Machine Translated by Google

Chemosphere 308 (2022) 136189

Contents lists available at ScienceDirect

Chemosphere

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

Electrochemical regeneration of granular activated carbon using an AQS (9,10-anthraquinone-2-sulfonic acid)/PPy modified graphite plate cathode

*
Xiao Ye, Wangfeng Cai, Ding Lu, Ruonan Liu, Yingdong Wu, Yan Wang

School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, PR China

HIGHLIGHTS GRAPHICAL ABSTRACT

• A modified AQS/PPy-GP cathode was used

in electrochemical regeneration of GAC.

• Regeneration parameters were optimized

by RSM-BBD method. • The
modified AQS/PPy-GP cathode accelerated
organics degradation and improved
regeneration efficiency. • AQS/PPy-
GP is economically efficient for its low energy
consumption.

ARTICLE INFO ABSTRACT

Handling editor: E. Brillas In the present study, we investigate the regeneration efficiency of Rhodamine B (RhB)-saturated granular activated carbon
(GAC) in an electrochemical regeneration system by using a 9,10-anthraquinone-2-sulfonic acid/polypyrrole modified
Keywords: graphite plate (AQS /PPy-GP) cathode. The response surface methodology based on the Box-Behnken design (RSM-BBD)
Activated carbon
approach was used to optimize regeneration parameters, whereby the optimum condition of the independent variables
Electrochemical regeneration
was as follows: applied current = 155 mA, concentration of supporting electrolyte = 0.13 M, and regeneration time = 7 h.
Adsorption
Cathode The electrochemical regeneration system with the AQS/PPy GP electrode achieved high regeneration efficiency and
Rhodamine B significantly reduced energy consumption. H2O2 with concentration generated in the electrolysis system was notably
increased, and the time of complete degradation of organics was shortened by 25% compared to the electrode without
modification. The mechanism for RhB degradation was proposed as AQS acting as a catalyst to promote the formation of
H2O2. The regeneration study showed that AQS/PPy-GP cathode had appreciable reusability for GAC regeneration with
a regeneration efficiency of 76.6% after 8 regeneration cycles. In summary, the electrochemical regeneration based on
AQS/PPy-GP cathode would have practical industrial applications in treating spent activated carbons.

1.Introduction pollution of industrial wastewater. Organics and heavy metal contamination from
industrial activities, such as textile, dye manufacturing, smelting and electroplating,
The rapid industry developments lead to the increasingly critical pose serious water threats (Bai et al., 2019).

* Corresponding author.
E-mail addresses: yexiao@tju.edu.cn (X. Ye), wfcai@tju.edu.cn (W. Cai), ludingde@tju.edu.cn (D. Lu), liuruonan@tju.edu. cn (R. Liu), yingdongwu@tju.edu.cn
(Y. Wu), zhuwangyan@tju.edu.cn (Y. Wang).

