Journal of Colloid and Interface Science 564 (2020) 428–441

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Journal of Colloid and Interface Science

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

A coupling technology of capacitive deionization and MoS2/

nitrogen-doped carbon spheres with abundant active sites for efficiently
and selectively adsorbing low-concentration copper ions
Zhengle Hao a,b,c,d, Yanmeng Cai a,b,c,d, Yue Wang a,b,c,d,⇑, Shichang Xu a,c,d, Jixiao Wang a,b,c,d
a
Chemical Engineering Research Center, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
b
State Key Laboratory of Chemical Engineering, Tianjin 300072, PR China
c
Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072, PR China
d
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

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

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

Article history: Conventional techniques like electrodialysis, evaporation concentration cannot efficiently and selectively
Received 1 August 2019 separate valuable heavy metals ions (VHMI) from electroplating rinse wastewater due to VHMI’s low con-
Revised 6 December 2019 centration and other ions’ competitive adsorption. To realize the separation, a coupling technology was
Accepted 15 December 2019
proposed which combines capacitive deionization (CDI) technique suitable for separating low-
Available online 28 December 2019
concentration ions and the few-layer molybdenum disulfide/N-doped carbon spheres (FL-MoS2/NCS)
composite capable of selectively adsorbing copper ions (Cu2+), a representative VHMI. The FL-MoS2/
Keywords:
NCS composite was successfully prepared by one-pot method and used as the cathode and anode in a
Valuable heavy metal
Capacitive deionization
CDI cell. Electrosorption experiments in the CDI cell showed that the FL-MoS2/NCS electrode (cathode)
Few-layer molybdenum disulfide/N-doped can efficiently adsorb low-concentration Cu2+ (23.63 mg/L) with a saturated adsorption capacity of
carbon spheres 1199.63 mg/g at 0.8 V. In the competitive environment (Cu2+/Na+/Fe3+), the FL-MoS2/NCS electrode can
Low concentration selectively adsorb Cu2+ still with a high adsorption capacity of 1071.6 mg/g greatly outnumbering that
Copper ions of Na+ (199.2 mg/g) and Fe3+ (262.8 mg/g), despite the high concentrations of both NaCl (500 mg/L)
Adsorption and FeCl3 (80 mg/L). Furthermore, the XPS test and competitive adsorption results proved that the effi-
cient and selective adsorption of the FL-MoS2/NCS electrode for Cu2+ was synergistically promoted by
electrical double layer (EDL) and complexation of Cu2+ with FL-MoS2/NCS.
Ó 2019 Elsevier Inc. All rights reserved.

1. Introduction

⇑ Corresponding author at: Chemical Engineering Research Center, School of

The rapid development of science and technology is inseparable
Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China.
from the use of heavy metals, especially valuable heavy metals.
E-mail address: tdwy75@tju.edu.cn (Y. Wang).

https://doi.org/10.1016/j.jcis.2019.12.063
0021-9797/Ó 2019 Elsevier Inc. All rights reserved.
 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Meanwhile, a large amount of wastewater containing valuable
heavy metal ions (VHMI) has been produced, such as copper, gold
and so on [1]. In particular, industrial electroplating rinse wastew-
ater is the main source of the wastewater containing VHMI [2]. The
direct discharge of rinse wastewater not only poses a serious threat
to human health and the environment, but also causes waste of
valuable heavy metal resources [1]. Therefore, it is urgent to
develop a technology that can efficiently separate VHMI from elec-
troplating rinse wastewater.
At present, two main difficulties exist in separating VHMI from
rinse wastewater: one is the low adsorption capacity due to the
low concentration of VHMI in the rinse wastewater (below
50 mg/L), and the other is the failure to selectively separate VHMI
from rinse wastewater due to the competitive effects of other ions,
such as common salt ions [3]. Conventional technologies such as
electrodialysis and evaporation concentration cannot solve these
two difficulties at the same time, so VHMI cannot be efficiently
separated from the rinse wastewater [3]. For one thing, capacitive
deionization (CDI) technology, also called electrosorption technol-
ogy, has received wide attention owing to its suitability for sepa-
rating low-concentration ions [4]. This is because charged ions
are enriched around the electrode at an applied voltage and
adsorbed into the electrical double layer (EDL) formed at the
electrode/solution interface. Therefore, the removal of low-
concentration ions in water is achieved [5,6]. However, CDI tech-
nology has no selectivity for ion adsorption in the above process
[7]. For another thing, molybdenum disulfide (MoS2) has attracted
attention due to the selective adsorption of VHMI in an environ-
ment containing competitive ions [8,9]. This is because MoS2
which is rich in sulfur (soft base) can preferentially interact with
VHMI (soft acid) based on hard-soft-acid-base theory, so that VHMI
can be separated from wastewater [10,11]. However, MoS2 as a
conventional adsorbent is mainly used to treat wastewater con-
taining high-concentration VHMI, and the process for treating rinse
wastewater containing low-concentration VHMI is not mature
enough [12].
In order to address the two difficulties of separating VHMI from
rinse wastewater, we can integrate the advantages of CDI technol-
ogy and MoS2 to achieve efficient separation of low-concentration
VHMI. Zhang et al. used 2H phase MoS2 as a CDI electrode material
to adsorb low-concentration Pb2+ (<6 mg/L) [13]. The results
showed that Pb2+ can be well removed with an adsorption capacity
of 86.26 mg/m2 due to the cooperation of electrosorption and
chemisorption, which proves the feasibility of removing low-
concentration VHMI by combining CDI technology with MoS2.
However, the easy agglomeration and small interlayer spacing of
the generally prepared 2H phase MoS2 result in insufficient utiliza-
tion of internal sulfur atoms (active sites) [8,14,15]. Also, the 2H
phase MoS2 has poor conductivity and hydrophilicity, which
affects the performance of MoS2 as an electrode material [16,17].
In response to these problems, many researchers have integrated
MoS2 with carbon material such as carbon nanotubes [18,19], acti-
vated carbon fiber cloth [20], grapheme [21], etc. to prepare com-
posites for use in batteries and supercapacitors. The resulting
composite possesses enlarged interlayer spacing, good dispersion,
conductivity and hydrophilicity. However, these carbon materials
either involve the use of costly raw materials or undergo sophisti-
cated and environmentally unfriendly preparation steps. In con-
trast, the preparation of polydopamine-derived carbon spheres
by direct polymerization of dopamine is low-cost, easily prepared,
and environmentally friendly [22,23]. Also, the polydopamine-
derived carbon spheres are abundant in nitrogen heteroatoms,
which can not only improve the conductivity and hydrophilicity
of the material, but also selectively adsorb VHMI [24–26].
Here, a coupling technology of capacitive deionization and few-
layer molybdenum disulfide/N-doped carbon spheres (FL-MoS2/
429
NCS) composite for efficiently and selectively adsorbing low-
concentration Cu2+ was investigated. The structure, morphology
and composition information of the composite were obtained by
physical characterization. The FL-MoS2/NCS composite was made
into an electrode and the electrochemical performance of the FL-
MoS2/NCS electrode was investigated by electrochemical worksta-
tion. Besides, the electrodes were used as the cathode and anode to
construct a CDI cell for electrosorption experiments. Copper ions
(Cu2+) was chosen as a representative of valuable heavy metals
to investigate the adsorption behavior of VHMI by electrosorption
experiments in the CD cell. Firstly, the electrosorption performance
of the FL-MoS2/NCS electrode (cathode) for low-concentration Cu2+
was studied in copper chloride (CuCl2) solution. Furthermore, the
adsorption selectivity of the FL-MoS2/NCS electrode (cathode) for
Cu2+ was investigated in the competitive environment (Na+, Fe3+).
The adsorption mechanism was revealed by adsorption kinetics,
intra-particle diffusion, adsorption isotherm models and X-ray
photoelectron spectroscopy measurement.
2. Experimental sections
2.1. Materials
Dopamine hydrochloride, ammonia aqueous solution (28%-
30%), Sodium molybdate dihydrate, Thiourea, Copper chloride, Iron
chloride hexahydrate, Sodium chloride, and 1-Methyl-2-
pyrrolidinone were purchased from Aladdin Industrial Corpora-
tion. Ethanol was purchased from Li Anlong Bohua (Tianjin)
Pharmaceutical Chemical Co., Ltd. All chemicals were analytical
reagents and used as received without any further purification.
2.2. Preparation of materials
Preparation of polydopamine spheres (PDAS): As reported in
the previous literature [23], first, 90 mL of deionized water,
40 mL of absolute ethanol and 0.6 mL of ammonia aqueous solu-
tion (28%-30%) were uniformly mixed. Then, 0.5 g of dopamine
hydrochloride was dissolved in 10 mL of deionized water and
added dropwise to the above mixture solution. Finally, the reaction
was carried out for 37 h with gentle stir at room temperature. The
obtained PDAS were washed several times with deionized water
and absolute ethanol before being dried at 60 °C overnight.
Preparation of FL-MoS2/NCS: As shown in Fig. 1, firstly, the
PDAS prepared above (0.2 g) were dispersed into 20 mL of ethanol
solution (ethanol’s volume fraction: 50%) via ultrasonication for
1 h, then 2.18 g of sodium molybdate dihydrate and 2.06 g of
thiourea were dissolved in deionized water (50 mL) to form a
transparent solution. The PDAS suspension was added to the above
transparent solution and stirred for 30 min, and then concentrated
hydrochloric acid was added to adjust the pH to about 1. After that,
the above suspension was transferred to a hydrothermal synthesis
reactor and maintained at 200 °C for 24 h. During the hydrother-
mal process, MoO2
4 are adsorbed on the surface of the PDAS due
to the rough surface of the PDAS, abundant catechol base and chi-
none base, and positive zeta potential (8.77 mV). Meanwhile, H2S
generated by thiourea at high temperature and pressure is also
adsorbed on the rough surface of the PDAS. Subsequently, the FL-
MoS2 nanosheets grow on the surface of PDAS by the reaction of
H2S with MoO2
4 . After cooling down, the obtained FL-MoS2/PDAS
was washed several times with deionized water and absolute etha-
nol, and dried at 60 °C overnight. Finally, the dried product was
calcined at 800 °C for 2 h under a nitrogen atmosphere to obtain
FL-MoS2/NCS with good conductivity and crystallinity. For compar-
ison, the product was prepared without adding PDAS under the
430 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441

