward Cr(VI) at higher temperatures [47].
3.3. Mechanisms for adsorption of Cr(VI)
The high adsorption capability of mPC toward Cr(VI) was not solely
due to the high SBET, the functional groups of mPC formed during pyrol-
ysis of WPT also greatly enhanced Cr(VI) removal. FTIR spectra (Fig. 6)
of mPC before and after Cr(VI) adsorption were recorded to obtain the
wavenumber changes on surface groups in the range from 4000 to
400 cm−1. As shown in the diagram, abundant groups were found on
the carbon surface. The bonds at 3437, 1608, 1384, 1060, and
670 cm−1 were attributed to the O\\H stretching vibration, aromatic
rings vibration coupled to conjugated C_O, C\\H in-plane bending,
C\\O vibration of ether or phenolic, and C\\H out-of-plane bending of
aromatics, respectively [45–50]. After adsorption of Cr(VI), an obvious
absorption peak corresponding to Cr_O or Cr\\O was observed for
mPC-Cr, indicating that Cr(VI) was successfully adsorbed onto the sur-
face of the carbon sample. Furthermore, the characteristic peaks of
O\\H and C\\O were weakened or even vanished, and the peak of
C\\H at 1384 cm−1 was markedly enhanced, implying that these groups
might be involved in the adsorption procedure through ion exchange or
reduction reactions [51]. Meanwhile, the wavenumber of C_O bending
red-shifted from 1608 to 1590 cm−1, thus it was reasonable to assume
that C_O might also participate in Cr(VI) adsorption [52].
To further explore the mechanisms of adsorption, the XPS spectra
(Fig. 7) of mPC before and after Cr(VI) adsorption were investigated in
more detail. The total survey spectrum (Fig. 7a) showed that the main
elements of mPC were C, O, N, and Cl, and their corresponding contents
are listed in Table S2. Compared with mPC, the O and Cr contents of
mPC-Cr increased to 10.45 and 1.96 At.%, respectively, and obvious
peaks ascribed to Cr 2p3/2 and Cr 2p1/2 were found at 577 and 587 eV
[53], indicating that chromium ions were successfully adsorbed on the
adsorbent surface, consistent with the FTIR analysis. Fig. 7b shows the
high-resolution Cr 2p narrow-spectrum scan. Through peak parsing,
the two secondary energy level peaks at 587.9 and 578.1 eV were as-
cribed to Cr 2p1/2 and Cr 2p3/2 of Cr(VI), respectively. Meanwhile, char-
acteristic peaks corresponding to Cr 2p1/2 and Cr 2p3/2 of Cr (III) were
found at 585.7 and 575.9 eV, implying that partial Cr(VI) was reduced
to the less-toxic Cr(III) at the interface between adsorbents and adsor-
bents during adsorption [54]. Fig. 7c shows the C 1 s spectrum of mPC
before and after adsorption. As for mPC, the peaks at 284.7, 285.4, and
288.7 eV were ascribed to C\\H, C\\OH, and C_O, respectively [55].
After adsorption, the peak became broader and the relative intensity
Table 4
Thermodynamic parameters for Cr(VI) adsorption onto mPC.
Temperature ln K0 △G0 △S0 △H0
(K) (kJ·mol−1) (J·(K·mol)−1) (kJ·mol−1)
288.15 0.393 −0.941 25.67 6.45
298.15 0.496 −1.229 – –
−1.428 – –
308.15 0.563
501
Ref.
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
This study
Fig. 6. FTIR spectra analysis of mPC before and after adsorption Cr(VI).