https://doi.org/10.1016/j.chemosphere.2022.136189
Received 19 May 2022; Received in revised form August 19, 2022; Accepted 21 August 2022 Available
online 26 August 2022
0045-6535/© 2022 Elsevier Ltd. All rights reserved.
Machine Translated by Google
X. Ye et al.
Many treatment systems like flocculation, combined biological processes, and membrane
filtration are applied to treat wastewaters with taining toxic or recalcitrant organic pollutants.
Amongst these technologies, adsorption with media having a large surface area and
microporous structure, like activated carbon, is a mature and effective method to remove
organic pollutants and heavy metals (Saleh et al., 2017). Despite its many advantages, a
more economical and environmentally friendly option is regeneration. However, these
options are often limited by their limited longevity. Mature regeneration methods such as
thermal, chemical, and microbial processes have limitations such as high energy
consumption and carbon loss, porosity deterioration, and slow regeneration rates (Garcia-
Rodriguez et al., 2020). In contrast, electrochemical methods appear promising in
overcoming these limitations because of their strong oxidability, high efficiency, and
avoidance of chemical reagents and temperature (Martinez-Huitle and Ferro, 2006; Oller
et al., 2011), allowing the reuse of activated carbon after multiple cycles of adsorption and
regeneration.
The electrochemical regeneration process allows the spent activated carbon to be
placed between two oppositely charged electrodes.
Desorption then occurs when an electric current is applied, and the adsorbed pollutants
are subsequently degraded in the appropriate conditions (McQuillan et al., 2018).
Generally, the cathode regeneration of activated carbon can achieve much better
regeneration efficiency than anodic regeneration. The mechanism of cathodic regeneration
involves the oxidation process by electrogenerated H2O2 as an intermediate species
through indirect cathodic oxidation and electrostatic repulsion as a consequence of the
polarization of the activated carbon (Berenguer et al., 2010). Notably, the electrogenerated
H2O2, an important oxidant and bleach, can be used for the in-situ oxidation of pollutants
for wastewater treatment (Wang et al., 2021; Chen et al., 2022). H2O2 formation occurs
easily as oxygen reduction can occur over a wide range of pH values and is favored on
steel and carbon electrodes (McQuillan et al., 2018). Thus, the property of electrochemical
regeneration is affected by the properties of the used cathode materials.
Since the cathode material directly influences the generation rate of active components
for contaminants degradation, such as ÿOH and H2O2 (Pipi et al., 2014), it is highly desired
to develop an efficient cathode for their production. One way to improve the efficiency of
the cathode is to use a conventional carbon-based material as a substrate and introduce
other high-performance materials on its surface to promote the production of H2O2 and
enhance oxidative degradation efficiency. Carbo naceous materials have been extensively
studied as cathode materials for electrochemical regeneration due to their low catalytic
activity for H2O2 decomposition, high over-potential for H2 evolution, available active sites,
and excellent stability and conductivity (Brillas et al., 2009; Brouzgou et al., 2016; Roth et
al., 2016; Ramirez-Pereda et al., 2018).
Quinones can reduce O2 through electrocatalysis and further generate H2O2 under acidic
conditions (Eqs. (1)–(3)) (Zhou et al., 2018b). An thraquinones (Q) accepts electrons to
produce hydroquinone (H2Q), and subsequently, H2Q is reduced to semiquinone (SQÿ- )
by the Oÿ ÿ 2 1
produced by anthraquinone-activated O2. Activated carbon as catalysts activates H2O2 to
ÿOH (Fortuny et al., 1998), promoting activated carbon regeneration and faster organics
degradation. However, quinones have disadvantages such as poor electrical conductivity,
difficult recovery, and easy loss of catalyst in the reaction process, limiting their application
in electrocatalysis. As a typical conductive polymer, a conductive polymer of polypyrrole
(PPy) has good conductivity and environmental stability and is easy to prepare (Gao et al.,
2017). It could combine with other materials to promote the dispersion of catalysts and
improve the electrochemical properties of electrodes (Long et al., 2019).
Considering the excellent properties, firm coating, and high cathodic activity of PPy and
AQS through electro-polymerization, attaching 9, 10-anthraquinone-2-sulfonic acid/
polypyrrole (AQS/PPy) film on graphite plate (GP) is a feasible method for electrochemical
regeneration. However, there is limited use of the 9,10-anthraquinone-2-sulfonic acid/
polypyrrole modified graphite plate (AQS/PPy-GP) and
2
Chemosphere 308 (2022) 136189
application in the electrochemical regeneration system. Therefore, we set out to investigate
these properties and put forward our research to advance this topic in the field.
Q + 2eÿ + 2H+ÿH2Q (1)
H2Q + O2ÿQ + H2O2 (2)
H2Q + %Oÿ 2 ÿSQÿÿ + H2O2 (3)
In this study, we synthesized a AQS/PPy-GP cathode and investigated the
electrochemical regeneration of granular activated carbon (GAC) and degradation of
organics. Rhodamine B (RhB) was selected as the adsorbate because it is often detected
in high concentrations in many industrial wastewaters (Tian et al., 2016). RhB has potential
toxicity, mutagenicity, and carcinogenicity (Bai et al., 2011). Additionally, the response
surface methodology based on the Box-Behnken design (RSM-BBD) mathematical model
was used to optimize the regeneration efficiency of GAC. The performance of the AQS/
PPy-GP cathode was compared with bare GP in terms of the regeneration efficiency of
GAC, degradation of desorbed pollutants, and electrode stability. This work is expected to
provide novel information and lay the groundwork for electrochemical regeneration of the
spent adsorbent by optimizing the electrode.
2. Materials and methods
2.1. Chemicals and materials
The granular activated carbon (HPZ-03(1100)) was produced by Fujian Xinsen Carbon
Industry Co., Ltd. RhB, Sodium sulfate (Na2SO4), and 9,10-anthraquinone-2-sulfonic acid/
polypyrrole (AQS) were pur chased from Shanghai Meryer Chemical Technology Co., Ltd.
Pyrrole was purchased from Shanghai McLean Biochemical Technology Co., Ltd. and
titanium potassium oxalate (C4H2K2O10Ti) was purchased from Shanghai Ron. All
reagents are analytically pure. The Ti coated with iridium oxide and ruthenium oxide (Ti/
IrO2–RuO2), and graphite plates were purchased from Hebei Chengshuo Metal Material
Co., Ltd. and Tianjin Suqian Co., Ltd. respectively. All solutions were prepared with
deionized water (18.25 Mÿ cm2).
2.2. Adsorption experiments
GAC was first washed repeatedly with deionized water, then boiled in deionized water,
and finally dried in a vacuum at 105 ÿC for 24 h.
Batch experiments determined the adsorption isotherms. Two grams of GAC were added
to flasks containing 200 mL of RhB solutions with concentrations between 100 and 1000
M, and flasks were sealed and shaken at 25 ÿC and 200 rpm until equilibrium was reached.
Solutions after adsorption equilibrium were filtered with a 0.45 ÿm PES mem brane. The
amount of RhB adsorbed at equilibrium (qe, mg gÿ calculated via Eq. (4):