Fig. 1. Schematic illustration of the preparation process of FL-MoS2/NCS.

same conditions, and were named as Bare MoS2 and MoS2 before
and after calcination, respectively.
2.3. Characterization
Morphology, structure, and composition information were char-
acterized by field emission scanning electron microscope (SEM)
(Hitachi S-4800), field emission transmission electron microscope
(TEM) (Philips Tecnai G2 F20), X-ray diffraction (XRD) (Bruker D8-
Focus), Raman (Renishaw inVia reflex) and X-ray photoelectron
spectroscopy (XPS) (PHI5000 VersaProbe, Japan). The specific surface
area and pore structure were tested by using a Quantachrome Nova
station. The mass fraction of MoS2 in the composite was analyzed by
thermogravimetric analyzer (Netzsch STA449F3). The hydrophilicity
of the composite was analyzed by employing the contact angle ana-
lyzer (DataPhysics Instruments, Germany).
2.4. Preparation of electrodes
The Coating method was used to prepare the electrodes in this
work [27]. First, active materials (FL-MoS2/NCS or MoS2),
polyvinylidene fluoride (PVDF) and graphite powder were pre-
pared into electrode slurry at a ratio of 8:1:1 by using N-methyl-
2-pyrrolidone (NMP) as a solvent. Then, the obtained slurry was
coated on the surface of graphite paper with a scraper and dried
at room temperature. In addition, the MoS2 electrode was also pre-
pared by the same procedure.
2.5. Electrochemical performance measurements
Cyclic voltammetry (CV), galvanostatic charge-discharge (GCD)
and electrochemical impedance spectroscopy (EIS) tests were con-
ducted in 1 M NaCl solution by using the electrochemical worksta-
tion (PARSTATTM 4000A) under a three-electrode system. The
system includes a platinum electrode as the counter electrode, a
saturated calomel electrode (SCE) as the reference electrode, and
a FL-MoS2/NCS electrode or a MoS2 electrode as the working elec-
trode. The potential range of CV measurement was between
0.6
and 0.4 V. The calculation of the specific capacitance was based
on Eq. (1) by means of the CV curves.
R E2
idE
C¼ E1
ð1Þ
2mv ðE2
E1Þ
The EIS test was performed with an AC amplitude of 10 mV and
the frequency ranges from 0.01 Hz to 100 kHz. The specific capac-
itance (Ci, Fg
1) was derived from the imaginary part of the impe-
dance spectrum based on Eq. (3):
 
 1 
Ci ¼   ð3Þ
2pfmZ im 
where f (Hz) is the scanning frequency, Zim (X) is the imaginary part
of the impedance spectrum, and m (g) is the mass of the active
material in the electrode.
2.6. Electrosorption experiment
In order to investigate the electrosorption performance of the
FL-MoS2/NCS electrode, electrosorption experiment was carried
out in a CDI cell at 25 °C. The CDI cell was assembled by using
the FL-MoS2/NCS electrode as the cathode and anode, and the dis-
tance between the two electrodes is 1 cm. The test voltage (0.8 V)
is provided by a direct current regulated power supply. The
copper-containing rinse wastewater was simulated by 270 mL of
50 mg/L CuCl2 solution (Cu2+ concentration: 23.63 mg/L) with a
pH of 4.5. After the electrode reached saturated adsorption, the
electrode was placed in a 1 M nitric acid solution for desorption.
Then, this electrode was adopted again for the adsorption of
Cu2+, and the reusability of the electrode was evaluated by repeat-
ing 5 cycles. The above experiments were repeated for three times.
In the competitive adsorption experiments (binary systems: Cu2+/
Na+ and Cu2+/Fe3+; ternary system: Cu2+/Fe3+/Na+), the effects of
the presence of competitive ions on the adsorption performance
of Cu2+ on the FL-MoS2/NCS electrode were investigated in CuCl2
solution (50 mg/L). The concentration of Cu2+ was measured by
using inductively coupled plasma optical emission spectrometer
(ICP-OES). In our experiments, the adsorption capacity is defined
as follows:
ðC 0
C e ÞV
q¼ ð4Þ
m
where C0 and Ce (mg/L) represent the initial and final concentra-
tions, respectively, V is the total volume (mL) of CuCl2 solution,
and m is the mass of the electrode material.
3. Results and discussion

