Journal of Environmental Chemical Engineering 9 (2021) 106072

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Journal of Environmental Chemical Engineering

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

Enhanced electrocatalytic degradation of bisphenol A by graphite/β-PbO2

anode in a three-dimensional electrochemical reactor
Mohammad Reza Samarghandi a, Amin Ansari b, Abdollah Dargahi c, *, Amir Shabanloo d, *,
Davood Nematollahi b, Mohammad Khazaei a, Hassan Zolghadr Nasab d, Yaser Vaziri d
a
Department of Environmental Health Engineering, Faculty of Health and Research Center for Health Sciences, Hamadan University of Medical Sciences, Hamadan, Iran
b
Faculty of Chemistry, Bu-Ali-Sina University, Hamedan, Iran
c
Social Determinants of Health Research Center, Ardabil University of Medical Sciences, Ardabil, Iran
d
Department of Environmental Health Engineering, Hamadan University of Medical Sciences, Hamadan, Iran

A R T I C L E I N F O A B S T R A C T

Editor: Despo Kassinos In this study, the electrocatalytic synergy of the graphite/β-PbO2 anode and granular activated carbon (GAC)
particles electrodes for bisphenol A (BPA) degradation are investigated in a three-dimensional electrochemical
Keywords: reactor (3DER). The graphite/β-PbO2 anode was prepared by anodic deposition method and the electrocatalytic
Synergy properties of lead oxide film were studied by FESEM, XRD, EDX-mapping, linear sweep voltammetry and
Three-dimensional electrochemical reactor
accelerated lifetime test techniques. The effect of five independent variables including pH, Na2SO4 concentra­
Graphite/β-PbO2 anode
tion, current density, GAC amount, and reaction time on the system response was optimized by an orthogonal
Optimization
Electrocatalytic degradation central composite-genetic algorithm (OCCD-GA). The results showed that β-PbO2 crystals were deposited as
completely compact pyramidal clusters on the graphite surface. In addition, the service life and oxygen evolution
potential (OEP) for the electrocatalytic layer of β-PbO2 were 90 h and 2 V, respectively. Based on the developed
quadratic model (R2 > 0.99 and p-value < 0.0001), the optimal points for pH, Na2SO4 concentration, current
density, GAC amount, and reaction time were predicted to be 4.6, 0.074 mol L− 1, 35.7 mA cm− 2, 25 g, and 80
min, respectively. Under optimal conditions, BPA removal efficiency in 3DER system and separate application of
electrocatalytic degradation and GAC were obtained 98.8%, 72.2% and 9.75%, respectively. Thus, the electro­
catalytic synergy of 3DER system due to lead oxide layer and GAC particle electrodes in BPA degradation was
calculated to be 35.5%. LC-MS analysis was used to identity the intermediates formed during BPA degradation.
The final degradation intermediates were short-chain acids including adipic acid, malonic acid and, acetic acid.

1. Introduction
Bisphenol A (BPA) is a widely used chemical in the polycarbonate
plastics and epoxy resins industries. Contamination of water sources
with BPA is occurred through both untreated industrial wastewater and
landfill leachate [1]. Due to the high biological resistance of BPA, it can
be measured in μg L− 1 concentrations in water sources. In addition,
research shows that BPA has a high potential to accumulate in humans
and other living organisms [2,3]. BPA is an endocrine disrupting com­
pound whose negative effects can be seen even at low concentrations of
ng L− 1 [4,5]. Proper treatment of industrial wastewater containing BPA
is a management strategy to reduce the concentration of this toxic
pollutant in aquatic environments. However, due to the toxicity and
high resistance of BPA, conventional biological treatment systems are
not able to remove it and require adapted microorganisms [6]. In recent
years, electrochemical advanced oxidation processes (EAOPs) were used
for the degradation bio-refractory and toxic organic pollutants [7–10].
Simple design, no sludge production and no need for additional chem­
icals, versatility, high efficiency and environmental friendliness are the
main advantages of EAOPs [11]. However, the main drawback of these
systems is the mass transfer limitation, which reduces the efficiency of
the system, increases energy consumption, and thus increases treatment
costs [12].
Simultaneous application of EAOP with particle electrodes such as
granular activated carbon (GAC) due to its high specific surface area and
high electrical activity increases the mass transfer coefficient and thus
reduces the system energy consumption [13]. This performance
improvement is due to the synergy of electrocatalytic degradation and

* Corresponding authors.
E-mail addresses: a.dargahi29@yahoo.com (A. Dargahi), shabanlo_a@yahoo.com (A. Shabanloo).