) was
(Co ÿ Ce)V
qe = (4)
mGAC
where V is the volume of solution (L), mGAC is the mass of GAC (g), and C0, Ce (mg Lÿ
1
respectively. ) are initial and equilibrium concentrations of RhB,
23. Preparation of AQS/PPy-GP cathode
GP was immersed in acetone, 1 M H2SO4, and 3% hydrogen peroxide solution with
a constant temperature of 90 ÿC for 1 h, then subsequently rinsed with deionized water
several times and dried in an oven at 105 ÿC
for 1 h. AQS/PPy film was electrodeposited on the GP on an electro chemical workstation
where the pretreated GP, platinum sheet, and the
Machine Translated by Google
X. Ye et al.
Ag/AgCl electrode (sat. KCl, 0.195 V vs. SHE) were used as a working
electrode, a counter electrode, and a reference electrode, respectively.
The electrolyte solution contained 0.5 M H2SO4, 0.1 M pyrrole, and 5 mM
AQS. This solution was charged with N2 for 20 min prior to adding pyrrole to
ensure it was in an N2-saturated condition. The electro chemical station
applied a constant potential of +0.8 V for 420 s to obtain the AQS/PPy modified
electrode. The composite electrode was then cleaned and dried at 60 ÿC for
12 h.
2.4. GAC electrochemical regeneration
The regeneration device was comprised of a Ti/IrO2–RuO2 anode (30 mm
* 50 mm * 2 mm), a graphite plate cathode (30 mm * 50 mm * 2 mm), Ti
sheets, and an electrode chamber made of acrylic frames (Fig. 1). The
electrodes were situated vertically and parallel at a distance of 8 mm. The
perforated plexiglass plate was placed in the cathode area, which was 3 mm
away from the cathode, and GAC was filled in the gaps between the orifice
plate and the cathode to form a three-dimensional electrode. Both module
ends were reinforced with 8 mm thick plex iglass plates and sealed with
silicone rubbers to ensure contact between Ti sheets and electrodes. We
performed the experiment in the circulation mode, where a peristaltic pump
circulated the electrolyte (200 mL of Na2SO4) between the electrode chamber
and the storage tank.
We designed the regeneration experiments by response surface
methodology and studied the effects of applied current, supporting electrolyte,
and regeneration time on regeneration efficiency. The adsorbed GAC was
dried at 105 ÿC, cooled to atmospheric temperature, then placed between the
cathode and the perforated plexiglass plate for electrochemical regeneration.
Finally, the adsorption process was repeated. The regeneration efficiency was
evaluated with Eq. (5):
qe,r
RE = × 100% (5)
qe,v
where qe,v, and qe,r are the adsorption capacity of virgin and regenerated
GAC, respectively.
The energy consumption was calculated using Eq. (6):
UI
EC( kWh kgÿ 1) = (6)
1000mGAC
where U corresponds to the voltage of the electrochemical cell (V), I is the
applied current (A), t is the regeneration time (h), mGAC is the mass of GAC
(kg), and 1000 is the conversion factor.
2.5. Analytical methods
Cyclic voltammetry (CV), linear sweep voltammetry (LSV), and
electrochemical impedance spectroscopy (EIS) were used to characterize the
electrochemical properties of the prepared electrode. The content of H2O2
was quantitatively analyzed by the potassium titanium oxalate method with an
ultraviolet spectrophotometer (UV-2550, Shimadzu
Fig. 1. Electrochemical reactor scheme.
3
Chemosphere 308 (2022) 136189
company, Japan) (Zhang et al., 2019). The surface morphology of GP and
GAC and EDS spectra of GP were characterized by a scanning electron
microscope (SEM, Hitachi S-4800, Japan). Fourier transform infrared (FTIR)
spectra were obtained on a Nicolet-380 Fourier trans form infrared
spectroscopy with a DTGS detector. The surface elemental composition was
obtained by X-ray photoelectron spectroscopy (XPS)
(ESCALAB 250XI, ThermoFisher, United States). The RhB concentration was
determined with a UV–visible spectrophotometer at 553.5 nm. The solution's
chemical oxygen demand (COD) concentration was measured with a COD
detector (COD-571, Leica company, China). The specific surface area and
pore volume of GAC were analyzed by N2 adsorp tion/desorption isotherm at
77 K on an analyzer (Autosorb-iQ2-MP, Quantachrome, USA) (Li et al., 2014).
3. Results and discussion
3.1. Characterization of the modified cathode
SEM micrographs and EDS spectra were conducted to investigate the
effect of AQS/PPy film modification on electrode morphology and characteristics.
The surface of the GP appeared smooth (Fig. 2a) (See original SEM in Fig.
SM-1). The morphology of PPy film exhibited a uniform layer, and PPy/AQS
film exhibited a rough and granular surface feature on the GP surface (Fig. 2b
and c). Compared with the GP elec trode, the AQS/PPy-GP electrode showed
favorable surface character istics and thus may have a higher surface catalytic
activity. After modifying GP with PPy (PPy-GP), the elements N and S are
observed, and the proportion of O increases (Fig. 2b). The increase in S and
O are attributed to the H2SO4 electrolyte used for electrodeposition. With
additional AQS doping, the proportion of C element increases evidently (Fig.
2c). The chemical EDS analysis indicates that AQS and pyrrole were
successfully attached to GP, and the increased roughnesses also increased
the active surface area to a large extent, thereby increasing the opportunity
for the target material to contact the active site. As shown in Fig. 2d, the
current densities of oxidation and reduction peaks of AQS/ PPy-GP electrode
are about 19.6 times and 12.2 times higher than GP, respectively. Incorporating
AQS in the PPy matrix significantly improved the current generation over a
broader potential range and increased ORR activity in the presence of O2. It
also suggests the enhancement of specific capacitance because of the
increased surface area of the electrode, as verified by Fig. 2e.
The EIS measurements were recorded in N2-saturated solutions to further
assess the electrochemical performance of the electrodes (Fig. 2f). Based on
the equivalent circuit model (Rs (QRct) (QW0)), the EIS measurements results
were simulated accordingly (Table SM1). The slopes in the low-frequency
region of the two curves were very close, representing the same low ion
diffusion resistance of GP and AQS/PPy GP electrodes. The semicircle in the
high-frequency region represents the electrode's internal resistance of electron
transfer (Rct), which directly reflects the electrode's electrochemical activity
and the electron transfer's difficulty on the electrode surface. The Rct of AQS/
PPy-GP (103 ÿ) was significantly lower than that of GP (387 ÿ), suggesting it
has better kinetic behavior and charge transfer capability (Long et al., 2018).
Above all, the GP electrode was modified by AQS doping into conductive
polymer PPy by electrochemical deposition, which improved the electrochemical
activity and reduced the GP electrode's resistance.
3.2. Adsorption models
The Langmuir isotherm model represents monolayer adsorption onto an
adsorbent (Trellu et al., 2018), whereas the Freundlich model is suitable for a
highly heterogeneous surface of a multilayer absorption onto an adsorbent
(Kundu et al., 2018). As indicated by the high R2 (0.9922) of Langmuir than
Freundlich isotherm (R2 = 0.9422), the adsorption on GAC mainly involves
monolayer adsorption and is consistent with previous relevant reports
(Kadirvelu et al., 2005)
Machine Translated by Google