where E1, E2 (V) are the initial and terminal potential, i (A) is the
instantaneous current, v (V/s) is the scan rate, and m (g) is the mass
of the active material in the electrode. The GCD test was conducted
at different current densities. The discharge specific capacitance is
calculated from the GCD curve by the following formula:
It
C¼
mDV
where I (A) is the constant current during charging and discharging,
t (s) is the discharge time, m (g) is the mass of the active material in
the electrode, and DV (V) is the potential window during discharge.
3.1. Material characterization
The morphology of PDAS, FL-MoS2/NCS and MoS2 was investi-
gated by SEM. As shown in Fig. 2(a) and (b), dopamine hydrochlo-
ride successfully self-assembled into PDAS with a particle size of
about 540 nm (Fig. S1) and a rough surface. As displayed in Fig. 2
ð2Þ (e) and (f), although MoS2 is laminated structure (Fig. 2(f)), large
amount of pure MoS2 nanosheets agglomerate into a cauliflower-
like structure (Fig. 2(e)). In sharp contrast to MoS2, it can be clearly
found that the FL-MoS2 nanosheets are well dispersed on the sur-
face of NCS with wrinkled and curved edges (Fig. 2(c) and (d)). The
 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Fig. 2. SEM images of (a and b) PDA spheres, (c and d) FL-MoS2/NCS, (e and f) MoS2.
results indicate that the presence of PDAS greatly alleviates the
agglomeration effect of MoS2 nanosheets in the hydrothermal
process.
The layer numbers of MoS2 and FL-MoS2/NCS were studied by
TEM, as depicted in Fig. 3. A large number of MoS2 nanosheets
stacked together can be observed in Fig. 3(a) and (b), which is con-
sistent with the results of SEM. As shown in Fig. 3(c), the layer
number of MoS2 is approximately 10 layers, and the interlayer
spacing is 0.63 nm which is larger than that of commercial MoS2
(about 0.615 nm) [15]. The expansion between layers can be attrib-
uted to the insertion of thiourea and ethanol into the interlayer of
MoS2 during the hydrothermal process. Fig. 3(d) and (e) clearly
show a distinct interface between the FL-MoS2 nanosheets and
the NCS, indicating that the FL-MoS2 nanosheets are well dispersed
on surface of NCS. The layer number of FL-MoS2 nanosheets loaded
on the NCS is mostly below 5 layers and the expanded interlayer
spacing is 0.65 nm. It is because the presence of NCS does not only
prevent the tendency of FL-MoS2 nanosheets to aggregate, but also
further enlarge the interlayer distance of FL-MoS2 nanosheets.
Meanwhile, as depicted in the circled part in Fig. 3(f), the FL-
MoS2 nanosheets possess many defects. The enlarged interlayer
distance and defects not merely increase the active adsorption
sites of FL-MoS2 nanosheets, but also reduce the diffusion length
of ions [28]. The element distribution and structure of FL-MoS2/
NCS were further studied by energy dispersive X-ray spectroscopy
431
(EDX). Fig. 3(h)–(k) manifest that the presence and distribution of
C, N, S and Mo elements. C and N elements are evenly distributed
in the middle of the carbon spheres (Fig. 3(h) and (i)) while Mo and
S elements are uniformly distributed in the outside of the carbon
spheres (Fig. 3(j) and (k)). The above SEM and TEM results prove
that the FL-MoS2/NCS composite were successfully prepared.
The crystalline phases and the interlayer spacing of the prod-
ucts were examined by XRD, as illustrated in Fig. 4(a) and (b).
Fig. 4(a) shows that both MoS2 and FL-MoS2/NCS have diffraction
peaks of five crystal planes of (0 0 2), (1 0 1), (1 0 3), (1 0 5) and
(1 1 0), which are consistent with the hexagonal crystal structure
of MoS2 (JCPDS card No. 37-1492) [29]. The diffraction peak of
(0 0 2) crystal plane of Bare MoS2 is split into two peaks which
appear at about 9° and 18°, respectively. This suggests that the
interlayer spacing of MoS2 nanosheets before calcination is about
0.98 nm [30], which can be attributed to the interlayer expansion
caused by superfluous thiourea and ethanol macromolecules
embedded in interlayer of MoS2 nanosheets during hydrothermal
process. However, after calcination of Bare MoS2 at high tempera-
ture under the nitrogen atmosphere, the diffraction peak of the
(0 0 2) crystal plane is again transformed into that of MoS2 with
hexagonal crystal structure. It is predominantly because thiourea
and ethanol macromolecule embedded in the interlayer are
removed during the calcination process. Meanwhile, the position
of diffraction peak of the (0 0 2) crystal plane after calcination
432 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Fig. 3. TEM images (a and b) and HRTEM image (c) of MoS2, TEM images (d and e) and HRTEM image (f) of FL-MoS2/NCS, annular dark-field STEM image (g) and EDX
elemental mapping images of (h) C, (i) N, (j) S, (k) Mo in a single FL-MoS2/NCS.
shifted to a lower angle (13.9°) (Fig. 4(b)). This phenomenon indi-
cates that the interlayer spacing of MoS2 after calcination
(0.63 nm) is greater than the standard value (0.615 nm), which
can be also reflected in Fig. 3(c). This result can be attributed to
the fact that although embedded thiourea and ethanol macro-
molecules are eliminated at high temperature, the residual lattice
defects have resulted in the formation of an enlarged interlayer
spacing. Compared with MoS2, the diffraction peak of the (0 0 2)
crystal plane of FL-MoS2/NCS appears at 13.5° and the intensity
is greatly reduced, indicating that the interlayer distance is further
expanded to 0.65 nm [15,31], which is consistent with the result of
HRTEM image (Fig. 3(f)). This is primarily because the presence of
NCS further inhibits the growth of the (0 0 2) crystal plane of FL-
MoS2 nanosheets. The selected area electron diffraction pattern
(SAED) (Fig. 4(d)) verifies that FL-MoS2/NCS is a polycrystalline
structure, and all diffraction rings coincide with the diffraction
peaks corresponding to XRD.
Raman spectra further illustrates the successful loading of FL-
MoS2 nanosheets on NCS. As for FL-MoS2/NCS, the typical E12g and
A1g vibration modes of FL-MoS2 appear at 379.9 cm
1 and
403.4 cm
1, respectively, and the peaks at 1368 cm
1 and
1599 cm
1 correspond to the D and G bands of carbon (Fig. 4(c))
[32]. Furthermore, it is found from the inset of Fig. 4(c) that the fre-
quency difference between A1g (378.1 cm
1) and E12g (404.4 cm
1)
of MoS2 (26.3 cm
1) is greater than that of FL-MoS2/NCS
(23.5 cm
1), which indicates that the layer number of FL-MoS2
nanosheets in FL-MoS2/NCS is less than that of MoS2 [33–35].
The chemical composition of FL-MoS2/NCS and the chemical
states of S and Mo were analyzed by XPS. The XPS survey spectrum
of FL-MoS2/NCS demonstrates that C, N, Mo, S exist in the compos-
ite and the atomic ratio of S to Mo is about 2 (Fig. 5(a)), which
matches the stoichiometry value of MoS2. In the high-resolution
spectrum of C1s (Fig. 5(b)), the characteristic peaks of CAN, CAC
and CAO appear at 284.7, 285.6 and 287.5 eV. The high-
resolution spectrum of N1s shows that the peaks at 395.4, 397.3
and 401.4 eV are attributable to Mo-N, pyridinic N and pyrrolic N
(Fig. 5(c)). As shown in Fig. 5(d), the peaks at 229.5 and 232.7 eV
correspond to Mo3d5/2 and Mo3d3/2, indicating the existence of
Mo4+. Meanwhile, the small peak at 226.8 eV can be ascribed to
the presence of S2
. The high-resolution spectrum of S 2p displays
characteristic peaks at 162.3 and 163.5 eV (Fig. 5(e)), which are
derived from the S2p3/2 and S2p1/2 orbitals of S2
, respectively [36].
In order to obtain the pore structure and specific surface area of
FL-MoS2/NCS and MoS2, nitrogen adsorption-desorption measure-
ments were performed on the two materials, as shown in Fig. 6
(a) and (b). The isotherms of the two materials are typical type
IV with type H3 hysteresis loop, indicating the presence of meso-
porous structures (Fig. 6(a)). FL-MoS2/NCS has a pore size distribu-
tion of about 2–2.5 nm calculated by the BJH method (Fig. 6(b)),
which is mainly derived from the interlaced FL-MoS2 nanosheets
and NCS. A large number of mesopores can act as a ‘‘reservoir”
for ions and accelerate the rate of ions migration [31]. According
to Fig. 6(a), the specific surface area of the two materials was
obtained by the BET method. The specific surface area of FL-
MoS2/NCS is 43.87 m2/g, which is 3.3 times that of MoS2
 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Fig. 4. (a) XRD patterns of FL-MoS2/NCS, MoS2 and Bare MoS2, (b) the (0 0 2) plane peak of XRD of FL-MoS2/NCS, MoS2, (c) Raman spectra of FL-MoS2/NCS, MoS2 (inset of c:
Raman spectra of E12g and A1g vibration modes), (d) SAED pattern of FL-MoS2/NCS.
(13.23 m2/g). The large specific surface area can provide more
active sites for ions adsorption.
In order to further obtain the mass fraction of FL-MoS2
nanosheets and carbon spheres in the composite, TGA measure-
ments of MoS2 and FL-MoS2/NCS were carried out, separately. As
shown in Fig. 6(c), the mass of MoS2 remains basically unchanged
below 350 °C, while the sharp mass loss between 350 and 500 °C
can be ascribed to the oxidation of MoS2 into MoO3 in the air atmo-
sphere. Compared with MoS2, the weight loss of FL-MoS2/NCS goes
through two processes. Firstly, the mass loss below 350 °C can be
attributed to the evaporation of the adsorbed water in the material.
Secondly, the weight loss between 350 and 515 °C is due to the
conversion of FL-MoS2 nanosheets to MoO3 and the decomposition
of NCS. The mass fractions of FL-MoS2 nanosheets and NCS in FL-
MoS2/NCS were calculated to be 94.31% and 5.69%, respectively.
Moreover, the NCS improve the hydrophilicity of the FL-MoS2/
NCS electrode with a contact angle of 62°, which is lower than
the 96° of the MoS2 electrode. (Fig. 6(d)). This phenomenon can
be attributed to the abundant nitrogen heteroatoms in NCS
[37,38]. The enhanced hydrophilicity demonstrates that NCS can
indeed improve the wettability of the material, which can facilitate
the diffusion of ions into the pores of the electrode and improve
the adsorption performance of CDI [39].
3.2. Electrochemical properties
The electrochemical properties of FL-MoS2/NCS and MoS2 elec-
trodes were investigated by CV measurements. The results of the
CV test are shown in Fig. 7(a) and (b). Fig. 7(a) depicts the CV
curves of the FL-MoS2/NCS and MoS2 electrodes at 5 mV/s in 1 M
NaCl solution. According to the Eq. (1), the specific capacitance of
the FL-MoS2/NCS electrode (472.2 F/g) is much higher than that
of the MoS2 electrode (176.1 F/g). For one thing, the high specific
capacitance of the composite can be attributed to the fact that good
433
dispersion of FL-MoS2 nanosheets, the enlarged interlayer spacing
and rich defects reduce the diffusion resistance of ions and
enhance the kinetics of ion transport [40]. Moreover, the improved
hydrophilicity of FL-MoS2/NCS can also accelerate the transport of
ions. The Inset of Fig. 7(b) shows that the CV curves maintain a
good rectangular shape as the scan rate increases from 5 to
100 mV/s, which demonstrates ideal EDL capacitance behavior.
However, the shape of the CV curve is fusiform at a scan rate of
200 mV/s. This is because the ions can only be adsorbed on the sur-
face but can’t reach the interior of the material at high scan rates,
resulting in the distortion of the CV curve and a sharp decline in
the specific capacitance. Fig. 7(b) clearly displays that the specific
capacitance of the FL-MoS2/NCS electrode shows a decreasing
trend with increasing scan rate, but it is always higher than that
of the MoS2 electrode. The result verifies that ions can migrate
rapidly to the surface and interior of the FL-MoS2/NCS electrode
due to low diffusion resistance.
GCD test was performed to further understand the electro-
chemical behaviors of the composite as shown in Fig. 7(c)–(e).
The GCD measurements of the FL-MoS2/NCS and MoS2 electrodes
show a symmetrical isosceles triangle curve (Fig. 7(c)), which indi-
cates that the two electrodes exhibit ideal EDL capacitance behav-
ior. As displayed in Fig. 7(c), the discharge time of the FL-MoS2/NCS
electrode at 1 A/g is greater than that of the MoS2 electrode, sug-
gesting the specific capacitance of the FL-MoS2/NCS electrode cal-
culated by Eq. (2) is higher than that of the MoS2 electrode. Besides,
the GCD curves of the FL-MoS2/NCS electrode still maintain a sym-
metrical triangle with increasing current density (inset of Fig. 7(d)),
showing excellent charge and discharge characteristics. Mean-
while, the specific capacitance of the FL-MoS2/NCS electrode shows
a downward trend with the increase of current density (Fig. 7(d)),
but it is still higher than that of the MoS2 electrode. Besides, the
internal resistance of the composite causes an IR drop in the initial
portion of the charge and discharge curves. The variation of IR drop
434 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441