https://doi.org/10.1016/j.jece.2021.106072
Received 20 April 2021; Received in revised form 15 June 2021; Accepted 15 July 2021
Available online 18 July 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
M.R. Samarghandi et al.
the sorption/electrosorption of pollutants on the surface of the metal
oxide anode and the GAC particle electrode [14]. This hybrid system is
known as the three-dimensional electrochemical reactor (3DER). By
applying a suitable electric field, the GAC particles are polarized and
produce a large number of bipolar microelectrodes [15]. Organic con­
taminants are adsorbed on the anode surface of the microelectrodes and
then destroyed, leading to continuous regeneration of GAC [13]. As
shown in Eqs. (1) and (2), another role of the GAC catalyst is to produce
hydroxyl radicals (HO• ) by cathodic reduction of oxygen (O2) at the
surface of microelectrodes [16].
O2 + 2H+ + 2e− →H2 O2 (1)
(2)
GAC surface
H2 O2 ̅̅̅̅̅̅̅̅→HO•
The anode material has a significant effect on the electrocatalytic
degradation of organic pollutants. The PbO2 anode is a non-active anode
with excellent electrocatalytic performance in the production of HO•
radicals. Simple construction, long service life, and high oxygen evolu­
tion potential are other advantages of this anode [17]. Mineralization of
organic contaminants is done at the anode surface through Eqs. (3) and
(4) [10,18]. Titanium is used as the most common substrate for the
production of PbO2 anodes [19–21]. However, Ansari and Nematollahi
showed that the electrocatalytic performance of PbO2 film on graphite
electrode substrate (graphite/β-PbO2) is significantly improved [22].
PbO2 + H2 O→PbO2 (HO• ) + H+ + e– (3)
PbO2 (HO• ) + organics→PbO2 + mCO2 + nH2 O + H+ + e– (4)
Optimizing multivariate processes with the one-factor-at-a-time
(OFAT) method is complex and requires a large number of experi­
ments [23]. Central composite design (CCD) is a powerful tool for
modeling the effects of independent variables on system response
[24–26]. Genetic algorithm (GA) is also an optimization method that
uses the model proposed by CCD to predict the system response at the
optimal points of variables [27].
To the best of our knowledge, no study has been performed to
investigate the electrocatalytic synergy of graphite/β-PbO2 anode and
GAC particle electrodes in the 3DER system for BPA degradation. The
graphite/β-PbO2 anode was prepared by electrodeposition method and
the electrocatalytic properties of lead oxide film were studied by FESEM,
XRD, EDX-mapping, linear sweep voltammetry and accelerated lifetime
test techniques. The effect of five independent variables including so­
lution pH, Na2SO4 electrolyte concentration, current density, GAC
amount, and reaction time on BPA removal efficiency was modeled and
optimized by the CCD-GA method. Under optimal conditions, the elec­
trocatalytic synergy of the lead oxide film and GAC particle electrodes
was studied by comparing the kinetic coefficients. Finally, degradation
pathway was proposed for BPA mineralization in the 3DER system.
2. Material and methods
2.1. Chemicals
BPA (C15H16O2, ≥ 99%), lead nitrate (Pb (NO3)2, ≥ 99%), sodium
fluoride (NaF, ≥ 99%), sodium sulfate (Na2SO4, ≥ 99%), nitric acid
(HNO3, ≥ 90%), sulfuric acid (H2SO4, ≥ 98%), sodium hydroxide
(NaOH pellets, ≥ 98%), and GAC (8–10 mesh) were purchased from
Merck Company. Graphite sheets were provided from Atlas Tajhiz
Mandegar Co., Tehran, Iran.
2.2. Preparation of graphite/β-PbO2 anode
The graphite/β-PbO2 anode was prepared by electrochemical pre­
cipitation method. For this purpose, the graphite substrates were first
polished and then sonicated in 40% sodium hydroxide solution for
2
Journal of Environmental Chemical Engineering 9 (2021) 106072
15 min. The prepared substrates were washed several times with
distilled water and then dried by hot air. Anodic precipitation of PbO2
film on graphite substrate was performed in a single-compartment cell
with a constant current (MEGATEK, MP-3005, China). The prepared
graphite sheet with dimensions of 10 cm × 3 cm × 0.2 cm was used as
the anode and two stainless-steel sheets with the same dimensions were
used as the cathode. Electrodeposition was performed at a current
density of 7.5 mA cm− 2 for 180 min in a 0.1 M nitric acid solution