X. Ye et al. Chemosphere 308 (2022) 136189

Fig. 2. SEM photographs and EDS spectra of bare (a) GP, (b) PPy-GP, and (c) AQS/PPy-GP, respectively. (d) Comparison of the CV and (e) LSV curves of GP and H2SO4. (f) Nyquist plot of GP and
ÿ1
in 0.1 mmol Lÿ 1
AQS/PPy-GP in ÿ 0.9-0.7 V at 5 mV s AQS/PPy-GP electrodes at 100 kHz-10 mHz at 10 mV at open-circuit
potentials (inset: equivalent circuit simulated by ZimpWin).

Fig. 3. (a) Adsorption isotherm and (b) adsorption kinetics of rhodamine B on GAC (V = 200 mL, mGAC = 2 g, t = 24 h and T = 25 ÿC for adsorption isotherm test; V =
1
mGAC = 2 g, C0 = 100 mg Lÿ and T = 25 ÿC for adsorption kinetic test). 200 mL,

(Fig. 3a). According to Hall et al. (1966), the characteristics of the adsorption, 0 < RL < 1 for favorable adsorption, RL = 1 for linear
Langmuir adsorption can be estimated from a dimensionless adsorption, and RL > 1 for unfavorable adsorption. The RL values
separation factor (RL, calculated by Eq. (7)), that is, RL = 0 for irreversible ob tained were in the range 0.59–0.13 for different initial RhB

4
Machine Translated by Google

X. Ye et al. Chemosphere 308 (2022) 136189

concentrations of 100–1000 M, indicating the highly favorable adsorption of RhB onto supporting electrolyte concentration, and regeneration time of the regeneration efficiency
GAC. of GAC in the electrochemical regeneration method, were evaluated and optimized by

1 RSM-BBD.
RL = (7)
1 + KLC0
3.3.1. Applied current
1 The rate of reaction increases with an increase in applied current. In Fig. 4a, the
where KL is the Langmuir constant (mg Lÿ adsorbate ), and C0 is the initial
1 GAC regeneration efficiency gradually increased as the applied current increased to
concentration (mg Lÿ ).
To investigate the adsorption mechanism and potential rate determining steps, the about 155 mA at supporting electrolyte =

adsorption kinetics of RhB was studied by pseudo-first-order (PFO), pseudo-second- 0.13 M and regeneration time = 7 h. Applied current is a critical parameter in the

order (PSO), and Elovich ki netic models (Fig. 3b). The high R2 (0.9902) value and high electrochemical reaction process because it is the driving force of contaminant

initial adsorption rate (0.2613 (mg gÿ chemisorption) is the dominant mechanism during
1 1
the RhB adsorption onto GAC, which hÿ )) of the Elovich model indicate that
is similar to other reports (Gad and El-Sayed, 2009; Lian et al., 2020 ).The mathematical
forms of Table SM2 were obtained by fitting the experimental data.
degradation and controls the rate of Faraday reactions occurring on any given electrode
surface (McQuillan et al., 2018). The regeneration efficiency increased with the current
increase because the oxidation reaction rate increased, and more ÿOH was produced in
the system, thus enhancing the mineralization of pol lutants (Bakheet et al., 2013).
Furthermore, GAC was used as the catalyst to promote the decomposition of H2O2 to
form highly oxidizing radicals (Lucking et al., 1998). At the same time, an increase in the

The overall results of adsorption experiments show that the high adsorption capacity applied current results in increases in the electrode potential and the polarization of the

and kinetics for RhB adsorption make GAC an excellent adsorbent for removing RhB GAC surface and maintains a high surface charge, consequently increasing the

from water. However, the strong interactions between RhB molecules and carbon electrostatic repulsions between the GAC surface and pollutants to promote desorption
surfaces make GAC adsorbed RhB's regeneration difficult. (Zhan et al., 2016). However when the applied current exceeds 155 mA, the regeneration
efficiency slightly decreases because H2O2 is reconverted to O2, hindering the formation
of ÿOH, or ÿOH is converted to O2 at high currents (You et al., 2013).

3.3. Optimization of the operating conditions

The effects of independent variables, including applied current, Additionally, H2O2 is an ÿOH scavenger, thus reducing the regeneration

Fig. 4. Response surface plot showing the interaction effects of the operating parameters.