Fig. 5. (a) XPS of FL-MoS2/NCS survey spectrum, (b-e) high-resolution spectra of C 1s, N 1s Mo 3d, and S 2p.

with current density during discharge of the two electrodes is pre-
sented in Fig. 7(e). It can be found that the IR drop of the FL-MoS2/
NCS electrode rises with increasing current density and is smaller
than that of the MoS2 electrode, which can be attributed to the
reduced electrode resistance due to the presence of NCS. The excel-
lent electrochemical properties of the composite are also high-
lighted in the excellent cycle stability. The CV curve of the FL-
MoS2/NCS electrode after 100 cycles maintained the initial shape
of the first cycle, indicating good electrochemical stability (Fig. 7
(f)). In summary, the above CV and GCD test results fully prove that
the FL-MoS2/NCS electrode possesses excellent electrochemical
performance.
In order to study the resistance and capacitive behavior of the
composite, the EIS test was performed. Fig. 8(a) and (b) are the
Nyquist plots of the two electrodes and the enlarged part of the
Nyquist plots in the high frequency region, respectively. The equiv-
alent series resistance of the FL-MoS2/NCS electrode (x-intercept:
0.25 X) in the high frequency region (including the solution resis-
tance, the active material resistance and the contact resistance) is
smaller than that of MoS2 electrode (0.48 X). Meanwhile, it can be
clearly seen from Fig. 8(b) that the Nyquist curve of the MoS2 elec-
trode displays a 1/4 arc in the high frequency region while the
Nyquist curve the FL-MoS2/NCS electrode is absent, verifying that
the charge transfer resistance of the FL-MoS2/NCS electrode is
 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Fig. 6. (a) N2 adsorption/desorption isotherm, (b) the pore size distribution (inset of b: partial enlarged detail) and (c) TGA curves of FL-MoS2/NCS and MoS2, (d) water contact
angles on the surfaces of FL-MoS2/NCS and MoS2 electrodes.
lower than that of the MoS2 electrode. Aforementioned results are
mainly originated from a large amount of Sp2 C and nitrogen atoms
in the NCS that can simultaneously improve the conductivity of the
FL-MoS2/NCS. The slope of the straight line of FL-MoS2/NCS elec-
trode in the low frequency region is greater than that of MoS2 elec-
trode (Fig. 8(a)), which represents the FL-MoS2/NCS electrode has
lower Warburg diffusion resistance. So the above results indicate
that electrons and ions have a larger migration driving force in
the FL-MoS2/NCS electrode.
In addition, the charging resistance of the FL-MoS2/NCS and
MoS2 electrodes change with frequency as depicted in Fig. 8(c).
The charging resistance represents a process in which ions diffuse
from the solution into the electrode pores, calculated by subtract-
ing the high frequency impedance of 100 kHz from the real impe-
dance at a specific frequency. The FL-MoS2/NCS electrode exhibits
lower charging resistance in the low frequency range of 0.01–10 Hz
(Fig. 8(c)) compared to the MoS2 electrode, which is predominantly
ascribed to the improved dispersion, the interlayer distance and
hydrophilicity of FL-MoS2/NCS. However, the charging resistance
of the FL-MoS2/NCS electrode is basically the same as that of the
MoS2 electrode in the range of 10–100,000 Hz, because the ions
can only migrate to the surface of the two electrodes and the inte-
rior adsorption sites are not fully utilized.
In order to further investigate the relationship between the
dynamic specific capacitance and frequency, the specific capaci-
tance of electrodes at different frequencies is calculated from Eq.
(3). Fig. 8(d) shows that the specific capacitance of the FL-MoS2/
NCS electrode decreases with increasing frequency. And the FL-
MoS2/NCS electrode possesses a higher specific capacitance
(437 F/g) than that of the MoS2 electrode (162 F/g) at the low fre-
quency of 0.01 Hz, which conforms that the active sites inside the
electrode can be thoroughly utilized at the low frequency. This
result coincides with the conclusion from previous CV measure-
435
ment. In summary, the above electrochemical test results demon-
strate the excellent electrochemical performance of the FL-MoS2/
NCS electrode, which can guarantee a satisfactory CDI performance.
Here, the FL-MoS2/NCS electrode was used in the following elec-
trosorption experiments.
3.3. Adsorption kinetics of Cu2+ on the electrode
In order to investigate the mechanism and potential rate-
controlling steps of the adsorption process, including mass transfer
and chemical reaction processes, kinetic models have been
employed to further analyze the crucial factors affecting the
adsorption of Cu2+ on the FL-MoS2/NCS electrode. In general,
pseudo-first-order kinetic, pseudo-second-order kinetic and
intra-particle diffusion models have been adopted to evaluate the
experimental data. The linear forms of pseudo-first-order (5) and
pseudo-second-order kinetics (6) models are as follows:
Lnðqe
qt Þ ¼ Lnqe
k1 t ð5Þ
t 1 t
¼ þ ð6Þ
qt k2 q2e qe
where qt (mg/g) and qe (mg/g) are the adsorption capacity at time t
(h) and equilibrium, and k1 (h
1) and k2 (gmg
1h
1) are the
pseudo-first-order and pseudo-second-order kinetics adsorption
rate constants, respectively.
In addition, ion diffusion (mass transfer) plays an important role
in the solid-liquid adsorption process. In order to better under-
stand the diffusion mechanism in the adsorption process, the
intra-particle diffusion model equation is adopted for analysis.
The intra-particle diffusion model can be expressed as Eq. (7):
qt ¼ ki t 1=2 þ C ð7Þ
436 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441