containing 0.5 M lead nitrate and 0.05 M sodium fluoride [19].
The surface morphology and chemical composition of the prepared
electrode were studied by Field emission scanning electron microscopy
(FESEM, FEI-Nova NanoSEM 450) and energy-dispersive X-ray spec­
troscopy mapping (EDX; Bruker XFlash6L10) analysis, respectively.
Crystallite structure of PbO2 film was studied by X-ray diffraction
analysis (XRD, Ultima IV, Rigaku). The oxygen evolution potential for
the graphite/β-PbO2 electrode was investigated by linear sweep vol­
tammetry (LSV). LSV and cyclic voltammetry (CV) measurements were
performed at room temperature using the Autolab PGSTAT-20 instru­
ment monitored with the Electrochemical System Software (Nova). A
glassy carbon disc (1.8 mm2) was used as a working electrode. The
counter electrode and references electrode were a platinum wire and
Ag/AgCl (3 M) electrode, respectively. The cyclic voltammetry experi­
ments were accomplished in a conventional three-electrode one-
compartment glass cell. An accelerated lifetime test was used to deter­
mine the stability of the graphite/β-PbO2 anode. The experiment was
performed in a conventional three-electrode cell system containing
2.0 M H2SO4 at 200 mA cm− 2 at room temperature. Working, reference,
and counter electrodes were graphite/β-PbO2, saturated calomel elec­
trode (SCE), and platinum wire, respectively. The cell potential was
monitored periodically during the test. The time elapsed to increase the
cell potential to 10 V is reported as the service life of the graphite/
β-PbO2 anode [28].
2.3. Electrocatalytic degradation of BPA in 3DER system
All degradation experiments were performed in a batch electrolytic
cell containing 250 mL of BPA solution. GAC was rinsed several times
with distilled water and then dried at 105 ◦ C for 24 h. Then, to eliminate
the effect of GAC adsorption in degradation reactions, GAC was
completely mixed with BPA solution before application in 3DER system
(Pre-exposed GAC) for 15 cycles of 80 min. The graphite/β-PbO2 anode
and the stainless-steel cathode (No. 316) with the same dimensions
(10 cm × 3 cm) were placed parallel to each other inside the electric cell
at a distance of 4 cm. Different amounts of GAC in the range of 5–25 g
were packed in a plastic net between the anode and cathode. An air
pump and a diffuser with a flow rate of 2.5 L min− 1 were used to stir the
contents of the cell. A DC power supply (DAZHENG PS-305D, China) was
used to supply current density in the range of 7.5–37.5 mA cm− 2.
Schematic of the 3DER was provided in Fig. 1. Optimization of the 3DER
system was performed at a constant BPA concentration of 45 mg L− 1.
Na2SO4 in the range of 0.02–0.1 mol L− 1 was used as the supporting
electrolyte. The pH of the samples was adjusted in the range of 3–10 by
0.5 mol L− 1 H2SO4 and NaOH solutions (pH meter; SensION, HACH). At
the end of the reaction time, in the range of 10–80 min, a suitable
amount of reaction solution was withdrawn from the reactor for the
necessary analysis.
2.4. Analytical methods
The absorbance of residual BPA was measured by a UV–vis spec­
trophotometer (DR6000, HACH) at a maximum wavelength of 278 nm
[29]. BPA mineralization were investigated by a total organic carbon
analyzer (TOC, Elementar Analysensysteme GmbH, Germany). A liquid
chromatography-mass spectrometry (LC-MS) analysis (Shimadzu LCMS
2010 A) equipped with an Eclipse Atlantis T3 C18 column
(2.1 × 150 mm, 3 µm) was used to identify the intermediates. A 60:40
M.R. Samarghandi et al.
Fig. 1. Schematic of the 3DER (1. DC power supply 2. Anode, 3. Cathode, 4. GAC pack, 5. Air diffuser and 6. Air pump).
(v/v) mixture of acetonitrile and water was used as a mobile phase at a
flow rate of 0.3 mL min− 1 at ambient temperature. BPA removal effi­
ciency and its kinetics were calculated by Eqs. (5) and (6).
[BPA]0 − [BPA]t
η (%) = × 100
[BPA]0
[BPA]t
ln = − kobs × t
[BPA]0
In this equation, η indicates the BPA removal efficiency (%). [BPA]0
and [BPA]t are the concentration of BPA (mg L− 1) at t = 0 min and t = t
min, respectively. kobs and t are pseudo-first-order kinetic coefficient
(min− 1) and reaction time (min), respectively. The electrocatalytic