5
Machine Translated by Google
X. Ye et al.
efficiency when excessive H2O2 is generated in the system (Yao et al.,
2016).
3.3.2. Supporting electrolyte
The regeneration efficiency is significantly improved when the
electrolyte concentration increases from 0.01 M to 0.13 M at applied
current = 155 mA and regeneration time = 7 h (Fig. 4b). The variation in
electrolyte concentration directly affects ion exchange rate and the
reduction of electrostatic resistance between electrodes and electrolyte,
consequently enhancing the oxidation system's performance by improving
electrochemical reactions such as reduction of oxygen to H2O2 at the
surface of the cathode and GAC particles ( Asgari et al., 2021). However,
regeneration efficiency changes are not apparent when the electrolyte
concentration increases from 0.13 M to 0.2 M. The applied voltage
gradually decreases with the increase of electrolyte concentration,
reducing the driving force of the electrolytic reaction.
Meanwhile, sulfate ions adsorbed on the electrode surface occupy
several active sites and hinder the production of OH.
Fig. 5. (a) Regeneration efficiency and energy consumption for GAC. (b) H2O2 accumulation and (c) COD evolution with different electrodes under circulated
operation. (d) N2 adsorption-desorption BET isotherms and (e) pore size distribution curves of the virgin, RhB-saturated, and regenerated GAC.
6
Chemosphere 308 (2022) 136189
3.3.3. Regeneration time
Longer regeneration time can improve GAC regeneration efficiency.
The efficiency improvement can increase the degradation time of all
processes involved in the oxidation mechanism at the prolonged reaction
time. Additionally, the increase in reaction time significantly affects the
concentration of H2O2 in the system and, eventually, the concentration
of reactive radicals (Asgari et al., 2021). Thus, there is a greater chance
for RhB molecules to make contact with active radicals. How ever, when
the regeneration time exceeds 7 h (Fig. 4c), the regeneration efficiency
decreases with increased regeneration time, partly due to oxidation by-
products adsorbing onto the GAC surface (Berenguer et al., 2010).
Above all, we used the RSM-BBD model to optimize the regeneration
conditions. The optimum condition of the independent variables was as
follows: applied current = 155 mA, the concentration of supporting
electrolyte = 0.13 M, and regeneration time = 7 h. The detail of the
optimization process can be found in Text SM1.
Machine Translated by Google
X. Ye et al.
3.4. Effect of adsorption-regeneration cycles on the electrochemical
Under optimal operational regeneration conditions, 8 consecutive cycles
of RhB adsorption and regeneration were carried out with GP and AQS/PPy-
GP cathodes, respectively. Fig. 5a shows the calculated RE and EC values
during the multiple cycles. Higher RE was achieved for the AQS/PPy-GP
cathode in cycles, indicating good stability and high cat alytic activity. The
GAC treated with GP and AQS/PPy-GP maintained a regeneration capacity
of 63.5% and 76.6% after 8 cycles, respectively.
Therefore, these suggest that the modified cathode is feasible for practical
operation. Additionally, the EC of the system with AQS/PPy-GP was lower
than that with GP, which may be due to the low resistance of AQS/PPy-GP,
thus reducing the voltage required for regeneration as demonstrated by Fig.
2f . With the AQS/PPy-GP cathode, we achieved 97.3% regeneration
efficiency at only an energy consumption of 1.38 kWh kgÿ which is superior
1
, consumption efficiency of thermal gasification and microwave
to the energy
regeneration methods. Under optimized regeneration conditions, the REs
and ECs obtained during the consecutive regeneration cycles are generally
comparable to or better than those reported for the other electrodes (Table
SM3). Compared with different electrodes, the AQS/PPy-GP electrode may
represent a more environmentally-friendly and suitable material to regenerate
spent GAC.
We further explored the role of AQS/PPy-GP cathode in H2O2 generation,
in which H2O2 content was monitored in the electrolysis process. Fig. 5b
shows that the AQS/PPy-GP cathode accumulates a higher H2O2
concentration than GP during the electrolysis process, indicating that the
AQS/PPy-GP cathode surface has active groups, strengthening the reaction
of anthraquinone catalyzing O2 to form H2O2 on its surface (Eqs. (1)–(3)). In
addition, we observed an accumulation of H2O2 during the first 60 min of
electrolysis, followed by decay and a subsequent plateau within 120 min.
The attenuation of H2O2 is not only related to the continuous 2-electron
reduction reaction of H2O2 (Eq. (8)) (Zhang et al., 2015) but also to its
activation on the GAC surface (Eqs. (9-10) ), generating hydroxyl radicals
and superoxide radical anions (Georgi and Kopinke, 2005). Additionally,
GAC can be used as a catalyst to promote its regeneration without other
chemicals (Zhou et al., 2019). Further more, the observed plateau is likely
due to H2O2 destruction by GAC balancing its electrogeneration at the
cathode. Thus, H2O2 is the precursor of ÿOH, and the higher concentration
of H2O2 provides the possibility to improve the regeneration efficiency by
accelerating the degradation of organics.
H2O2 + 2H+ + 2eÿ ÿ2H2 (8)
H2O2 + ACÿAC+ + OHÿ + %OH (9)
H2O2 + AC+ÿAC + H+ + %OH (10)
To verify the degradation of organics in this system, the concentration of
chemical oxygen demand (COD) in the solution was detected. In Fig. 5c, the
COD values quickly reached an initial peak but then decreased considerably
with the reaction time of regeneration. This trend indicates that the initial
oxidation rate of organics is far lower than the desorption rate (Wang and
Balasubramanian, 2009) but then de sorbs more slowly than it mineralizes
as the regeneration proceeds. After replacing GP with the AQS/PPy-GP
cathode, the reduction rate of COD is significantly accelerated, and the time
for complete degradation of or ganics is reduced by 25%. The reason is that
catalyst doping increases reaction rates by reducing the activation energy,
like increasing the rate of H2O2 generation, which is consistent with the
results in Fig. 5b. As mentioned above, RhB molecules can be oxidized by
H2O2 species generated from AQS/PPy-GP with promoted oxygen reduction,
