Journal of Hazardous Materials 394 (2020) 122534

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Journal of Hazardous Materials

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A WO3/PPy/ACF modified electrode in electrochemical system for T

simultaneous removal of heavy metal ion Cu2+ and organic acid
Jiaqi Suna, Lifen Liua,b,*, Fenglin Yanga
a
Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science & Technology, Dalian University of Technology, Dalian,
116024, China
b
School of Ocean Science and Technology, Dalian University of Technology, Panjin, China

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Editor: Xiaohong Guan Heavy metal ions and organic acids are common pollutants in electroplating wastewater. Effective and economic
Keywords: treatment of such wastewater needs novel technologies. In this study, WO3/PPy-1/ACF electrode was prepared
WO3/PPy/ACF using a hydrothermal modification method and it has large specific area (788.27 m2 g−1), high areal capacitance
Electrochemical system (2.58 F cm−2 under 5 mA cm−2 charge and discharge) and excellent conductivity. The modified electrode was
Heavy metal used in an electrochemical system with activated carbon fiber felt (ACF) as counter electrode. The system si-
Copper multaneously and successfully removed 97.8 % Cu2+ and 80.1 % citric acid (CA) from a simulated electroplating
Citric acid wastewater (typically 100 mg L−1 Cu2+ and 800 mg L−1 CA) in five- hour optimized operation. The influence of
operating parameters (circulating inflow rate, applied voltage and influent pH) on the treatment performance
was compared. There is interplay between Cu2+ reductive deposition and CA oxidation. The synergetic elec-
trochemical treatment mechanism involves formation of hydrogen peroxide, free radicals, and catalytic effect of
Cu species was proposed. This electrochemical system which is low-cost, easy to operate and highly efficient,
may be applicable in treating acid-wash or electroplating wastewater, containing heavy-metal ions and organic
acids.

⁎
Corresponding author at: Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science & Technology, Dalian
University of Technology, Dalian, 116024, China.
E-mail address: lifenliu@dlut.edu.cn (L. Liu).