synergy of lead oxide films and GAC particle electrodes was calculated
by Eq. (7) [16]. The energy consumption (EC) for degradation of 1 g of
BPA (kW h g− 1 BPA) was calculated by Eq. (8) [30].
k1 − k2 − k3 − k4
Electrocatalytic synergy(%) = × 100
k1
UIt
EC =
([BPA]0 − [BPA]t )V
k1 and k2 are the kinetic coefficients of BPA removal in 3DER system
with graphite/β-PbO2 and graphite anodes, respectively. k3 shows the
kinetic coefficient of BPA removal in the electrocatalytic degradation
system without the presence of GAC. k4 also represents the kinetic co­
efficients of BPA removal in separate applications of GAC without
electrochemical processes. U and I are the voltage (V) and current (A) of
the electrochemical oxidation system, respectively. t (h) is the time of
the electrochemical process. V (L) is the volume of the treated solution.
[BPA]0 and [BPA]t are the concentration of BPA (mg L− 1) at time t = 0 h
and t = t h, respectively.
2.5. Experimental design with CCD and process optimization with GA
Response Surface Methodology (RSM) has been widely used to
design various toxic contaminant removal processes [31–34]. CCD is one
of the most widely used statistical methods of RSM that can be used to
model the effects of operational parameters on system response [35,36].
In the present study, the linear, interactive, and quadratic effects of five
operating parameters including initial solution pH, Na2SO4 electrolyte
concentration, current density, GAC amount, and reaction time at five
levels (− α, − 1, 0, +1, +α) on BPA removal efficiency (System response)
was modeled by a full orthogonal CCD (OCCD). For an OCCD, the value
of α (level distance) is calculated by Eq. (9) [24].
Journal of Environmental Chemical Engineering 9 (2021) 106072
(√̅̅̅̅̅̅ )1/2
α=
Nf − f
(9)
2
In this equation, N is the total number of experiments and f is the
(5) number of experiments at the factorial points. To calculate N and f, Eqs.
(10) and (11) were used, respectively.
(6) N= 2K + 2K + C(K = 5) (10)
f = 2K (11)
In this equation, K is the number of operational parameters or in­
dependent variables; in this study, K = 5. C is also the number of ex­
periments repeated at the center point. Accordingly, a 5-level, 5-factor
full OCCD consists of 50 tests (N) of which 32 tests are at factorial points
(f = 2K); 10 tests are at axial points (2K), and 8 tests are at center points
(C) [26]. By placing the values of N and f in Eq. (9), the values of α were
obtained to be 2. Table 1 shows the five operational parameters and
(7) their five levels. To increase the accuracy of the study in predicting the
response, the designed experiments were performed with three repli­
cations. Fifty tests designed with experimental and predicted removal
(8)
efficiency can be seen in Table 2. Test design and data analysis were
performed with Design-Expert 12.0 software. GA technique was used to
predict the system response in optimal conditions. GA is an optimization
method based on Charles Darwin’s theory of survival of the fittest.
Optimization begins with creating a random population that provides
appropriate solutions to a problem. In the following, the best solution is
used to create a new population, on the assumption that it is better than
the previous one. This process continues until the best possible solution
and optimal conditions are obtained. MATLAB R2013a software was
used to optimize the process by the GA method [37].
3. Results and discussion
3.1. Characterization of the graphite/β-PbO2 anode
FESEM images of graphite substrate and graphite/β-PbO2 anode with
different magnifications were shown in Fig. 2(a)–(d). As shown in Fig. 2
(a), the surface of the graphite bare substrate consists of homogeneous
graphite flakes on a micro-scale. Fig. 2(b)–(d) clearly shows the
compact, uniform, crack-free and clustered structures of PbO2 electro­
deposited on the graphite substrate [9]. XRD pattern of graphite/β-PbO2
anode is presented in Fig. 2(e). All observed diffraction peaks at 2θ
= 25.4◦ (110), 32◦ (101), 36.2◦ (200), 40.4◦ (112), 45◦ (022), 49.2◦
(211), 52.2◦ (220), 55◦ (002), 58.9◦ (310), 60◦ (112), 62.7◦ (301), 67◦
(202) and 74.5◦ (321) belong to the tetragonal β-PbO2 structures which
3
M.R. Samarghandi et al. Journal of Environmental Chemical Engineering 9 (2021) 106072