Fig. 7. (a) CV curves of FL-MoS2/NCS and MoS2 electrodes at a scan rate of 5 mV/s, (b) the specific capacitance of FL-MoS2/NCS and MoS2 electrodes at different scan rates
(inset of b: CV curves of FL-MoS2/NCS electrode), (c) GCD curves of FL-MoS2/NCS and MoS2 electrodes at a current density of 1 A/g, (d) the specific capacitance (inset of d: GCD
curves of FL-MoS2/NCS electrode) and (e) iR drop of FL-MoS2/NCS and MoS2 electrodes at different current densities, (f) Cycling performance of FL-MoS2/NCS electrode at a
scan rate of 50 mV/s.

where ki (mgg
1h
1/2) is the rate constant of the intra-particle dif-
fusion model and C is the intercept, representing the thickness of
the liquid film.
The kinetics fitting results at 25 °C are shown in Fig. 9(b)–(d). It
can be observed from Fig. 9(b) and (c) that the linear correlation
coefficient of the pseudo-first-order kinetic (R2 = 0.996) is higher
than that of the pseudo-second-order kinetic (R2 = 0.988), indicating
that the electrosorption process at 0.8 V conforms to the pseudo-
first-order kinetic and is controlled by diffusion. Generally, the
adsorption process can be divided into three stages: the ions diffuse
from the bulk solution to the electrode surface; the ions pass
through the liquid film of the electrode surface to the interior of
the electrode material; the ions combine with the active sites. In
the electrosorption process, for one thing, the synergetic effect of
electric field force and forced convection greatly reduces the
diffusion resistance, which promotes the enrichment of low-
concentration Cu2+ from the bulk solution to the periphery of the
electrode surface. Furthermore, the diffusion resistance is reduced
and the internal active sites (S and N) can be fully utilized due to
the enlarged interlayer distance of the FL-MoS2/NCS. Therefore, the
cooperation of the above advantages greatly promotes the adsorp-
tion of Cu2+ on the FL-MoS2/NCS electrode with a high adsorption
capacity of 1199.63 mg/g which is much higher than the adsorption
capacity obtained in other studies [11,41]. However, when the
applied voltage is 0 V, the pseudo-second-order kinetic model can
better describe the adsorption process, which is controlled by
chemisorption and the adsorption capacity drops sharply to only
48.4 mg/g (Fig. S2). This is attributed to the increase in ionic diffu-
sion and migration resistance due to the absence of electric field
force. Only a tiny proportion of Cu2+ are enriched to the exterior sur-
face of the electrode for complexation with the active sites, while the
interior active sites are not efficiently utilized. Therefore, the high
 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Fig. 8. (a) Nyquist plots of FL-MoS2/NCS and MoS2 electrodes, (b) the enlarged part of Nyquist plots in the high frequency region, (c) charging resistance and (d) specific
capacitance of FL-MoS2/NCS and MoS2 electrodes as a function of frequency.
adsorption capacity at 0.8 V proves that the electric field force from
the CDI technique greatly increases the diffusion (rate-controlling
step) rate of low-concentration Cu2+.
Furthermore, the high adsorption capacity is inseparable from
the use of FL-MoS2/NC. The specific reasons are as follows: firstly,
good hydrophilicity improves the wetting performance between
the electrolyte and the electrode, and the electrosorption perfor-
mance at the interface; secondly, the enlarged interlayer spacing,
abundant defects and mesoporous structure accelerate the migra-
tion of ions and enhance the adsorption capacity; finally, the inter-
action between the abundant S, N active sites (soft base) and Cu2+
(hard acid) greatly facilitates the adsorption of Cu2+. In summary,
the coupling technology of CDI and FL-MoS2/NCS can be used to
efficiently adsorb low-concentration Cu2+.
As displayed in Fig. 9(d), the fitting results of the intraparticle
diffusion kinetic model show a multi-linear relationship. This
result indicates that the adsorption process can be divided into
two stages, namely the diffusion of Cu2+ to the electrode surface
and the migration to the interior of the electrode material until sat-
urated adsorption. The straight line does not pass through the ori-
gin, suggesting that intraparticle diffusion is not the only step to
control the adsorption process [42]. Liquid film diffusion is also
inferred to be a significant factor affecting the adsorption process,
which is consistent with the kinetic fitting results.
Reusability is one of the important issues of the electrode.
According to the adsorption-desorption cycles, the reusability of
the FL-MoS2/NCS electrode is shown in Fig. 9(e). After five cycles,
the capacity retention still remained above 94.5%, indicating that
the electrode could well be well regenerated and reused.
3.4. Adsorption isotherms of Cu2+ on the electrode
In order to study the interaction between adsorbed ions and
electrode materials, many adsorption isotherm models were
437
proposed. Langmuir, Freundlich and Temkin isotherm models have
been widely applied to solid-liquid adsorption processes. There-
fore, the experimental data were fitted by using the above three
models. Among them, Langmuir isotherm is based on the following
assumptions: (1) monolayer adsorption; (2) homogeneous adsor-
bent surface; (3) Each active site on the surface of the adsorbent
can only adsorb one molecule while no interaction between these
adsorbed molecules. However, the Freundlich isotherm is based on
the assumption that adsorbates are adsorbed onto a heterogeneous
surface by multilayer adsorption. The Langmuir, Freundlich and
Temkin isotherm models are given as Eqs. (8), (9) and (10),
respectively:
K L Ce
qe ¼ qmax ð8Þ
1 þ K LCe
1
qe ¼ K F C e n ð9Þ
qe ¼ BlnðK T C e Þ ð10Þ
where qe (mg/g) and Ce (mg/L) are the adsorption capacity and con-
centration at adsorption equilibrium, respectively, qmax (mg/g) rep-
resents the maximum adsorption capacity; KL (L/mg) KF (mg/g) and
KT (L/g) are the Langmuir, Freundlich and Temkin adsorption con-
stants, respectively; n is the characteristic constant of adsorption
intensity, and B (J/mol) is the constant associated with the heat of
adsorption.
The fitting results of the adsorption isotherm models at 25 °C
are shown in Fig. 10. The adsorption capacity shows an upward
trend with the increase of Cu2+ concentration at 0.8 V, because
the migration of Cu2+ to the interior of the electrode material is
more favorable due to the stronger driving force at a higher con-
centration. Thus, the active sites of the electrode material can be
thoroughly utilized. For another thing, the correlation coefficient
of Freundlich isotherm (R2 = 0.9455) is higher than the other
438 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441