https://doi.org/10.1016/j.jhazmat.2020.122534
Received 12 November 2019; Received in revised form 8 March 2020; Accepted 11 March 2020
Available online 12 March 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
J. Sun, et al.
1. Introduction
Because of the toxicity and carcinogenic nature of heavy metal ions,
heavy metal pollution controls are of priority concerns. Heavy metal
containing wastewaters from industrial processes such as electro-
plating, mining/smelting and circuit board plating, even at low con-
centrations, may cause concerns for ecosystem and human health (Cai
et al., 2019; Bautista-Patacsil et al., 2019). It is common that electro-
plating heavy metal wastewater also contains organic pollutants (Qin
et al., 2018) such as citric acid (CA).
To remove heavy-metal ions, conventional technologies such as
adsorption, physiochemical, electrochemical and deionization pro-
cesses have been used (Azimi et al., 2017). However, the electro-
chemical treatments (electrodeposition, electrocoagulation, electro-
flotation and electrodialysis) involving the use of intense electric field
up to dozens of volts (de Mello Ferreira et al., 2013; Min et al., 2019;
Duan et al., 2017), lead to higher energy consumption and operating
cost.
To remove the coexisted organic compounds in electroplating
wastewater, advanced oxidation process is used to meet the discharge
standard of chemical oxygen demand (COD). Simply adopting con-
ventional treatment processes will not work for simultaneous removal
of heavy metal and organic pollutants. New treatment processes in-
volving multiple mechanisms have been attempted. For example,
electrocoagulation and electrowinning was combined in a three staged
process to recover copper and remove COD with the anodic generated
Al3+ ions (Stergiopoulos et al., 2019). Simultaneous removal of metal
ions (Cr3+) and neutral organics (acetyl acetone) could be achieved via
complexation and electrodialysis (Jiang et al., 2018). And combined
electro-Fenton treatment with chemical precipitation also removed
COD and Zn2+ (Ghosh et al., 2011). Systems of oxidation and deioni-
zation, simple but more effective in synchronically removing heavy
metal ions and organic matters are desired.
Newly arisen deionization systems, capacitive deionization (CDI)
and electro-deionization (EDI), using low-cost electrodes, have been
reported for removing heavy metal ions through electrostatic or elec-
trochemical interactions (Cao et al., 2019; Zhang et al., 2019a; Zhao
et al., 2019; Huang et al., 2014). Weak electric field (usually below
1.5 V) enabled the removal of charged ionic species (Tang et al., 2019;
Uzun and Debik, 2019; Lado et al., 2017). In CDI or EDI, apart from
electro-adsorption, there are irreversible faradaic side-reactions
(Shapira et al., 2016; Zhang et al., 2018). Electric field and functional
electrodes could integrate electro-adsorption and electrochemistry in
such systems to promote heavy metal and/or other pollutants removal.
Metal ions such as Cu2+, Zn2+, Ni2+, Fe3+ etc. are precursors for
(electrochemical) preparation of electro-active catalytic species (Song
et al., 2019; Gao et al., 2015; Farahbakhsh and Sanjabi, 2019; Ling
et al., 2018). The metal or metal oxides (such as Cu and Cu2O) in-situ
generated electrochemically may have excellent electrochemical cata-
lysis activity that could be used in oxidation of organic pollutants.
Therefore, electro-adsorption and electrochemically active species can
be combined in one system to achieve high efficient treatment of
wastewater containing both heavy metal ions and organic pollutants.
But either in CDI or EDI, there are no such reports.
To build such an enhanced electrochemical system, functional
electrodes are indispensable. Carbon-based electrode (activated carbon,
carbon cloth and carbon fiber etc.) are competitive in mechanical sta-
bility, conductivity, specific surface area and economic benefits.
Activated carbon fiber (ACF, in the form of felt) electrodes are common
for capacitive applications (Baur et al., 2015). Modifying carbon-based
material with electro-active metal oxides and conductive polymers can
form functional electrode and enhance system performance by synergy
mechanisms (Xue et al., 2018; Srimuk et al., 2017). Tungsten trioxide
(WO3) is an attractive electro-active material with multiple oxidation
states, which has been widely used in electrode modification for sen-
sors, super capacitors and other electrochemical devices (Lee et al.,
2
Journal of Hazardous Materials 394 (2020) 122534
2015; Shinde et al., 2017). Flaky WO3 decorated carbon cloth electrode
has promoted capacitance and ion electro-adsorption (Gui and
Blackwood, 2018). Conductive polymers like polyaniline (PANI) and
polypyrrole (PPy) can promote the conductivity, capacitance and
electrochemical properties of electrodes (Liu et al., 2015; Ji‡ et al.,
2019; Wang et al., 2015; Zou et al., 2010). PPy has been applied in
removing metal ions such as Pb2+, Cr2+ and Cu2+, etc. (Zhang et al.,
2019b; Fang et al., 2018).
In this study, co-existed pollutants (Cu2+ and CA) in simulate in-
dustrial wastewater were simultaneously treated using ACF (in the form
of felt) based and modified electrodes in an electrochemical system. The
ACF electrode was modified with electro-active materials of WO3 and
conductive polymer of PPy by one-step hydrothermal method. Series
comparison in structure, morphology and electrochemical properties of
WO3/PPy-1/ACF (volumetric 0.1 % pyrrole versus total) were con-
ducted. It was chosen as the cathode with the counter electrode of raw
ACF, because of the excellent capacitance, specific area and electro-
chemical properties. The system operating conditions including inflow
rate, supplied voltage and influent pH were optimized and the perfor-
mance in simultaneous removing Cu2+ and CA (represented by COD)
were measured. To better understanding this enhanced electrochemical
system in integrated functions/interactions between Cu2+ and CA re-
moval, the mechanism was studied and proposed.
2. Experiment
2.1. Preparation of electrode
All the chemicals were bought and used without further purifica-
tion. Pure water was used during the all experiment processes.
Commercial activated carbon fiber felt (SA1000-1500, Nantong
Shuangan Activated Carbon Filter Material Co., Ltd.) served as the
substrate material of electrode after thoroughly washed by acetone,
pure water and ethanol respectively and was cut to 4.5 × 7.0 cm2
(0.40 ± 0.01 g) before use.
Modified one-step hydrothermal method (Zheng et al., 2019) was
adopted to coat WO3 and PPy on ACF (in the form of felt). Typically,
60 mL 0.1 M sodium tungstate dihydrate (Na2WO4%2H2O) solution was
stirred for 30 min and the pH was slowly adjusted to 1.5 using 2 M nitric
acid (HNO3) solution. Then 0.5 M sodium nitrate (NaNO3) and certain
amount of pyrrole was added and stirred for another 20 min before
transferred into a 100 mL polytetrafluoroethylene hydrothermal reactor
with a slice of pretreated ACF. After that, the reactor was sealed and
heated to 180 °C for 14 h with a rate of 5 °C min−1. After naturally
cooling down to room temperature, the modified ACF electrode was
taken out and washed by pure water for several times until the extra
WO3/PPy on the surface was removed. The electrodes prepared with
0%, 0.05 %, 0.1 % and 0.2 % (volume ratio versus total) pyrrole ad-
dition were denoted as WO3/ACF, WO3/PPy-0.5/ACF, WO3/PPy-1/ACF
and WO3/PPy-2/ACF respectively and kept in wet before use. For