while AQS work as a catalyst (Bao et al., 2012). Likewise, this can occur by
ÿOH radicals generated from H2O2 catalyzed by the GAC. As a result, the
pores blocked by organics were reduced, resulting in the increased
regeneration efficiency of the GAC.
7
Chemosphere 308 (2022) 136189
To support the above observations, the BET method was carried out of
GAC before and after electrochemical regeneration (Fig. 5d and e).
According to Brunauer's classification (Brunauer et al., 1940), all samples
exhibit a combined feature of type I and type IV isotherms, indicating that
the GAC has micropores and mesopores. The BET surface area of the virgin
1 for the satu
GAC decreases from 914 to 561 m2 gÿ rated AC, whereas
the micropore volumes and mesopore volumes decrease (Table SM4). After
regeneration, the micropore volume of the GAC was largely recovered (Fig.
5e). These observations suggest that the adsorbed RhB and its oxidation by-
products have mainly been removed from the GAC, indicating that
electrochemical regeneration can recover GAC's porosity. Compared with
the GP cathode, the GAC regenerated with AQS/PPy-GP cathode recovered
in surface area and micropore volume more thoroughly because the AQS/
PPy-GP cathode allowed to desorb more compounds faster and reduced the
blockage of pores of GAC by accelerating the degradation of organics, and
consequently improving the regeneration ability of GAC. SEM micrographs
of GAC before and after regeneration show that the small particles on the
GAC surface are no longer visible after treatment (Fig. SM1d-f). After 8
regeneration cycles, a more irregular surface was observed. This is in
accordance with the constant friction of the particles and the high potentials
used, giving rise to possible oxidation (Acuna-Bedoya et al., 2020). However,
the structure of GAC did not change significantly. The diffraction peaks of
hexagonal carbon (120) and (012) at around 22.8ÿ
and 43.9ÿ were well-preserved after 8 cycles of regeneration (Fig. SM2a),
and no other prominent diffraction peaks were observed.
FTIR spectrum of GAC (Fig. SM2b) show that the band at 3600-3000 1 is
attributed to O–H stretching vibration of hydroxyl groups and cmÿ 1 and
2810 cmÿ are
1 chemisorbed water. The bands at 2820 cmÿ
ascribed to the aliphatic C–H stretching vibration of CH, CH2, and CH3.
Furthermore, the characteristic band at around 1020 cmÿ to 1 corresponds
the ether radicals exist in different structural environments. Consisting of
previous results, the spectra of regenerated GAC did not significantly differ
from virgin GAC, confirming that the structural integrity of the regenerated
GAC is well-preserved. We also compared the internal resistance of electron
transfer (Rct) of fresh and used AQS/PPy-GP electrodes (Fig. SM3). We
found that Rct slightly increased (from 103 to 159 ÿ), indicating the
degradation of AQS/PPy film and the loss of its electronic conductivity in the
presence of ÿOH and H2O2 for the 8 runs used electrode. This explains the
decrease in the regeneration efficiency of GAC in Fig. 5a and verifies the
stability of the AQS/PPy-GP electrodes.
Finally, the modification of surface composition of GAC following
regeneration cycles was analyzed by XPS. Fig. SM4 shows the decon
evolution of C1s peak of the carbon at 284.5 eV. The existing oxygen
functional groups on the surface of the virgin GAC comprised C–C, C–O and
C– –O. Following regeneration, regenerated GAC displayed a new peak at
around 290 eV, corresponding to pp* aromatic rings transitions.
The peak intensity of the oxygen-containing functional groups increased after
regeneration. The presence of oxygen functional groups on the surface of
carbonaceous materials can affect both organic adsorption and oxygen
reduction reaction (Garcia-Rodriguez et al., 2020), thus these changes may
improve the adsorption of RhB and ultimately restore the regeneration
capacity of GAC.
3.5. The proposed regeneration mechanism
A possible electrochemical regeneration mechanism is proposed (Fig. 6).
O2 is generated on the anode and then transported to the vicinity of the
cathode (Zhou et al., 2018a). At GP cathode, O2 in solution is reduced
electrochemically to generate H2O2 or as an electron acceptor (Eqs. (11-12)),
to generate Oÿ 2ÿ and subsequently, the Oÿ ÿ 2 produced in
solution are active and continue to accept electrons to generate H2O2 (Eq.
(13)). At the AQS/PPy-GP cathode, Q are reduced to SQÿ- by one electron
from the cathode (Eq. (14)), and subsequently, the SQÿ- com bines with O2
to form O2 ÿ- as an electron donor (Eq. (15)) (Tatsumi et al.,
Machine Translated by Google
X. Ye et al.
Fig. 6. Schematic illustration of the mechanism of electrochemical regeneration.
1998). Q accepts electrons to form H2Q, and subsequently, the conversion of
O2 ÿ- to H2O2 is accelerated when catalyzed by H2Q (Eqs. (2) and (3)). This is
consistent with the test results for the content of H2O2 generated by the two
working electrodes (Fig. 5b). Additionally, if the applied electric field is large
enough, conductive GAC particles are polarized due to the shift in their electric
charge, converting each GAC particle into a charged microelectrode, with one
anodic and one cathodic side (Zhang et al., 2013) . Therefore, charged GAC
particles can induce the electro adsorption/desorption pollutants and their
Faraday reaction so that the adsorbed organic matter can be electrolytically
degraded (McQuillan et al., 2018). Additionally, GAC can improve system
performance and increase the formation of ÿOH by forming H2O2 at cathodically
polarized particles and degrading it to ÿOH (Eq. (16))
(Fortuny et al., 1998; Banuelos et al., 2014).
O2 + 2H+ + 2eÿ ÿH2O2
O2 + eÿ ÿ O%ÿ 2
O%ÿ
2
+ eÿ + 2H+ÿH2O2
Q+e ÿ ÿSQ%ÿ
SQ%ÿ + O2ÿO%ÿ
2
+Q
GAC + H2O2ÿGAC+ + OHÿ + %OH
In summary, the reduction of molecular oxygen on the electrode surface to
H2O2 is accelerated by anthraquinone catalysis. The accumulation of H2O2
content is higher in the AQS/PPy-GP regeneration system than in the GP,
leading to a higher ÿOH content. RhB can be easily oxidized to ÿOH, leading to
the cleavage of xanthene rings to form smaller aromatics (Fig. SM5). Further
oxidation of these aromatic in termediates by OH causes the ruptures of
benzene rings and the cleavage of C–N bonds to yield mainly aliphatic carboxylic