Fig. 9. Adsorption kinetics of Cu2+ on FL-MoS2/NCS electrode at 0.8 V and 25 °C (a), pseudo-first-order kinetic model (b), pseudo-second-order kinetic model (c), and intra-
particle diffusion kinetic model (d) for Cu2+ adsorption on FL-MoS2/NCS electrode, Recycling performance of FL-MoS2/NCS electrode (e).

adsorption isotherms, indicating that the Freundlich isotherm

model can better describe the electrosorption process. This result
indicates that the adsorption occurs at the heterogeneous interface
and is multilayer adsorption. What’s more, the value of adsorption
intensity n (1.22) of the Freundlich isotherm is greater than 1 ver-
ifies that the adsorption of Cu2+ on the FL-MoS2/NCS electrode is a
favorable process [12].

3.5. Adsorption mechanism

In order to further investigate the adsorption mechanism of FL-

MoS2/NCS on Cu2+, the electrode after adsorption was character-
ized by XPS. It can be seen from Fig. 11(a) that the FL-MoS2/NCS
electrode after the first adsorption contains C, N, Mo, S, Cu and F
elements, which proves that the FL-MoS2/NCS electrode does
adsorb Cu2+. Besides, the peak at 688.1 eV is derived from the F ele-
ment in the binder (PVDF) used in the preparation of the electrode.
Fig. 10. Isotherm models of Cu2+ adsorption on FL-MoS2/NCS electrode at 0.8 V and In the high-resolution spectrum of Cu 2p (Fig. 11(b)), the Cu 2p3/2
25 °C. peaks at 932.7 and 935.0 eV can be attributed to the Cu+ and Cu2+
 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Fig. 11. XPS spectra of FL-MoS2/NCS electrode after adsorption (a) survey spectrum, (b–d) high-resolution spectra of Cu 2p, S 2p and N 1s.
states, respectively, while the Cu 2p1/2 peaks at 952.8 and 954.9 eV
also correspond to Cu+ and Cu2+ states, respectively. In addition,
the peaks at 942.3, 944.4 and 962.6 eV also proved the presence
of Cu2+ state. The presence of Cu (I) in the electrode demonstrated
that low-concentration Cu2+ (soft acid) reacted with the S active
sites (soft base) in FL-MoS2/NCS (soft-soft interaction) to form
Cu2S, so that Cu2+ was immobilized on the electrode [43]. For
another thing, the presence of Cu2+ state in the electrode proved
that a part of Cu2+ in the solution is adsorbed on the electrode by
electrosorption (EDL). As shown in Fig. 11(c), the two peaks of
S2p3/2 and S2p1/2 after adsorption (162.5, 163.7 eV) shifted to a
higher binding energy than those before adsorption (162.3,
163.5 eV). This is due to the fact that S in FL-MoS2/NCS is affected
by a positive cation, demonstrating the soft-soft interaction
between Cu2+ and FL-MoS2/NCS [44]. In addition, as depicted in
Fig. 11(d), the peak of the pyrrolic N was transferred from
401.4 eV (before adsorption) to 402.3 eV (after adsorption), which
also confirmed the soft-soft interaction between Cu2+ (soft acid)
and pyrrolic N (soft base) [26]. The above results proved that the
adsorption of low-concentration Cu2+ on the electrode can be
attributed to the synergy between EDL and complexation of Cu2+
with the FL-MoS2/NCS, which is clearly shown in the schematic
diagram of adsorption mechanism (Fig. 12).
3.6. Effect of competitive ions on Cu2+ adsorption
The electroplating rinse wastewater contains various ions. In
order to investigate the effect of competitive ions on the adsorp-
tion of Cu2+ on the FL-MoS2/NCS electrode, competitive adsorption
experiments were carried out at 25 °C in binary and ternary
systems.
439
For the binary system (Cu2+ and Na+ or Cu2+ and Fe3+), as seen in
Fig. 13(a), the adsorption capacity of the FL-MoS2/NCS electrode for
Cu2+ still reaches 1193.4 mg/g under 0.8 V and 20 mg/L NaCl,
which remains basically unchanged compared with the adsorption
capacity without NaCl. The adsorption capacity for Cu2+ decreases
gradually with the increase of NaCl concentration. This is primarily
because sodium ions with a smaller hydration radius replace some
copper ions and occupy some spatial positions in the electrical
double layer under electrostatic force in the presence of a high con-
centration of NaCl, a drop in adsorption performance would be
resulted in. Meanwhile, a high adsorption capacity of 1095.6 mg/
g was maintained even though the NaCl concentration was as high
as 500 mg/L, indicating that the FL-MoS2/NCS electrode can still
selectively adsorb low-concentration Cu2+ in the presence of Na+.
This is predominantly because Na+ is hard acid while Cu2+ is soft
acid (Cu2+ softer than Na+) that can preferentially interact with
the abundant S and N active sites in the material. In addition, as
displayed in Fig. 13(b), the adsorption performance of the electrode
on Cu2+ decreases relatively more in the presence of FeCl3 than
NaCl, reducing from 1199.63 to 1048.2 mg/g at a concentration
of 80 mg/L FeCl3. This is mainly because of the strong electrostatic
force between Fe3+ with high valence and the electrode makes it
easier for Fe3+ to occupy some spatial positions in the EDL. Hence,
the contact of Cu2+ with active sites becomes relatively difficult.
However, a high adsorption capacity of 1048.2 mg/g was still
maintained when the FeCl3 concentration was 80 mg/L.
For the ternary system (Fig. 13(c)), under low-concentration
competitive ions (NaCl: 20 mg/L and FeCl3: 20 mg/L), the adsorp-
tion capacity of the electrode for Cu2+ was maintained
1189.2 mg/g with a capacity retention of 99.1% compared with
the adsorption capacity without competitive ions. However, the
adsorption capacity of the electrode for Cu2+ showed a downward
440 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Fig. 12. Schematic diagram of adsorption mechanism for Cu2+ on FL-MoS2/NCS electrode under 0.8 V.
Fig. 13. Effects of competitive ions on the adsorption of Cu2+.
trend with the increase of the competitive ion concentration. Gen-
erally, ions with a high valence state and a small hydrated radius
are more easily electroadsorbed [45]. Therefore, the priority of
ion electrosorption in the ternary system should be as follows:
Fe3+ > Cu2+ > Na+. However, in CuCl2 solution containing 500 mg/
L NaCl and 80 mg/L FeCl3, the adsorption capacity of Fe3+, Cu2+
and Na+ was 262.8, 1071.6 and 199.2 mg/g, respectively. Although
the adsorption capacity of Fe3+ is slightly higher than that of Na+,
the adsorption capacity of Cu2+ is much higher than that of Fe3+,
which is inconsistent with the above-mentioned electrosorption