contrast, PPy-1/ACF without Na2WO4%2H2O addition and ACF-h
without Na2WO4%2H2O and pyrrole addition were also prepared by the
same hydrothermal process.
2.2. Electrochemical test
The electrochemical tests were performed in a three-electrode
system where saturated calomel electrode and platinum sheet (1 × 1
cm2) were used as the reference and counter electrodes respectively.
The as-prepared modified electrodes directly served as working elec-
trode with an effective area of 1 × 1 cm2. Cyclic voltammetry (CV),
galvanostatic charge-discharge (GCD) and electrochemical impedance
spectroscopy (EIS) were tested by an electrochemical workstation
(CHI660E) in different electrolytes (100 mL) to evaluate the capacitive
and electrochemical properties of electrodes. The results of EIS were
fitted by the software of Zview.
J. Sun, et al.
Fig. 1. Structure diagram of the electrochemical system where 1-5 represent
separator, sealer, spacer, electrode and current collector respectively.
2.3. Characterization
The morphology of electrode was characterized by scanning elec-
tron microscopy (SEM, NOVA NANO SEM 450, USA) equipped with
energy dispersive X-ray spectrometer (EDX, USA). The specific area and
pore structure were tested by nitrogen adsorption and desorption
method (AS-1-MP-11, USA). The structure information was supplied by
Fourier infrared spectrum (FT-IR, EQUINOX55, Germany) and X-ray
diffraction (XRD, D/MAX-2400, Japan) with Cu Ka (λ ≈ 0.1541 nm) at
a scan rate of 10° min−1. X-ray photoelectron spectroscopy (XPS, K-
Alpha+, Germany) was performed to analyze the valence states of
elements.
2.4. Electrochemical system
The schematic diagram of this electrochemical system is exhibited
in Fig. 1. The structure is similar with a traditional CDI module but
without ion exchange membranes. Two electrodes were oppositely
placed and separated by a 0.8 cm thick separator. The internal volume
of this module was 24.5 mL. Graphite plates served as the current col-
lector and DC power was used to supply constant electric field.
The influent concentrations and volumes are respectively
100 mg L−1 Cu2+ and/or 800 mg L−1 CA and 100 mL. The intrinsic pH
of 100 mg L-1 Cu2+ +800 mg L-1 CA is 3 and the pH of the influent was
adjusted by 0.5 M sodium hydroxide (NaOH) solution or concentrated
sulfuric acid (H2SO4). Every time before experiment, both electrodes
were immersed in the same solution for half an hour. The effluent was
circulated and water samples were taken from the influent tank at a
certain time interval for analysis. The concentration of Cu2+ and H2O2
was measured by spectrophotometric method (Qi et al., 2011; Wang
et al., 2013) and CA was characterized by COD according to Chinese
N.E.P.A. standard (Chinese N.E.P.A., 2002). The electrodes, inflow rate,
supplied voltage and pH of the influent were compared and optimized
for this system.
3. Results and discussion
3.1. Morphological and BET analysis
SEM images of ACF, WO3/ACF and WO3/PPy-x/ACF (x = 0.5, 1, 2)
were displayed in Fig. 2(a–f). By using one-step hydrothermal method,
hexagonal WO3 could in-situ grow on activated carbon fibers in the
form of vertical arrangement. With increase of PPy ratio, the loading of
WO3 or WO3/PPy on ACF was increased until the pyrrole volume ratio
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Journal of Hazardous Materials 394 (2020) 122534
reached 0.1 % (WO3/PPy-1/ACF), then the modified component evenly
distributed and aligned along activated carbon fiber. From the EDX
mapping in Fig. 2 (h), elements of W, O, C and N distributed evenly on
WO3/PPy-1/ACF electrode surface (before use). However, when the
volume ratio of pyrrole increased to 0.2 % (WO3/PPy-2/ACF), granular
material was observed in Fig. 2 (f). The morphology of WO3/PPy-2/ACF
(Fig. S1) does not vary much comparing with that of WO3/PPy-1 in
Fig. 2 (g). Therefore, the granular shaped active material was the ag-
gregates from excessive WO3/PPy which did not spread evenly and
thinly on the substrate surface. WO3/PPy particles in WO3/PPy-2/ACF
were larger in size than that in WO3/PPy-1/ACF. The aggregated
modification materials were easy to fall off during the wash step. The
uneven loading could affect the electrochemical performance of mod-
ified electrode.
According to BET analyzation (Table 1), the substrate of ACF has
large intrinsic specific area of 1590.72 m2 g−1 with an average pore
diameter of 3.34 nm and a total pore volume of 0.54 m3 g−1. However,
after hydrothermal treatment in acidic environment, the microporous
structure in raw ACF was partially destroyed which resulted in an in-
crease of pore size and a decrease of pore volume. The SBET of ACF-h
sharply shrunk to 446.14 m2 g−1. Notably, after modified with WO3
and PPy, the specific area of electrode significantly enhanced. The fa-
vorable SBET of 788.27 m2 g−1 and the pore volumes of 0.33 m3 g−1
guaranteed the higher adsorption property of WO3/PPy-1/ACF than
ACF-h.
3.2. Structural characterization
XRD was performed to define the crystal structure of the modified
electrode (Fig. 3 (a)). The main peaks of WO3/ACF and WO3/PPy-1/
ACF at 2 θ = 14.0°, 22.8°, 24.4°, 26.8°, 28.2°, 33.6°, 36.6° and 37.6° are
in agreement with (1 0 0), (0 0 1), (1 1 0), (1 0 1), (2 0 0), (1 1 1), (2 0
1) and (2 1 0) crystal planes of WO3 (PDF #75-2187). Consequently, the
load of hexagonal WO3 on ACF was confirmed. Furthermore, the
stronger peak intensity of WO3/PPy-1/ACF than WO3/ACF indicates
the strengthened WO3 loading on carbon fibers with the existence of
PPy. However, the reported wide peak belonging to amorphous PPy at 2
θ = 21–25° (Sun et al., 2017) is difficult to be recognized due to its low
content in the composite electrode.
FT-IR spectra of ACF, ACF-h, WO3/ACF and WO3/PPy-1/ACF were
further characterized to confirm the compositing structure and the re-
sults were exhibited in Fig. 3 (b) and Table 2. ACF has stretching vi-
bration of OeH, and C]O and outer-bending vibration of CeH in
phenol, lactone, carboxyl, and ketone (Shin et al., 1997). The broad
peaks between 1000 cm−1 and 1200 cm−1 belong to the single-bonded
oxygen groups in phenols, lactones and ethers (Chen and Wu, 2004).
After hydrothermally treated in acid environment, the peaks at
3200–3600 cm−1 and 1540 cm−1 significantly increased, which in-
dicates the increase of hydroxyl groups, carboxyl-carbonate structure
and nitrate groups due to the introduction of carboxylic groups (Chen
and Wu, 2004). These functional groups may have positive effect to
copper ions adsorption (Huang and Su, 2010). After loaded with WO3,
characteristic peaks in the form of WeO and WeOeW appeared in
850 cm−1 and 721 cm−1 in WO3/ACF electrode. In the spectrum of
WO3/PPy-1/ACF, new peaks at 1545 cm−1 and 1102 cm−1 are attrib-
uted to the pyrrole ring stretching modes and ]CeH plan deformation
vibration respectively (Sun et al., 2017; Shin et al., 1997), and the weak
transmittances demonstrate the low content of pyrrole. The red-shift of
peaks such as OeH, CeO and WeOeW and the diminishment of car-
boxylic groups suggest the compositing structure of WO3 and PPy on
ACF. Moreover, comparing with WO3/ACF, the specific peaks asso-
ciated with WO3 in WO3/PPy-1/ACF was significantly strengthened
which confirms the positive effect of PPy to WO3 loading.
XPS was performed to investigate the elemental composition and
valence states of WO3/PPy-1/ACF. As shown by the survey spectrum of
WO3/PPy-1/ACF (before use) in Fig. 3 (c), elements of W, O, C, N and
J. Sun, et al. Journal of Hazardous Materials 394 (2020) 122534