acids. Compared with the parent compound, these oxidation byproducts have
smaller molec ular sizes and are much less firmly bound with the GAC surface
(Liu et al., 2017). Therefore, they can be easily desorbed from GAC, and
regeneration comparably restores the porosity and adsorption capacity of GAC.
4. Conclusions
In the present study, we have successfully synthesized AQS/PPy-GP
cathode and achieved high regeneration efficiency of activated carbon, faster
organics degradation, and low system energy consumption. The isotherm and
kinetics study suggested that the experimental adsorption
Chemosphere 308 (2022) 136189
data perfectly fit the Langmuir and Elovich models, indicating mono layer and
chemical adsorption. The independent variables' optimum condition was
optimized with the RSM-BBD model, whereby applied current = 155 mA,
concentration of supporting electrolyte = 0.13 M, and regeneration time = 7 h.
AQS/PPy-GP has a higher efficiency in terms of RhB degradation and energy
consumption than bare GP, which the catalysis of anthraquinones could explain.
During the first regenerator ation, we achieved 97.3% regeneration efficiency
at an energy consumption of 1.38 kWh kgÿ PPy-GP system was 10% lower
1
than that of GP, which verified , and the energy consumption of the AQS/
that the resistance of AQS/PPy-GP cathode is much lower than that of GP when
assessed by EIS. The regeneration efficiency of the GAC treated with AQS/PPy-
GP was maintained at 76.6% after 8 consecutive cycles.
H2O2 generated in the electrolysis system increased, and the time of complete
degradation of organics was shortened by 25%. After regen eration, the total
pore volume and BET surface area were restored, and the structural integrity of
the regenerated GAC was preserved. More over, the proposed regeneration
mechanism suggested that AQS acts as a catalyst to promote the formation of
H2O2. This work lays the ground work in presenting AQS/PPy-GP as more
applicable as an economical and practical cathode material in the electrochemical
regeneration of activated carbons for the treatment of wastewaters resulting
from rapid developments in industrial processes.
Author contributions statement
Xiao Ye: Investigation, Formal analysis, Visualization, Writing – original
draft., Wangfeng Cai: Conceptualization, Funding acquisition, Project
administration., Ding Lu: Supervision, Writing – review & editing., Ruonan Liu:
Validation, Data curation., Yingdong Wu: Methodology, Supervision, Yan
Wang: Methodology, Resources.
Declaration of competing interest
(eleven)
The authors declare that they have no known competing financial interests
or personal relationships that could have appeared to influence the work
(12)
reported in this paper.
(13)
Data availability
(14)
No data was used for the research described in the article.
(fifteen)
Acknowledgments
(16)
The authors thank AiMi Academic Services (www.aimieditor.com)
for the English language editing and review services.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi. org/
10.1016/j.chemosphere.2022.136189.
References
Acuna-Bedoya, J., Comas-Cabrales, JA, Alvarez-Pugliese, CE, Marriaga-Cabrales, N.,
2020. Evaluation of electrolytic reactor configuration for the regeneration of
granular activated carbon saturated with methylene blue. J. Environ. Chem. Eng. 8,
104074.
Asgari, G., Seid-mohammadi, A., Rahmani, A., Samadi, MT, Salari, M., Alizadeh, S.,
Nematollahi, D., 2021. Diuron degradation using three-dimensional electro
peroxone (3D/E -peroxone) process in the presence of TiO2/GAC: application for real
wastewater and optimization using RSM-CCD and ANN-GA approaches.
Chemosphere 266.
Bai, CP, Xiong, XF, Gong, WQ, Feng, DX, Xian, M., Ge, ZX, Xu, NA, 2011.
Removal of rhodamine B by ozone-based advanced oxidation process. Desalination
278, 84–90.
Bai, J., Chao, YQ, Chen, YM, Wang, SZ, Qiu, RL, 2019. The effect of interaction
between bacillus subtilis DBM and soil minerals on Cu(II) and Pb(II) adsorption.
J. Environ. Sci. 78, 328–337.
8
Machine Translated by Google
X. Ye et al.
Bakheet, B., Yuan, S., Li, ZX, Wang, HJ, Zuo, JN, Komarneni, S., Wang, YJ, 2013.
Electro-peroxone treatment of orange II dye wastewater. Water Res. 47, 6234–6243.
Banuelos, JA, Ei-Ghenymy, A., Rodriguez, FJ, Manriquez, J., Bustos, E., Rodriguez,
A., Brillas, E., Godinez, LA, 2014. Study of an air diffusion activated carbon
packed electrode for an electro-fenton wastewater treatment. Electrochim.
Acta 140, 412–418.
Bao, M., Wang, D., Liu, SY, Kuang, L.L., Sun, J., Wang, F., Wen, Y.X., 2012.
Electrodeposition and electrocatalytic activity of Cu2O film on stainless steel
substrate. Appl. Surf. Sci. 258, 8008–8014.
Berenguer, R., Marco-Lozar, JP, Quijada, C., Cazorla-Amoros, D., Morallon, E., 2010.
Electrochemical regeneration and porosity recovery of phenol-saturated granular
activated carbon in an alkaline medium. Carbon 48, 2734–2745.
Brillas, E., Sires, I., Oturan, MA, 2009. Electro-fenton process and related
electrochemical technologies based on fenton's reaction chemistry. Chem. Rev. 109,
6570–6631.
Brouzgou, A., Song, S., Liang, Z.-X., Tsiakaras, P., 2016. Non-precious electrocatalysts
for oxygen reduction reaction in alkaline media: latest achievements on novel carbon
materials. Catalysts 6.
Brunauer, S., Deming, L., Deming, E.W., Teller, E., 1940. On a theory of the van der waals
adsorption of gases. J. Am. Chem. Soc. 1723–1732.
Chen, Z., Geng, S., Xiao, J., Zhao, F., Wang, K., Wang, Y., Tsiakaras, P., Song, S., 2022.
2ÿ
Understanding the selectivity trend of water and sulfate (SO4 ) oxidation on metal
oxides: on-site synthesis of persulfate, H2O2 for wastewater treatment. Chem. Eng. J.
431.
Fortuny, A., Font, J., Fabregat, A., 1998. Wet air oxidation of phenol using active carbon
as catalyst. Appl. Catal. B Environ. 19, 165–173.
Gad, HM, El-Sayed, AA, 2009. Activated carbon from agricultural by-products for the
removal of rhodamine-B from aqueous solution. J. Hazard Mater. 168, 1070–1081.
Gao, F.F., Du,
A potential-controlled ion pump based on a three-dimensional PPy@GO membrane
for separating dilute lead ions from wastewater. Electrochim. Minutes 236, 434–442.
Garcia-Rodriguez, O., Villot, A., Olvera-Vargas, H., Manager, C., Andres, Y., Lefebvre,