Table 1
Operational parameters and their study area.
Independent variables Symbols Unit Coded levels

− 2 − 1 0 +1 +2

pH A – 3 4.75 6.5 8.25 10

Na2SO4 concentration B mol L− 1 0.02 0.04 0.06 0.08 0.1
Current density C mA cm− 2 7.5 15 22.5 30 37.5
GAC amount D g 5 10 15 20 25
Reaction time E min 10 27.5 45 62.5 80

Table 2
The experimental and predicted removal efficiency of BPA in 3DER system.
Run Coded variablesa BPA removal (%) Run Coded variables BPA removal (%)

A B C D E Experimental Predicted A B C D E Experimental Predicted

1 − 1 − 1 − 1 − 1 1 68.80 68.91 26 − 2 0 0 0 0 69.90 69.73

2 0 0 0 0 0 69.10 69.56 27 0 0 0 0 2 85.40 85.29
3 1 1 1 − 1 1 74.80 74.80 28 − 1 − 1 − 1 − 1 − 1 53.30 53.80
4 1 1 − 1 1 − 1 58.20 58.91 29 − 1 1 − 1 − 1 1 71.80 71.90
5 − 1 − 1 − 1 1 − 1 60.90 60.72 30 0 0 0 2 0 75.60 75.39
6 0 0 0 0 0 69.60 69.56 31 1 − 1 1 − 1 − 1 55.90 55.72
7 − 1 1 − 1 − 1 − 1 55.50 55.55 32 0 − 2 0 0 0 64.30 64.29
8 − 1 1 − 1 1 1 79.10 79.33 33 − 1 − 1 − 1 1 1 76.50 76.34
9 0 0 0 0 0 70.00 69.56 34 1 − 1 1 1 − 1 62.10 62.07
10 0 0 0 0 0 69.40 69.56 35 − 1 − 1 1 − 1 1 74.90 75.06
11 − 1 − 1 1 1 − 1 65.10 65.63 36 1 − 1 1 1 1 79.90 79.52
12 0 0 0 0 0 69.80 69.56 37 − 1 − 1 1 1 1 82.60 82.49
13 0 0 0 0 0 70.10 69.56 38 1 − 1 − 1 1 1 73.20 73.37
14 0 0 0 0 0 69.30 69.56 39 1 1 1 − 1 − 1 56.30 56.63
15 0 0 0 0 0 69.00 69.56 40 1 1 − 1 − 1 1 69.80 69.49
16 − 1 1 1 1 1 84.40 84.65 41 1 − 1 − 1 1 − 1 57.40 57.16
17 0 0 2 0 0 73.30 73.56 42 1 − 1 − 1 − 1 1 66.30 66.50
18 0 0 0 0 − 2 51.60 51.50 43 0 2 0 0 0 68.40 68.20
19 1 1 1 1 − 1 63.30 62.99 44 − 1 1 1 1 − 1 66.60 66.55
20 1 − 1 1 − 1 1 72.50 72.65 45 − 1 − 1 1 − 1 − 1 59.10 58.71
21 0 0 0 − 2 0 61.60 61.60 46 1 1 − 1 − 1 − 1 52.80 52.56
22 − 1 1 1 − 1 1 77.50 77.21 47 − 1 1 − 1 1 − 1 62.60 62.47
23 − 1 1 1 − 1 − 1 59.70 59.63 48 1 1 1 1 1 81.60 81.67
24 1 − 1 − 1 − 1 − 1 50.70 50.80 49 0 0 − 2 0 0 63.80 63.33
25 2 0 0 0 0 63.80 63.76 50 1 1 − 1 1 1 76.10 76.36
a
A, B, C, D, and E represent the independent variables defined in Table 1.