Fig. 2. SEM images of (a) ACF, (b) WO3/ACF, (c) WO3/PPy-0.5/ACF, (d, f) WO3/PPy-1/ACF (before use), (e) WO3/PPy-2/ACF, (g) WO3/PPy-1/ACF (after use) and
(h) EDX mapping results of WO3/PPy-1/ACF before and after use.

Table 1 Na absorbed on the surface of electrode were presented. The core level
BET surface area, pore diameter and volume of ACF, ACF-h and WO3/PPy-1/ spectra of W 4f and N 1s were given in Fig. 3 (d) and (e). The dis-
ACF. assembled peaks of W 4f7/2 and W 4f5/2 at 35.9 eV and 38.1 eV re-
Electrode BET surface area Average pore Total pore volume spectively, with the splitting of 2.1 eV represent the W6+ oxidation
(m2 g−1) diameter (nm) (m3 g−1) state in WO3 (Shinde et al., 2017). The neutral N and N+ state in the
form of N-C and N-H structures in pyrrole were confirmed by the de-
ACF 1590.72 3.34 0.54
convoluted peaks of N 1s at 399.8 eV and 400.9 eV respectively (Sun
ACF-h 446.14 4.26 0.26
WO3/PPy-1/ 788.27 3.34 0.33 et al., 2017).
ACF

Fig. 3. (a) XRD patterns of WO3/ACF and WO3/PPy-1/ACF. (b) FT-IR spectra of ACF, ACF-h, WO3/ACF and WO3/PPy-1/ACF. (c) XPS survey spectra of WO3/PPy-1/
ACF before and after use. (d) W 4f and (e) N 1s core level spectra of WO3/PPy-1/ACF before use and (f) Cu 2p after use.

4
J. Sun, et al. Journal of Hazardous Materials 394 (2020) 122534

Table 2
The groups revealed from FT-IR spectra of ACF, ACF-h, WO3/ACF and WO3/PPy-1/ACF.
Group Wavenumber (cm−1) Refs.

ACF ACF-h WO3/ACF WO3/PPy-1/ACF

OeH 3255 3253 3253 3420 Fang et al. (2018)

CeH 2923 2923 2920 2920 Shin et al. (1997)
C]O 2361, 1714, 1540 2361, 1714, 1540 2361, 1713, 1547 2365, 1720, 1602 Fang et al. (2018), Chen and Wu (2004)
CeC, C]C, CeN 1456 1456 1461 1461, 1411 Shin et al. (1997), Gaikwad et al. (2016)
Pyrrole ring – – – 1545 Shin et al. (1997)
CeO 1019 1033 1179 1255 Chen and Wu (2004)
]CeH – – – 1102 Sun et al. (2017)
WeO – – 850 825 Sun et al. (2017), Shin et al. (1997)
WeOeW – – 714 726 Shin et al. (1997)
CeH 654 673 673 668 Fang et al. (2018)

Fig. 4. The electrochemical performance of ACF, ACF-h, WO3/ACF and WO3/PPy-x/ACF(x = 0.5, 1 and 2) in 1 M NaCl solution. (a) CV curves of the electrodes under
5 mV s−1 scan rate. (b) CV curves of WO3/PPy-1/ACF under different scan rate and (c) the related areal capacitances. (d) GCD curves of the electrodes under
5 mA cm−2 and (e) the related areal capacitances. (f) EIS fitting curves of the electrodes under 5 mV cm−2 and the equivalent circuit.

3.3. Electrochemical characterization of electrode with certain pseudo-capacitance characteristics.

CV curves of ACF, ACF-h, WO3/ACF and WO3/PPy-x/ACF (x = 0.5,
1, 2) in 1 M NaCl solution at a scan rate of 5 mV s−1 from −0.5 to 0.6 V
were obtained. As shown in Fig. 4(a), the closed curve area increased
with the loading of PPy. WO3/PPy-1/ACF electrode has higher capa-
citance than WO3/PPy-0.5/ACF due to the positive effect of PPy. The
lower capacitance of WO3/PPy-2/ACF than WO3/PPy-1/ACF should be
attributed to the uneven loading of active materials according to the
SEM in Section 3.1. The raw ACF without modification has high elec-
trochemical activity and its areal capacitance was calculated to be
1.70 F cm−2. However, there was a sharp decline of areal capacitance to
0.37 F cm−2 for ACF after hydrothermal treatment (ACF-h). Although
the treatment in acidic condition inhibited the capacitive performance
of ACF, the rough surface and functional groups supplied more sites for
catalysts loading. After modification, the WO3/PPy-1/ACF electrode
displayed higher areal capacitance (1.80 F cm−2) than raw ACF. In
addition, the rectangular-shaped CV curves of ACF and WO3/PPy-1/
ACF, with symmetric wide peaks, indicate their excellent capacitance
The CV curves of WO3/PPy-1/ACF under different scan rates and
the related capacitance were displayed in Fig. 4(b) and (c). The de-
crease of capacitance with the increasing scan rate confirms the mi-
crostructure of the electrode, which demands more ions diffusing time
to the pores at higher scan rate in the electrolyte (Yang and Zou, 2014).
The diffusion limitation of WO3/PPy-1/ACF electrode, which was lar-
gely decided by the property of substrate (commercial ACF) as well as
active material, indicates insufficient mesoporosity for high current
loads or quick scan rates (Kierzek et al., 2004). However, according to
EIS results (Table 3), the modified highly microporous electrode has the
lowest ions diffusion resistance and total impedance among the series of
modified electrodes, which indicates its better diffusion property in
electrolyte than ACF and ACF-h.
The capacitance properties of the as-prepared electrodes were
further investigated by the galvanostatic charge-discharge
method under 5 mA cm−2 applied current (Fig. 4 (d)). The discharge
time and related capacitance follow the sequence of WO3/PPy-1/
ACF > ACF > WO3/PPy-2/ACF > WO3/PPy-0.5/ACF > WO3/