O., 2020. Impact of the saturation level on the electrochemical regeneration of
activated carbon in a single sequential reactor. Carbon 163, 265–275.
Georgi, A., Kopinke, F.D., 2005. Interaction of adsorption and catalytic reactions in water
decontamination processes part I. oxidation of organic contaminants with hydrogen
peroxide catalyzed by activated carbon. Appl. Catal. B Environ. 58, 9–18.
Hall, KR, Eagleton, LC, Acrivos, A., Vermeulen, T., 1966. Pore-and solid-diffusion
kinetics in fixed-bed adsorption under constant-pattern conditions. Ind. Eng. Chem.
Fundamental 5, 212–223.
Kadirvelu, K., Karthika, C., Vennilamani, N., Pattabhi, S., 2005. Activated carbon from
industrial solid waste as an adsorbent for the removal of rhodamine-B from aqueous
solution: kinetic and equilibrium studies. Chemosphere 60, 1009–1017.
Kundu, S., Chowdhury, IH, Naskar, MK, 2018. Hierarchical porous carbon
nanospheres for efficient removal of toxic organic water contaminants of phenol
and methylene blue. J Chem Eng Data 63, 559–573.
Li, J., Li, XY, Zhou, G.Q., Wang, W., Wang, C.W., Komarneni, S., Wang, Y.J., 2014.
Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared
by desilication with NaOH solutions. Appl. Catal. A-Gen. 470, 115–122.
Lian, Q., Ahmad, ZU, Gang, DD, Zappi, ME, Fortela, DLB, Hernandez, R., 2020. The
effects of carbon disulfide driven functionalization on graphene oxide for enhanced
Pb(II) adsorption: investigation of adsorption mechanism . Chemosphere
248, 126078.
Liu, S., Wang, Y., Wang, B., Huang, J., Deng, S., Yu, G., 2017. Regeneration of rhodamine
B saturated activated carbon by an electro-peroxone process. J.Clean. Prod. 168,
584–594.
Long, B., Qiao, Z., Zhang, J., Zhang, S., Balogun, M.-S., Lu, J., Song, S., Tong, Y., 2019.
Polypyrrole-encapsulated amorphous Bi2S3 hollow sphere for long life sodium
ion batteries and lithium–sulfur batteries. J. Mater. Chem A. 7, 11370–11378.
Long, B., Yang, H., Wang, F., Mao, Y., Balogun, M.-S., Song, S., Tong, Y., 2018.
Chemically-modified stainless steel mesh derived substrate-free iron-based
composite as anode materials for affordable flexible energy storage devices.
Electrochim. Minutes 284, 271–278.
Chemosphere 308 (2022) 136189
Lucking, F., Koser, H., Jank, M., Ritter, A., 1998. Iron powder, graphite and activated
carbon as catalysts for the oxidation of 4-chlorophenol with hydrogen peroxide in
aqueous solution. Water Res. 32, 2607–2614.
Martinez-Huitle, CA, Ferro, S., 2006. Electrochemical oxidation of organic pollutants
for the wastewater treatment: direct and indirect processes. Chem Soc Rev 35,
1324–1340.
McQuillan, RV, Stevens, GW, Mumford, KA, 2018. The electrochemical regeneration
of granular activated carbons: a review. J. Hazard Mater. 355, 34–49.
Oller, I., Malato, S., Sanchez-Perez, JA, 2011. Combination of advanced oxidation
Processes and biological treatments for wastewater decontamination–a review. Sci.
Total Environ. 409, 4141–4166.
Pipi, AR, Sires, I., De Andrade, AR, Brillas, E., 2014. Application of electrochemical advanced
oxidation processes to the mineralization of the herbicide diuron.
Chemosphere 109, 49–55.
Ramirez-Pereda, B., Alvarez-Gallegos, A., Rangel-Peraza, JG, Bustos-Terrones,
YA, 2018. Kinetics of acid orange 7 oxidation by using carbon fiber and
reticulated vitreous carbon in an electro-fenton process. J. Environ. Manag. 213, 279–287.
Roth, H., Gendel, Y., Buzatu, P., David, O., Wessling, M., 2016. Tubular carbon
Nanotube-based gas diffusion electrode removes persistent organic pollutants by
a cyclic adsorption-electro-fenton process. J. Hazard Mater. 307, 1–6.
Saleh, TA, Sari, A., Tuzen, M., 2017. Effective adsorption of antimony(III) from aqueous
solutions by polyamide-graphene composite as a novel adsorbent. Chem Eng J 307,
230–238.
Tatsumi, H., Nakase, H., Kano, K., Ikeda, T., 1998. Mechanistic study of the autoxidation
of reduced flavin and quinone compounds. J. Electroanal. Chem. 443, 236–242.
Tian, JN, Olajuyin, AM, Mu, TZ, Yang, MH, Xing, JM, 2016. Efficient degradation of rhodamine
B using modified graphite felt gas diffusion electrode by electro-fenton process. Environ.
Sci. Pollut. Res. 23, 11574–11583.
Trellu, C., Oturan, N., Keita, FK, Fourdrin, C., Pechaud, Y., Oturan, MA, 2018.
Regeneration of activated carbon fiber by the electro-fenton process. Environ. Sci.
Technol. 52, 7450–7457.
Wang, K., Dai, Q., Hu, C., Tong, Y., Wang, Y., Song, S., Dai, L., 2021. Earth-abundant
metal-free carbon-based electrocatalysts for Zn- air batteries to power
electrochemical generation of H2O2 for in-situ wastewater treatment. Chem. Eng. J.
416.
Wang, L.Z., Balasubramanian, N., 2009. Electrochemical regeneration of granular
activated carbon saturated with organic compounds. Chem Eng J 155, 763–768.
Yao , WK, Wang , Water Res. 88, 826–835.
You, XY, Chai, LY, Wang, YY, Su, YR, Zhao, N., Shu, YD, 2013. Regeneration of
activated carbon adsorbed EDTA by electrochemical method. T. Nonferr. Metal.
Soc. 23, 855–860.
Zhan, JH, Wang, YJ, Wang, HJ, Shen, WH, Pan, XJ, Wang, JL, Yu, G., 2016.
Electro-peroxone regeneration of phenol-saturated activated carbon fiber: the effects
of irreversible adsorption and operational parameters. Carbon 109, 321–330.
Zhang, C., Jiang, YH, Li, YL, Hu, ZX, Zhou, L., Zhou, M.H., 2013. Three-dimensional
electrochemical process for wastewater treatment: a general review. Chem Eng J
228, 455–467.
Zhang, C., Zhou, M., Ren, G., Yu, X., Ma, L., Yang, J., Yu, F., 2015. Heterogeneous
electro-fenton using modified iron-carbon as catalyst for 2 ,4-dichlorophenol
degradation: influence factors, mechanism and degradation pathway. Water Res.
70, 414–424.
Zhang, H., Li, Y., Zhao, Y., Li, G., Zhang, F., 2019. Carbon black oxidized by air
calcination for enhanced H2O2 generation and effective organics degradation. ACS
Appl. Mater. Interfaces 11, 27846–27853.
Zhou, W. , Meng,
Commun. 100, 85–89.
Zhou, W., Rajic, L., Zhao, Y., Gao, J., Qin, Y., Alshawabkeh, A.N., 2018a. Rates of H2O2
electrogeneration by reduction of anodic O2 at RVC foam cathodes in batch and flow-
through cells. Electrochim. Acta 277, 185–196.
Zhou, Y., Lu, H., Wang, J., Zhou, J., Leng, X., Liu, G., 2018b. Catalytic performance of quinone
and graphene-modified polyurethane foam on the decolorization of azo dye acid red 18 by
shewanella sp. RQs-106. J. Hazard Mater. 356, 82–90.