order. This proves that the high adsorption capacity of Cu2+ is
mainly due to the stronger affinity (soft-soft interaction) between
Cu2+ (soft acid) and active sites (soft base: S and pyrrolic N). In con-
clusion, although the adsorption performance of the electrode on
Cu2+ is reduced under the interference of Fe3 and Na+, the electrode
can still efficiently and selectively adsorb Cu2+ with outstanding
adsorption capacity based on the soft-soft interaction.
In summary, based on XPS and competitive adsorption results,
it is proved that the coupling technology can be employed to effi-
ciently and selectively adsorb low-concentration Cu2+, which is
due to the soft-soft interaction between Cu2+ (soft acid) and the
active sites (soft base) of the composite. Therefore, given that most
VHMI are soft acids, it can be inferred that the coupling technology
can be used to adsorb most VHMI which is low-concentration.
4. Conclusions
In this paper, a coupling technology of capacitive deionization
and FL-MoS2/NCS with abundant active sites for efficiently and
selectively adsorbing low-concentration Cu2+ was deeply studied,
and the following conclusions were obtained.
(1) The newly obtained FL-MoS2/NCS composite possesses
abundant active sites and defects, enlarged interlayer spac-
ing and good hydrophilicity compare with modified materi-
als in other literatures [46–48].
(2) The FL-MoS2/NCS electrode exhibits outstanding electro-
chemical performance with a high specific capacitance
of 472.2 F/g and a low equivalent series resistance of
0.25 X.
(3) The adsorption capacity of the FL-MoS2/NCS electrode for
Cu2+ in the solution of 50 mg/L CuCl2, 500 mg/L NaCl and
80 mg/L FeCl3 was about 1071.6 mg/g at 0.8 V, which still
remains the same high level as it was in the solution of
50 mg/L CuCl2 solution (1199.63 mg/g), proving the good
selectivity of the composite for the adsorption of Cu2+.
(4) The XPS test further proved that the high efficiency
and selectivity of the FL-MoS2/NCS electrode for the
adsorption of Cu2+ was achieved by the synergistic effect of
EDL and complexation between Cu2+ and FL-MoS2/NCS
composite.
CRediT authorship contribution statement
Zhengle Hao: Data curation, Writing - original draft. Yanmeng
Cai: Conceptualization, Methodology, Software. Yue Wang: Visual-
ization, Investigation. Shichang Xu: Supervision. Jixiao Wang:
Writing - review & editing.
 Z. Hao et al. / Journal of Colloid and Interface Science 564 (2020) 428–441
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
This research is supported by the National Natural Science
Foundation of China (No. 21576190).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcis.2019.12.063.
References
[1] L. Jarup, Hazards of heavy metal contamination, Br. Med. Bull. 68 (2003) 167–
182.
[2] M.A. Martín-Lara, G. Blázquez, M.C. Trujillo, A. Pérez, M. Calero, New treatment
of real electroplating wastewater containing heavy metal ions by adsorption
onto olive stone, J. Cleaner Prod. 81 (2014) 120–129.
[3] C. Zhao, L. Zhang, R. Ge, A. Zhang, C. Zhang, X. Chen, Treatment of low-level Cu
(II) wastewater and regeneration through a novel capacitive deionization-
electrodeionization (CDI-EDI) technology, Chemosphere 217 (2019) 763–772.
[4] S. Porada, R. Zhao, A. van der Wal, V. Presser, P.M. Biesheuvel, Review on the
science and technology of water desalination by capacitive deionization, Prog.
Mater. Sci. 58 (2013) 1388–1442.
[5] H. Pan, J. Yang, S. Wang, Z. Xiong, W. Cai, J. Liu, Facile fabrication of porous
carbon nanofibers by electrospun PAN/dimethyl sulfone for capacitive
deionization, J. Mater. Chem. A 3 (2015) 13827–13834.
[6] L. Chang, Y. Hang Hu, 3D Channel-structured graphene as efficient electrodes
for capacitive deionization, J. Colloid Interface Sci. 538 (2019) 420–425.
[7] H. Li, L. Zou, L. Pan, Z. Sun, Using graphene nano-flakes as electrodes to remove
ferric ions by capacitive deionization, Sep. Purif. Technol. 75 (2010) 8–14.
[8] K. Ai, C. Ruan, M. Shen, L. Lu, MoS2 nanosheets with widened interlayer spacing
for high-efficiency removal of mercury in aquatic systems, Adv. Funct. Mater.
26 (2016) 5542–5549.
[9] J. Wang, W. Zhang, X. Yue, Q. Yang, F. Liu, Y. Wang, D. Zhang, Z. Li, J. Wang, One-
pot synthesis of multifunctional magnetic ferrite-MoS2-arbon dot nanohybrid
adsorbent for efficient Pb(II) removal, J. Mater. Chem. A 4 (2016) 3893–3900.
[10] F. Jia, X. Zhang, S. Song, AFM study on the adsorption of Hg2+ on natural
molybdenum disulfide in aqueous solutions, PCCP 19 (2017) 3837–3844.
[11] Q. Huang, J. Zhao, M. Liu, Y. Li, J. Ruan, Q. Li, J. Tian, X. Zhu, X. Zhang, Y. Wei,
Synthesis of polyacrylamide immobilized molybdenum disulfide
(MoS2@PDA@PAM) composites via mussel-inspired chemistry and surface-
initiated atom transfer radical polymerization for removal of copper (II) ions, J.
Taiwan Inst. Chem. Eng. 86 (2018) 174–184.
[12] C. Liu, F. Jia, Q. Wang, B. Yang, S. Song, Two-dimensional molybdenum
disulfide as adsorbent for high-efficient Pb(II) removal from water, Appl.
Mater. Today 9 (2017) 220–228.
[13] M. Zhang, F. Jia, M. Dai, S. Song, Combined electrosorption and chemisorption
of low concentration Pb(II) from aqueous solutions with molybdenum
disulfide as electrode, Appl. Surf. Sci. 455 (2018) 258–266.
[14] K.D. Rasamani, F. Alimohammadi, Y. Sun, Interlayer-expanded MoS 2, Mater.
Today 20 (2017) 83–91.
[15] Y. Li, Y. Liang, F.C. Robles Hernandez, H. Deog Yoo, Q. An, Y. Yao, Enhancing
sodium-ion battery performance with interlayer-expanded MoS2-PEO
nanocomposites, Nano Energy 15 (2015) 453–461.
[16] Z. Zhang, H. Zhao, Y. Teng, X. Chang, Q. Xia, Z. Li, J. Fang, Z. Du, K. Świerczek,
Carbon-sheathed MoS2 nanothorns epitaxially grown on CNTs:
electrochemical application for highly stable and ultrafast lithium storage,
Adv. Energy Mater. 8 (2018).
[17] Y. Song, Z. Jiang, B. Gao, H. Wang, M. Wang, Z. He, X. Cao, F. Pan, Embedding
hydrophobic MoS2 nanosheets within hydrophilic sodium alginate membrane
for enhanced ethanol dehydration, Chem. Eng. Sci. 185 (2018) 231–242.
[18] H. Zhou, R. Zhang, S. Song, C. Xiao, G. Gao, S. Ding, Dopamine-assisted
synthesis of MoS2 nanosheets on carbon nanotube for improved lithium and
sodium storage properties, ACS Appl. Energy Mater. 1 (2018) 5112–5118.
[19] C. Lee, S. Ozden, C.S. Tewari, O.K. Park, R. Vajtai, K. Chatterjee, P.M. Ajayan,