5
J. Sun, et al.
Table 3
Equivalent circuit fitting results of EIS.
Electrode Rs (Ω%cm2) Rct (Ω%cm2) Wd (Ω%cm2)
ACF 6.4 1.1 7.1
ACF-h 6.5 40.5 136.8
WO3/ACF 6.1 14.8 33.9
WO3/PPy-0.5/ACF 9.3 9.9 18.7
WO3/PPy-1/ACF 4.7 2.9 5.7
WO3/PPy-2/ACF 4.9 2.1 7.7
ACF > ACF-h. The symmetric GCD curves of the top three electrodes
with sequencing 2.58, 2.34 and 2.13 F cm−2 areal capacitance indicate
their excellent capacitive performance based on electric double layer
(Fig. 4 (e)). Moreover, the IR drop of WO3/PPy-1/ACF presents to be
the lowest which is corresponding to the following EIS results.
The conductivity of the as-prepared electrodes was analyzed by EIS
method and the equivalent circuit fitting results are exhibited in Fig. 4
(f). The plot of semicircle in the high frequency region in the EIS curve
relates to the impedance of both electrolyte and active materials where
ohmic resistance (Rs) and charge transfer resistance (Rct) could be ob-
tained. The inclined line in the low frequency region is corresponding to
the Warburg diffusion process (Shao et al., 2013). The slope of the in-
clined line is associated with the pure capacitive behavior and an ideal
capacitor is expected to display a vertical line to the real axis. In this
case, according to Table 3, raw ACF has great conductivity with small
charge transfer resistance of 1.1 Ω cm2. However, after hydrothermal
treatment in acid environment, both Rct and Warburg impedance (Wd)
of ACF-h increased tens of times to 40.5 Ω cm2 and 136.8 Ω cm2 re-
spectively. WO3 and PPy loading effectively accelerated the charge
transfer and diffusion rate. Specifically, WO3/PPy-1/ACF has the lowest
ohmic resistance of 4.7 Ω%cm2 which is similar with that of WO3/PPy-
2/ACF, among the series of modified electrodes. In addition, the in-
clined line of WO3/PPy-1/ACF in low frequency region consisting an
angle between 45° and 90° with the real axis implies the existence of
pseudo-capacitance process which is probably contributed by the redox
reactions of WO3 and PPy (Fatnassi and Es-Souni, 2015). Although the
Rct of WO3/PPy-1/ACF (2.9 Ω%cm2) is a little bit higher than ACF and
WO3/PPy-2/ACF, the total resistance of WO3/PPy-1/ACF (13.3 Ω%cm2)
is the smallest which indicates its superior conductivity.
To confirm the function of WO3 in WO3/PPy-1/ACF, electro-
chemical properties of PPy-1/ACF were compared with WO3/PPy-1/
ACF in Fig. S2. Significant enhancements in conductivity and capaci-
tance were observed. The WO3 and PPy composite in favorable ratio
(WO3/PPy-1) improved the electrochemical properties of electrode.
3.4. Electro-enhanced removal of Cu2+ and citric acid
Based on the above characterizations, WO3/PPy-1/ACF and ACF
with excellent electrochemical and capacitance properties are expected
to be the promising electrodes for deionization application. The per-
formance of the electrochemical system with different electrodes was
compared in Fig. 5 (a) and (b) under the circulating flow rate of 20 mL
min−1 and the voltage of 1.0 V.
The removal of positive charged copper ions is closely related to the
property of cathode. After modification, WO3/PPy-1/ACF had higher
electrochemical activity than ACF. Consequently, the system with the
cathode of WO3/PPy-1/ACF had better Cu2+ removal performance
than with ACF cathode. As the highest Cu2+ removal efficiency oc-
curred in WO3/PPy-1/ACF // ACF system, raw ACF is a suitable counter
electrode. Notably, in the WO3/PPy-1/ACF // ACF system, 68.8 % of
CA was simultaneously removed in 5 h besides the removal of 97.8 %
Cu2+, which is higher than the removal in WO3/PPy-1/ACF // WO3/
PPy-1/ACF (52.3 % of CA and 96.3 % of Cu2+) and ACF // ACF (54.8 %
of CA and 95.6 % of Cu2+) systems. This tendency could be explained
by the increased energy density input in the asymmetric systems than in
6
Journal of Hazardous Materials 394 (2020) 122534
the symmetric ones, since the different electrodes can make full use of
their different potential windows (Zhao and Zheng, 2015). Therefore,
the modified electrode of WO3/PPy-1/ACF is a promising cathodic
material which has remarkable performance in heavy metal/organic
acid (Cu2+/CA) complex wastewater treatment, especially in WO3/
PPy-1/ACF // ACF system.
Operating conditions including circulating flow rate, applied vol-
tage and pH in this WO3/PPy-1/ACF // ACF system were further in-
vestigated. As shown in Fig. 5 (c), under the same applied voltage of
1.0 V, the flow rate has little effect on heavy metal removal since more
than 92 % and 97 % of Cu2+ could be removed in 3 h and 5 h respec-
tively under all the flow rates of 10, 15 and 20 mL min−1. However, an
influence on CA removal could be observed and high flow rate was
counterproductive to the COD decrease. The different effects of flow
rates on Cu2+ and CA removal may relate to mechanism of this system.
Specifically, Cu2+ was removed by electro-adsorption and electro-
deposition, which were tightly associated with the electric field. In-
crease of flow rate from 10 to 20 mL min-1 could not enhance Cu2+
removal further since the removal in the system at 10 mL min-1 was
efficient enough. However, CA removal depends on the generation of
oxidizing species after Cu/Cu2O formation (see Section 3.5). The re-
moval of COD via electro-adsorption mechanism is slower than when
there are reduction and electrodeposition of Cu2+ in this system.
Therefore, lower flow rate with longer retention time benefits the re-
moval of organic pollutant in this system, and 10 mL min−1 was enough
for both efficient removal of Cu2+ and CA to save energy.
Applied voltage is an essential parameter which decides the per-
formance and the mechanism of this electric enhanced system. At 10 mL
min−1 inflow rate, the influence of applied voltage on the WO3/PPy-1/
ACF // ACF system was compared. According to Fig. 5 (d), Cu2+ re-
moval rate was significantly enhanced to 97.8 % in 5 h with the in-
crease of the applied voltage until 1.0 V, while further increase of ap-
plied voltage could only bring a little enhancement. It has been proved
that electro-adsorption of copper ions plays the leading role between
0.0 to 0.8 V where no electrodeposition takes place (Huang et al.,
2014). At 1.0 V, electro-adsorption and electrodeposition together ac-
celerated the Cu2+ removal. A small amount of Cu/Cu2O (characterized
in the following discussion) formed on the modified cathode enhanced
the COD removal rate to 80.1 % (5 h). The detailed mechanism is ex-
plained in Section 3.5. When the applied voltage further increased to
1.2 V, electrodeposition products would agglomerate to cover most of
the electrode surface and cause the decrease of adsorption (Huang
et al., 2014). Since no increase of deposited and reduced products of
Cu2+ was observed at 1.2 V than at 1.0 V, higher voltage with ag-