can be indexed with the standard JCPDS data card no. 89-2805 [38]. In
contrast, diffraction peaks appeared at 2θ = 23.6◦ (110), 28.5◦ (111),
33.1◦ (002) and 56.5◦ (113) belong to the α-PbO2 phase, which can be
indexed with JCPDS data card no. 72-2440 [9]. EDX spectrum and
EDX-mapping of graphite/β-PbO2 anode were presented in Fig. 3. The
elemental composition of the graphite/β-PbO2 anode consists of lead
and oxygen with a weight percentage (wt%) of 79.64 and 20.36,
respectively. Also, in the EDX spectrum, the carbon peak is not observed,
which indicates that the graphite substrate is well covered with PbO2
layers. The uniform distribution of lead and oxygen at the anode surface
is also clearly seen in mapping images.
Oxygen formation is a side reaction in the electrocatalytic degrada­
tion process of organic pollutants that leads to reduced current effi­
ciency during the process. The oxygen evolution performance of the
graphite/β-PbO2 electrode was investigated by LSV technique. The
linear polarization curve of the prepared electrode can be seen in Fig. 4
(a). Accordingly, the oxygen evolution potential (OEP) of graphite/
β-PbO2 electrode is 2 V, which is a desirable feature compared to
modified mixed metals oxide anodes such as Ti/SnO2-Sb2O3/stearic
acid-Yb-PbO2 (2 V) [39], Ti/SnO2-Sb2O3/α, β-PbO2 (2.09 V) [19],
Ti/SnO2-Sb2O3/Yb-doped PbO2 (1.9 V) [40], and Ti/Sn-SbOx/­
indium-doped PbO2 (2.08 V) [41]. The anode stability is one of the
important parameters for its application in real-scale applications. The
accelerated lifetime test was performed to judge the stability of the
prepared electrode. Fig. 4(b) shows the cell potential–time response of
graphite/β-PbO2 anode. As can be seen, the stable cell potential is about
3 V. However, the cell potential suddenly began to increase after 70 h
and eventually increased to more than 10 V after 90 h. In other words,
the service life of graphite/β-PbO2 anode is 90 h, which is longer than
the reported values for Pb/PbO2 (34 h at 250 mA cm− 2) [42], Ti/PbO2
(14 h at 250 mA cm− 2) [43] and Ti/PbO2-Co-Pr (84 h at 250 mA cm− 2)
[20] anodes.
3.2. The effect of operational parameters on electrocatalytic degradation
BPA
3.2.1. The effect of solution pH and Na2SO4 concentration
In this study, contour and 3D response surface plots were used to
show the interaction effects of operational parameters on system
response. The effect of the initial pH of solution on BPA removal effi­
ciency in interaction with Na2SO4 electrolyte concentration was pro­
vided in Fig. 5(a) and (b). As can be seen, at a constant concentration of
45 mg L− 1 BPA, a current density of 22.5 mA cm− 2, a GAC amount of
15 g, and a reaction time of 45 min, the BPA removal efficiency in­
creases with increasing solution pH from 3 to 4.64. However, with a
further increase in the solution pH in the range of 4.64–10, the BPA
removal efficiency was significantly reduced. Thus, the highest BPA
removal efficiency was 70.64% at a pH of 4.64 and the lowest removal
efficiency was 58.59% at a pH of 10.
Solution pH is one of the most important operational parameters
affecting the performance of electrocatalytic degradation processes.
Dissociation constant (pKa) for BPA has been reported in the range of
9.7–10.2, which means that at pHs below 9.7, BPA is in the molecular
form [44]. However, BPA molecules lose two ionizable hydrogen atoms

4
M.R. Samarghandi et al.
Fig. 2. (a) FESEM image of graphite substrate, (b)–(d) FESEM images of graphite/β-PbO2 anode. (e) XRD pattern of the graphite/β-PbO2 anode.
under strongly alkaline conditions (pH > 9.7), thus facilitating the
oxidation of the pollutant by HO• radicals [45]. Despite this feature for
BPA, in our study the highest removal efficiency was observed in acidic
conditions, the reasons for which are as follows; (i) the oxidation po­
tential of HO• is strongly dependent on the pH of the solution, so that as
the pH of the solution increases, the oxidation potential of HO• decreases
dramatically from about 2.4–2.7 V to about 1–1.29 V in alkaline con­
ditions [46]; (ii) in an anodic oxidation system, there is always a
competition between the oxygen evolution reaction and the electro­
catalytic degradation of organic matter on the anode surface. In alkaline
conditions, the oxygen evolution side reaction is enhanced, resulting in a
decrease in reaction current efficiency and a decrease in the degradation
efficiency of organic pollutants at the anode surface [47]. In contrast,
5
Journal of Environmental Chemical Engineering 9 (2021) 106072
acidic conditions improve the current efficiency for direct and indirect
oxidation of organic pollutants at the anode surface by controlling the
oxygen evolution reaction [48], (iii) with the occurrence of hydrogen
evolution reaction at the cathode surface, hydrogen ions (H+) are used
to form H2, which leads to an increase in solution pH, a decrease in
conductivity, and thus a decrease in the efficiency of the electrochemical
oxidation system [49]. In addition, the alkaline conditions of the solu­
tion lead to the formation of carbonates and bicarbonates, the most
important adverse effect of which is the scavenge of HO• radicals and
their removal from the solution [13].
In a study by Sun et al. for degradation of chloramphenicol in a 3DER
with Ti-Sn/γ-Al2O3 particle electrodes, the maximum removal efficiency
of chloramphenicol was in acidic conditions [50]. Also, in a study by Li
M.R. Samarghandi et al. Journal of Environmental Chemical Engineering 9 (2021) 106072

Fig. 3. EDX spectrum and EDX mapping of the graphite/β-PbO2 anode.