MoS2-carbon nanotube porous 3D network for enhanced oxygen reduction
reaction, ChemSusChem 11 (2018) 2960–2966.
[20] C. Wang, W. Wan, Y. Huang, J. Chen, H.H. Zhou, X.X. Zhang, Hierarchical MoS2
nanosheet/active carbon fiber cloth as a binder-free and free-standing anode
for lithium-ion batteries, Nanoscale 6 (2014) 5351–5358.
[21] M. Choi, J. Hwang, H. Setiadi, W. Chang, J. Kim, One-pot synthesis of
molybdenum disulfide–reduced graphene oxide (MoS2-RGO) composites and
their high electrochemical performance as an anode in lithium ion batteries, J.
Supercrit. Fluids 127 (2017) 81–89.
441
[22] Y. Liu, K. Ai, L. Lu, Polydopamine and its derivative materials: synthesis and
promising applications in energy, environmental, and biomedical fields, Chem.
Rev. 114 (2014) 5057–5115.
[23] K. Ai, Y. Liu, C. Ruan, L. Lu, G.M. Lu, Sp2 C-dominant N-doped carbon sub-
micrometer spheres with a tunable size: a versatile platform for highly
efficient oxygen-reduction catalysts, Adv. Mater. 25 (2013) 998–1003.
[24] Y. Li, Y. Liu, J. Shen, J. Qi, J. Li, X. Sun, J. Shen, W. Han, L. Wang, Design of
nitrogen-doped cluster-like porous carbons with hierarchical hollow
nanoarchitecture and their enhanced performance in capacitive deionization,
Desalination 430 (2018) 45–55.
[25] C. Yuan, X. Liu, M. Jia, Z. Luo, J. Yao, Facile preparation of N- and O-doped
hollow carbon spheres derived from poly(o-phenylenediamine) for
supercapacitors, J. Mater. Chem. A 3 (2015) 3409–3415.
[26] Q. Ji, C. Hu, H. Liu, J. Qu, Development of nitrogen-doped carbon for selective
metal ion capture, Chem. Eng. J. 350 (2018) 608–615.
[27] Y. Wang, X. Han, R. Wang, S. Xu, J. Wang, Preparation optimization on the
coating-type polypyrrole/carbon nanotube composite electrode for capacitive
deionization, Electrochim. Acta 182 (2015) 81–88.
[28] B. Chen, E. Liu, F. He, C. Shi, C. He, J. Li, N. Zhao, 2D sandwich-like carbon-
coated ultrathin TiO2@defect-rich MoS2 hybrid nanosheets: synergistic-effect-
promoted electrochemical performance for lithium ion batteries, Nano Energy
26 (2016) 541–549.
[29] Z. Lei, L. Xu, Y. Jiao, A. Du, Y. Zhang, H. Zhang, Strong coupling of MoS2
nanosheets and nitrogen-doped graphene for high-performance
pseudocapacitance lithium storage, Small 14 (2018) e1704410.
[30] Y. Liu, L. Jiao, Q. Wu, J. Du, Y. Zhao, Y. Si, Y. Wang, H. Yuan, Sandwich-
structured graphene-like MoS2/C microspheres for rechargeable Mg batteries,
J. Mater. Chem. A 1 (2013).
[31] B. Chen, H. Lu, N. Zhao, C. Shi, E. Liu, C. He, L. Ma, Facile synthesis and
electrochemical properties of continuous porous spheres assembled from
defect-rich, interlayer-expanded, and few-layered MoS2/C nanosheets for
reversible lithium storage, J. Power Sources 387 (2018) 16–23.
[32] X. Hu, Y. Li, G. Zeng, J. Jia, H. Zhan, Z. Wen, Three-dimensional network
architecture with hybrid nanocarbon composites supporting few-layer MoS2
for lithium and sodium storage, ACS Nano 12 (2018) 1592–1602.
[33] H. Liu, L. Xu, W. Liu, B. Zhou, Y. Zhu, L. Zhu, X. Jiang, Production of mono- to
few-layer MoS2 nanosheets in isopropanol by a salt-assisted direct liquid-
phase exfoliation method, J. Colloid Interface Sci. 515 (2018) 27–31.
[34] H. Li, Q. Zhang, C.C.R. Yap, B.K. Tay, T.H.T. Edwin, A. Olivier, D. Baillargeat, From
bulk to monolayer MoS2: evolution of Raman scattering, Adv. Funct. Mater. 22
(2012) 1385–1390.
[35] B. Chakraborty, H.S.S.R. Matte, A.K. Sood, C.N.R. Rao, Layer-dependent resonant
Raman scattering of a few layer MoS2, J. Raman Spectrosc. 44 (2013) 92–96.
[36] L. Zheng, T. Xing, Y. Ouyang, Y. Wang, X. Wang, Core-shell structured
MoS2@Mesoporous hollow carbon spheres nanocomposite for
supercapacitors applications with enhanced capacitance and energy density,
Electrochim. Acta 298 (2019) 630–639.
[37] S.L. Candelaria, B.B. Garcia, D. Liu, G. Cao, Nitrogen modification of highly
porous carbon for improved supercapacitor performance, J. Mater. Chem. 22
(2012).
[38] G. Rasines, P. Lavela, C. Macías, M.C. Zafra, J.L. Tirado, J.B. Parra, C.O. Ania, N-
doped monolithic carbon aerogel electrodes with optimized features for the
electrosorption of ions, Carbon 83 (2015) 262–274.
[39] J. Zhao, Y. Jiang, H. Fan, M. Liu, O. Zhuo, X. Wang, Q. Wu, L. Yang, Y. Ma, Z. Hu,
Porous 3D few-layer graphene-like carbon for ultrahigh-power
supercapacitors with well-defined structure-performance relationship, Adv.
Mater. 29 (2017).
[40] Z. Sun, Y. Yao, J. Wang, X. Song, P. Zhang, L. Zhao, L. Gao, High rate lithium-ion
batteries from hybrid hollow spheres with a few-layered MoS2-entrapped
carbon sheath synthesized by a space-confined reaction, J. Mater. Chem. A 4
(2016) 10425–10434.
[41] I. Liatsou, I. Pashalidis, C. Dosche, Cu(II) adsorption on 2-thiouracil-modified
Luffa cylindrica biochar fibres from artificial and real samples, and
competition reactions with U(VI), J. Hazard. Mater. 383 (2020) 120950.
[42] S. Chen, Q. Yue, B. Gao, Q. Li, X. Xu, Removal of Cr(VI) from aqueous solution
using modified corn stalks: Characteristic, equilibrium, kinetic and
thermodynamic study, Chem. Eng. J. 168 (2011) 909–917.
[43] X. Wang, J. Wang, X. Zhang, Q. Tian, M. Liu, N. Cai, Y. Xue, W. Chen, W. Li, F. Yu,
Nitrogen-doped Cu2S/MoS2 heterojunction nanorod arrays on copper foam for
efficient hydrogen evolution reaction, ChemCatChem 11 (2019) 1354–1361.
[44] L. Wu, H. Wang, H. Lan, H. Liu, J. Qu, Adsorption of Cu(II)-EDTA chelates on tri-
ammonium-functionalized mesoporous silica from aqueous solution, Sep.
Purif. Technol. 117 (2013) 118–123.
[45] L. Liu, X. Guo, R. Tallon, X. Huang, J. Chen, Highly porous N-doped graphene
nanosheets for rapid removal of heavy metals from water by capacitive
deionization, Chem. Commun. (Camb.) 53 (2017) 881–884.
[46] Y. Shin, G.E. Fryxell, W. Um, K. Parker, S.V. Mattigod, R. Skaggs, Sulfur-
functionalized mesoporous carbon, Adv. Funct. Mater. 17 (2007) 2897–2901.
[47] K.A. Krishnan, T.S. Anirudhan, Removal of mercury(II) from aqueous solutions
and chlor-alkali industry effluent by steam activated and sulphurised
activated carbons prepared from bagasse pith: kinetics and equilibrium
studies, J. Hazard. Mater. 92 (2002) 161–183.
[48] F. Jia, K. Sun, B. Yang, X. Zhang, Q. Wang, S. Song, Defect-rich molybdenum
disulfide as electrode for enhanced capacitive deionization from water,
Desalination 446 (2018) 21–30.