gregated depositions could not increase the cathodic catalytic activity.
In addition, higher voltage and current response than the optimum may
promote the side reactions at the anode and influence the current ef-
ficiency (Zhou et al., 2014). Therefore, the COD removal rate at 1.2 V
was lower than that of 1.0 V according to the insert of Fig. 5 (d). The
electrodeposition of copper at 1.0 V contributed to the optimal removal
of ionic and organic pollutants in WO3/PPy-1/ACF // ACF system.
Notably, in this system, the electrochemical reactions encourage the
synergistic removal of Cu2+ and CA, which is the major difference
comparing to the conventional EDI or CDI system. The benefit en-
hancement is expected for the removal of heavy metal and the organic
pollutants, taking advantages of the modified electrode and in-situ re-
duced copper or cupric oxide products under low electric field. The
detailed explanation of this system is presented in the following dis-
cussion (Section 3.5).
Apart from flow rate and applied voltage, pH value also plays an
important role in pollutant control chemistry. Its effect on the removal
of Cu2+ and CA in the electrochemical system (WO3/PPy-1/ACF //
ACF, 10 mL min−1, V = 1.0 V) was compared by operating with dif-
ferent influent pH varied from 1.4 to 4.0. In Fig. 5 (e) and (f), more than
97 % of Cu2+ could be efficiently removed at pH 2 and 3 in 5 h and
additional alkali slightly affected the Cu2+ removal efficiency at pH 4
J. Sun, et al.
Fig. 5. (a, b) The Cu2+ removal rate and efficiency in electrochemical systems with different electrodes (the insert in (b) is the 5 h COD removal rate). (c) Cu2+ and
5 h COD (insert) removal rate of WO3/PPy-1/ACF // ACF system with different inflow rates. (d) Cu2+ and 5 h COD (insert) removal rate of WO3/PPy-1/ACF // ACF
system with different applied voltages. (e) Cu2+ and (f) COD removal rates of WO3/PPy-1/ACF // ACF system with different influent pH.
but the 5 h removal rate still reached 91.2 %. However, too acid en-
vironment (pH = 1.4) has negative effect on Cu2+ removal, due to the
increase of competitive cations and copper dissolution and corrosion.
CA removal in 5 h was superior at pH 3, being 23.8 %, 33.8 % and 32.3
% higher than at pH 4, pH 2 and pH 1 respectively. The effect of pH on
CA removal could be explained by the optimum working condition for
the copper related Fenton-like process (Section 3.5) in this system (Lam
et al., 2007). Therefore, no extra chemical is needed for the Cu2+ and
CA removal in the system, which is eco-friendly and economic.
To further illustrate the modification effect of WO3 in pollutant
control, system of PPy-1/ACF // ACF was constructed and its perfor-
mance under optimized operating conditions was compared with WO3/
PPy-1/ACF // ACF in Fig. S3. As expected, higher removal rates of both
Cu2+ and CA were observed in WO3/PPy-1/ACF // ACF due to the
superior electrochemical properties of electrode WO3/PPy-1/ACF
comparing to PPy-1/ACF (Section 3.3). The active component of WO3
played an important role in electrochemical modification of electrode
for pollutant catalytic degradation in this system.
After operated for 5 h under optimized conditions (WO3/PPy-1/ACF
// ACF, 10 mL min−1, V = 1.0 V, pH = 3), the cathode was again
characterized and small amount of reddish brown deposit was observed
which indicates the electrodeposition along with electro-adsorption.
According to SEM and EDX in Fig. 2 (g) and (h), small particles asso-
ciated with element copper emerged on WO3/PPy-1/ACF. More con-
cretely, from the XPS survey spectrum in Fig. 3 (c), there are no other
elemental changes before and after experiment, except Cu 2p. The re-
solved doublets of Cu 2p3/2 (932.9 eV) and Cu 2p1/2 (952.7 eV) (Fig. 3
(f)) are attributed to reduced copper metal and/or cuprous oxide, which
confirmed the electrochemical reactions with electro-adsorption pro-
cess (Huang et al., 2014). The moderate electrodeposition could effec-
tively accelerate Cu2+ removal, and a little Cu/Cu2O on the surface of
electrode may also contribute to organic pollutant degradation.
To further confirm the interaction between Cu2+ and CA, com-
parative experiments without Cu2+ or CA in the influent were per-
formed in the optimized system (WO3/PPy-1/ACF // ACF, 10 mL
min−1, V = 1.0 V, pH = 3), and the results were exhibited in Fig. 6 (a)
and (b). Without Cu2+, in 5 h, only 62.7 % of COD was removed with
7
Journal of Hazardous Materials 394 (2020) 122534
the rate constant of 0.15, while the removal efficiency and rate constant
were enhanced to 80.1 % and 0.26 with the existence of Cu2+. The
promotion of Cu2+ to CA removal should be contributed to the en-
hanced electro-catalytic degradation brought by the electro-active
materials of Cu, Cu2O, and WO3 (Zou et al., 2010; Ai et al., 2008; Xu
et al., 2013; Wu et al., 2019; Liu and Zou, 2014; Hazarika and Manna,
2019) and Fenton-like process (Section 3.5) in this system. The en-
hanced current response of WO3/PPy-1/ACF electrode after test with
Cu2+ and CA confirmed the increased electrochemical performance
after Cu/Cu2O deposition (Fig. 6 (c)). Moreover, the contribution in
conductivity that CA brought to Cu2+ makes it easier for the electro-
chemical reactions. The existence of CA could also benefit the adsorp-
tion of Cu2+ (Chen et al., 2003) and accelerate the Cu2+ removal as
shown in Fig. 6 (b). The synergistic effect of Cu2+ and CA removal
demonstrates the excellent adaptability of this electrochemical system
to such heavy metal/organic acid complex wastewater.
3.5. Possible mechanism and explanation
The possible mechanism of this electrochemical system was pro-
posed in Scheme 1 and the detailed processes were demonstrated in the
following discussion.
At the beginning, ionic pollutants, including copper ions and citrate
ions, effectively migrated under low electric field and were electro-
adsorbed to the cathode and the anode. Owing to the excellent con-
ductivity and capacitance of the modified electrode, the promoted ad-
sorption process benefits the following redox reactions on the surface of
electrodes. Along with the electro-adsorption, the adsorbed Cu2+ ions
partially deposited on the surface of the cathode in the form of Cu/
Cu2O under the exact electric field. The reduction products of heavy
metal ions have excellent electrochemical property and may also form
new composites with the original cathodic materials (WO3, PPy and
activated carbon). Under the integrated functions of those above elec-
troactive components, electro-catalytic processes could contribute to
the organic pollutant (CA) removal.
To concrete the electro-enhanced catalytic mechanism of this
system, experiments about the oxidizing substance and free radicals
J. Sun, et al. Journal of Hazardous Materials 394 (2020) 122534