of C_O and C\\OH decreased slightly, whereas the relative intensity
of C\\H increased from 46.56% to 56.12% as shown in Table S3, thus it
was reasonable to assume that these groups took part in the reduction
reaction from Cr(VI) to Cr(III) [56]. The increase in C\\H content could
be ascribed to the oxidation reaction of C-OH and C_O. The possible re-
actions were as follows:
−C−H þ CrðVIÞ þ H2 O→−C−OH þ CrðIIIÞ þ Hþ ð7Þ
−C−OH þ CrðVIÞ þ H2 O→−C ¼ O þ CrðIIIÞ þ Hþ ð8Þ
C ¼ O þ CrðVIÞ þ H2 O→−COOH þ CrðIIIÞ þ Hþ ð9Þ
C−COOH þ CrðVIÞ þ H2 O→−C−H þ CrðIIIÞ þ Hþ þ CO2 ↑ ð10Þ
Furthermore, at pH of 2.0, the surface-bearing\\OH groups could be
neutralized by H+ ions and then converted into \\OH2+ sites, these
could combine with the negative Cr(VI) ions (HCrO4− and Cr2O72−) to
enhance the adsorption performance [57]. Possible reactions are de-
scribed by the following equations:
OH2 þ þ HCrO4 − ↔OH2 þ ⋯HCrO4 − ð11Þ
2OH2 þ þ Cr2 O7 2− ↔OH2 þ ⋯Cr2 O7 2− ⋯OH2 þ ð12Þ
Fig. 7d shows the O 1 s spectra of mPC before and after adsorption.
The peaks at 531.8 and 530.1 eV were attributed to C_O and MgO, re-
spectively [58,59]. Their intensities were calculated from the peak
areas, giving values of 66.77% for C_O and 33.23% for MgO. In mPC-
Cr, characteristic peaks of Cr\\O or Cr_O were detected at 530.6 eV,
validating the conclusions from the XPS total survey spectra and FTIR
analysis. Remarkably, the relative intensity of C_O was reduced to
around 33.78%, possibly owing to the reduction ability of C_O toward
Cr(VI). This result was consistent with the C 1 s spectral analysis.
Fig. 7e shows the Cl 2p spectra of mPC before and after adsorption. As
depicted in the diagram, the peaks at 202.3, 200.5, and 198.4 eV, were
attributed to C\\Cl 2p1/2, C\\Cl 2p2/3, and Cl−, respectively [60]. Com-
paring the contents of the above functional groups in mPC and mPC-
Cr, it was found that the intensity of Cl− dropped by 13.2% on account
of the ion exchange reaction between Cl− loaded on the surface of
mPC and anionic Cr(VI) (Eq. (13)). Besides, Cl− had a certain reducibil-
ity under acidic conditions, which could promote the reduction of Cr
(VI), thereby reducing its toxicity (Eq. (14)).
R2
− −
≡ C  Cl þ HCrO4 − → ≡ C  HCrO4 − þ Cl ð13Þ
0.99
–
– −
Cr2 O7 2− þ 6Cl þ 14Hþ →3Cl2 ↑ þ 2Cr3þ þ 7H2 O ð14Þ
502 Z. Xu et al. / Journal of Molecular Liquids 278 (2019) 496–504

Fig. 7. (a) XPS total survey spectra (a), high-resolution Cr 2p (b), C 1 s (c), O 1 s (d), and Cl 2p (e) spectra of mPC before and after Cr(VI) adsorption.

4. Conclusion
WPT-based mPC was synthesized via a pyrolysis approach in the
presence of MgCl 2. Based on physicochemical characterizations, it
was found that the surface area and total pore volume reached
1289 m2·g−1 and 3.14 cm3·g−1, respectively. Meanwhile, abundant
random stratification structure and oxygen-containing surface
groups were formed in the carbon matrix. The removal efficiency of
Cr(VI) markedly declined at higher ionic strength and pH, owing to
electrostatic repulsion and competitive adsorption. The adsorption
kinetics and isotherm could be explained by pseudo-second-order
and Freundlich models, and mPC showed distinctive sorption
properties toward Cr(VI) along with a high adsorption rate
(0.0029 g·mg −1 ·min−1 ) and maximum adsorption capability
(165.93 mg·g−1). The electrostatic effects between the protonated
mPC and anionic Cr(VI) and the reduction effects of surface groups
were confirmed as the main removal mechanisms. The ion exchange
reaction between Cl− and HCrO4− could also promote the removal of
Cr(VI). It was verified that mPC is a desirable adsorbent for Cr(VI)-
containing wastewater.
Acknowledgements
Financial support by National Natural Science Foundation of
China (21707090) and China Postdoctoral Science Foundation
(2017M611590).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2019.01.088.
 Z. Xu et al. / Journal of Molecular Liquids 278 (2019) 496–504
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