6
M.R. Samarghandi et al.
1 1
Fig. 4. (a) LSV of the graphite/β-PbO2 anode at a scan rate of 100 mV s−
for accelerated lifetime test of the graphite/β-PbO2 anode.
et al. for removal of acid orange 7 in a 3DER with TiO2-SiO2/GAC par­
ticle electrode, the optimum pH for 83.2% of decolorization was 3 [51].
Ji et al. used multi-response optimization to investigate the degradation
of rhodamine B in a 3DER with GAC particle electrodes. The optimum
pH for removing 60.13% of COD at 30 min reaction time was 5.99 [52].
Sowmiya et al. used GAC as a particle electrode in a 3DER system to
remove reactive black B. In their study, the optimal pH for mineraliza­
tion of reactive black B was reported to be 3 [53].
The interaction effect of different concentrations of Na2SO4 elec­
trolyte in the range of 0.02–0.1 mol L− 1 with pH was represented in
Fig. 5(a) and (b). It is well known that BPA removal efficiency is
dependent on Na2SO4 concentration. As shown in Fig. 5(a), at a constant
pH of 4.64, with increasing Na2SO4 concentration in the range of
0.02–0.07 mol L− 1, the removal efficiency increased from about 65 to
70.64%. However, with a further increase in Na2SO4 concentration in
the range of 0.07–0.1 mol L− 1, the removal efficiency, with a slight
decrease, has reached about 68.5%.
In the use of Na2SO4 as a supporting electrolyte, the degradation of
organic pollutants is mainly done by HO• at the anode surface. However,
in some pH values, Na2SO4 electrolyte may prevent the degradation of
organic matter in the electrocatalytic degradation system. In a study
conducted by Li et al. for the degradation of reactive blue 19 in an
electrochemical system, the highest removal efficiency was obtained in
the presence of Na2SO4 electrolyte at pH 5.5, because the production of
HO• is limited under strong alkaline and acidic conditions [54].
Increasing the concentration of Na2SO4 enhances the performance of
electrochemical degradation systems to remove organic pollutants by
improving electron transfer and increasing HO• production at the anode
surface [9]. However, increasing Na2SO4 from the optimal concentra­
tion leads to the accumulation of excess ions on the surface of the
cathode, anode, and particle electrodes, which prevents the degradation
of the contaminant [55,56]. In the study of Yao et al., increasing the
Na2SO4 concentration from 0.15 mol L− 1 reduced the electrocatalytic
degradation efficiency of thiamethoxam [57]. Also, in the study of Li
et al., the optimal concentration of Na2SO4 for removal of acid orange 7
was reported to be 0.07 mol L− 1 [51]. Guo et al. have used a 3DER with
a graphene/polyurethane particle electrode to remove levofloxacin. In
their study, the optimal concentration of Na2SO4 was 7 mmol L− 1, and
by increasing the concentration of Na2SO4 from 14 mmol L− 1, the sys­
tem performance was significantly reduced [58].
3.2.2. The effect of current density
The interaction effect of current density in the range of
7.5–37.5 mA cm− 2 and Na2SO4 electrolyte concentration on BPA
removal efficiency were presented in Fig. 5(c) and (d). It is well known
Journal of Environmental Chemical Engineering 9 (2021) 106072
in 0.25 mol L− Na2SO4 and pH = 6.0 and room temperature. (b) Cell potential–time curve
that with increasing current density, the efficiency of BPA removal in­
creases. At a constant concentration of 0.07 mol L− 1 Na2SO4 electrolyte,
the BPA removal efficiency increased from about 62 to 73.64% by
increasing the current density in the range of 7.5–37.5 mA cm− 2. The
lowest removal efficiency of BPA (57.3%) was observed in the current
density of 7.5 mA cm− 2 and the concentration of 0.02 mol L− 1 Na2SO4.
Increasing the current density leads to the production of higher amounts
of HO• at the anode surface, thereby increasing the contaminant
removal efficiency. In addition, an increase in current density may lead
to an increase in the production rate of HO• at the surface of polarized
particle electrodes through Eqs. (1) and (2), which also leads to an in­
crease in the oxidation rate of organic pollutants in a 3DER [58,59].
According to the reports, the operation of electrocatalytic degradation
systems in an optimal amount of current density prevents the occurrence
of unwanted side reactions such as the evolution of hydrogen and oxy­
gen at the surface of the cathode and anode electrodes [30,60]. These
side reactions compete with the removal of organic pollutants in the
degradation system, which results in a reduction in the system efficiency
in the removal of organic matter [61].
Wei et al. have reported an optimal current density of 30 mA cm− 2
for the pre-treatment of heavy oil refinery wastewater in a 3DER system
equipped with GAC particle electrodes [13]. In the study of Sun et al.,
the optimal current for degradation of chloramphenicol with
Ti-Sn/γ-Al2O3 particle electrodes was reported to be 0.1 A. Further in­
crease of current applied to the system in the range of 0.4–0.5 A not only
reduced the efficiency of pollutant removal but also led to a significant
increase in energy consumption [50].
3.2.3. The effect of GAC particle electrode and reaction time
In order to determine the effect of GAC on BPA removal efficiency in
the 3DER, the effect of GAC in the range of 5–25 g on removal efficiency
was investigated. Fig. 5(e) and (f) show the effect of GAC interaction and
reaction time on removal efficiency. As it turns out, the efficiency of BPA
removal depends on the GAC and the reaction time. BPA removal effi­
ciency increased with increasing GAC amount and reaction time. In GAC
interaction and reaction time, the lowest removal efficiency of 44.2%
was achieved at a GAC amount of 5 g and reaction time of 10 min, and
the highest removal efficiency of 91.4% was obtained at GAC amount of
25 g and reaction time of 80 min. Also, at a constant amount of 25 g
GAC, with increasing the reaction time in the range of 10–80 min, the
BPA removal efficiency increased from about 56 to 91.4% and at a
constant time of 80 min, with increasing the GAC amount from 5 to 25 g,
the system performance in removing BPA improved from about 78 to
91.4%.
GAC under the electric field leads to the formation of a large number
7
M.R. Samarghandi et al. Journal of Environmental Chemical Engineering 9 (2021) 106072