Fig. 6. (a) COD removal efficiency with/without the existence of Cu2+ (b) Cu2+ removal efficiency with/without the existence of citric acid in the electrochemical
system of WO3/PPy-1/ACF // ACF. (c) CV curves of WO3/PPy-1/ACF before and after experiment in 100 mg L-1 Cu2+ +800 mg L−1 CA electrolyte under 5 mV s−1
scan rate.

were performed. Electrochemical catalytic oxidation could occur in the

2Cu+ + O2 + 2H+ → 2Cu2+ + H2O2 (5)
modified cathode due to the O2 reduction and H2O2, %OH and %O2−
generation. As shown in Fig. 7 (a), H2O2 was detected under the opti- Cu+ + H2O2 + H+ → Cu2+ + %OH + H2O (6)
mized operating conditions during Cu2+ removal. The average con-
centration of H2O2 in 5 h was 2.17 mg L−1 under low electric field Cu + H2O2 + H+ → Cu+ + %OH + H2O (7)
(1.0 V) without aeration. H2O2 could be generated from the Fenton-like H2O2/%OH/%O2− + citric acid → degradation products (8)
process under electric field due to the formation of copper ions in dif-
ferent valence states (Ai et al., 2008). In addition, strong oxidants of % Free radical quenching experiments of OH and % %
O2−
were per-
OH and %O2− could also be generated under the catalytic effect of WO3, formed to confirm their existence with the scavengers of isopropyl al-
PPy and Cu/Cu2O on the cathode. These generated oxidizing species in cohol (IPA) and benzoquinone (BQ) (Liu et al., 2017). With the IPA or
the system, over the modified electrode of WO3/PPy-1/ACF and the BQ, %OH or %O2− could be respectively captured before function with
additional electroactive species (Cu/Cu2O) from Cu2+ ions (Zeng et al., CA, and the COD removal rates without the function of theses free ra-
2011; Mi et al., 2019; Liu et al., 2018), could function in the organic dicals were compared in Fig. 7 (b). Both %OH and %O2− contribute to CA
pollutant degradation and serve as an evidence of the synergistic effect removal in this system and the absence of %OH has greater impact on
of Cu2+ to CA removal. The specific reactions are listed as follows: the organic pollutant degradation because H2O2 is a supplementary
source of %OH. The degradation of CA under the attack of these free
Cu2+ + e− →Cu+ (1) radicals have been studied in the earlier reports (Meichtry et al., 2011)
Cu +
+e −
→ Cu (2) and small molecular acetone and carbon dioxide could be the final
products (Quici et al., 2007).
−
O2 + e → O2-
%
(3) Under low electric field, the free radical oxidation mechanism of the
catalytic cathode plays an important role in organic pollutant (CA)
%
O2− + 2H +
+ e- → H2O2 (4)

Scheme 1. Proposed reaction mechanism of the electrochemical system.

8
J. Sun, et al. Journal of Hazardous Materials 394 (2020) 122534

Energy consumption U%I%t (kW h) per unit

(t =40 min)
8.12 kW h kgremoved copper−1 (t =3 h);

(t =5 h)

−1
2.54 kW h kgCOD−1 (t =5 h)

copper
−1
copper

12.27 kW h kgremoved
11 kWh kgremoved
pollutant
Comparison of additional electric field and energy consumption of this electrochemical system and other traditional electrochemical treatment processes for heavy metal removal.

–
Energy consumption U%I%t (kW h) per unit

and ED ≈
1.25 kW h m−3 of treated solution

1.86 kW h per ton of wastewater

−1

2 kW h m-3 of treated solution

EL ≈ 3 kW h kgremoved copper
1.48 kW h m−3 of permeate
water

–
1.0 V applied voltage

7 V applied voltage
120 A m−2 current

current

200 A m−2 current

Additional electric

−1

−2
2.5 V cm

94 A cm
density

density

density
field

Fig. 7. (a) H2O2 generation of WO3/PPy-1/ACF // ACF electrochemical system

99.5 % of copper recovery from copper-containing

> 90 % of copper removal and recovery and 66.7

Copper recovery (99.9 %) and cyanide oxidation
under optimized operating conditions with 50 mL 100 mg L−1 Cu2+ solution
Electrochemically reduce Cr(VI) and split water
Simultaneous removal of 97.8 % of Cu2+ and

95.6 % of Ni(II) recovery from nickel plating

(using concentrated H2SO4 to adjust pH to 3). (b) Free radical quenching ex-
periments by adding 1 mM scavenger (IPA for %OH and BQ for %O2-) to Cu2+/CA
complex solution in the optimized electrochemical system.

removal, together with adsorption and direct anodic oxidation.

Therefore, even excessive copper ions were deposited on the surface of
%–68.4 % COD removal

the cathode and the electro-adsorption was reduced, CA removal would

not be affected but increase due to the enhanced catalytic process (Fig.
Application field

S4). However, in this circumstance, electro-adsorption of Cu2+ was

80.1% of COD

weakened and Cu2+ removal rate in 5 h slightly decreased to 95.0 %

wastewater

wastewater

which was mainly contributed by the electrodeposition. Thus, the

electro-enhanced simultaneous removal of Cu2+ and organic pollutant
could be achieved in this system with the WO3/PPy-1/ACF cathode and
the integrated electrochemical functions even in the long run.
A combination process of electrolysis (EL) and electrodialysis (ED)
A combined process of electrostatic repulsion, electrochemical

Electrowinning in a electroplating cell (Dutra et al., 2008)

Electrocoagulation treatment (Stergiopoulos et al., 2019)

3.6. Technological advantage and superiority

reduction, and precipitation (Duan et al., 2017)

To sum up, this optimized electric system with modified electrodes,

enhanced removal of heavy metal and organic pollutant expands CDI
Electrodeposition treatment (Li et al., 2019)

and EDI application in the similar system configuration. In practic-

ability, this electrochemical system is easy to operate and low-cost
Electrochemical system in this work

because no expensive material is needed. The electrochemical processes

are integrated with electro-adsorption by accurately controlling the
external electric field without other chemical addition. Compared with
CDI or EDI, this system has wider adaptability. And compared with
(Peng et al., 2011)
System and method

traditional electrodeposition and electrodialysis for heavy metal re-

moval, as shown in Table 4, this system has significant advantages of
lower energy consumption (calculated to be 1.25 kW h m−3) and fewer
side effects under weak electric field.
Table 4

Notably, instead of only transfer of pollutant from liquid to solid

phase in electro-adsorption and electrocoagulation, or the enrichment

9
J. Sun, et al.
and concentration in electrodialysis, the proved electrodeposition in
this system realized heavy metal recovery and reuse, besides electro-
adsorption. Treating the heavy metal ion as a resource and realizing its
in-situ use is more economic and cost-effective than only treat it as a
pollutant. It is applicable to use our synergetic electrochemical system
for effective removal of heavy metal ions as well as organic pollutants,
via electro-adsorption and electrochemical processes.
The electrochemical system with WO3/PPy-1/ACF electrode ex-
panded the applicability of traditional electrode and electric systems.
This work provides a new train of thought as well as data support for
the practical treatment of wastewater containing heavy metal/organic
pollutant.
4. Conclusion
Series ACF substrate electrodes were modified with WO3 and PPy by
using one-step hydrothermal method. The WO3/PPy-1/ACF has ex-
cellent conductivity and capacitance property (2.58 F cm−2). With a
specific area of 788.27 m2 g-1, this WO3/PPy-1/ACF electrode has great
potential in deionization application.
Electrochemical deionization and oxidation performances in si-
multaneously removing Cu2+ and CA of the systems constructed with
ACF and modified electrodes were compared. With WO3/PPy-1/ACF
cathode and ACF anode, the optimal operating conditions of inflow
rate, applied voltage and pH were 10 mL min−1, 1.0 V and 3, under
which 97.8 % Cu2+ and 80.1 % CA (in 5 h) were respectively removed.
Characterizations of the cathode used in this system indicate the for-
mation of a small amount of Cu/Cu2O on the electrode surface from
electrochemical reactions after electro-adsorption.
Specially, Cu2+ was not only removed but also in-situ used as the
electro-active substances for oxidizing organic pollutant (CA). Positive
interactions between Cu2+ and CA in this electrochemical system were
confirmed. The electro-deposited Cu/Cu2O and WO3/PPy-1 promoted
the removal rate of heavy metal ions (Cu2+) and organic acid (CA) due
to the integration of electro-adsorption, electrodeposition and electro-
chemical catalytic oxidation during deionization.
The advantages of this system treating heavy-metal/organic was-
tewater are: (1) the more thorough use of functions of electrode ma-
terials and electric field than the simple CDI or EDI system; (2) the
lower energy consumption and operating costs, and (3) the less side-
effect than conventional electrochemical technologies. The electro-
chemical system using modified electrode WO3/PPy-1/ACF, has greater
adaptability to treat wastewater with heavy metal/organic acid.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors would like to thank the National Natural Science
Foundation of China (No. 21677025) for financial support.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122534.
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