Fig. 5. The contour and 3D response surface plots to show the interaction effects of operational parameters at central points: (a) and (b) the interaction of pH and
Na2SO4, (c) and (d) the interaction of Na2SO4 and current density, (e) and (f) the interaction of reaction time and GAC amount.

8
M.R. Samarghandi et al. Journal of Environmental Chemical Engineering 9 (2021) 106072

of microelectrodes that these polarized particles are able to improve the

overall performance of the 3DER through Eqs. (1) and (2) [13]. In the
study conducted by Jung et al., the optimal GAC amount for greywater
treatment in a fluidized 3DER system was obtained to be 47.1 g by the
Box–Behnken design statistical method [49]. Also, in a study conducted
by Sowmiya et al. for the electrochemical degradation of Reactive Black
B with a GAC particle electrode, the optimal GAC value was 5 g [53].
Increasing the time of the electrocatalytic degradation process provides
more opportunities to perform Eqs. (3) and (4), which lead to the pro­
duction of more HO• radicals and an increase in the mineralization rate
of organic pollutants [62–65].
3.3. Modeling and optimization of BPA removal in 3DER system
To model BPA degradation in the 3DER system, 50 experiments were
designed by an OCCD. Table 2 shows the results of the experimental and
predicted removal of BPA. Data analysis showed that the changes in the
system response to the operating parameters follow a quadratic model
well (R2 > 0.9). To achieve a compact and robust model, parameters
with p-value > 0.05 were excluded from the model [24]. Accordingly,
the system response was affected by five linear effects (A, B, C, D, and E),
six interactive effects (AD, AE, BC, BE, CE, and DE), and five quadratic
effects (A2, B2, C2, D2, and E2). The ANOVA results were presented in
Table 3. For the reduced model, F-value and p-value were 2001.26 and
< 0.001, respectively, which designates that the proposed model is
significant for predicting the response. For Lack of Fit, these values were
0.6344 and 0.8133, respectively, which indicates that this parameter is
not statistically significant [9]. In other words, the model well fits with
the available data. The values of R2 and adj-R2 of the model were 0.9990
and 0.9985, respectively, which confirms the high accuracy of the
model. On the other hand, the close values of these two parameters
indicate that there are no unnecessary parameters in the model [27].
Diagnostic plots were used to further investigate the adequacy of the
model. Fig. S1(a) shows that almost all data points are distributed on the
center straight line, indicating a normal distribution of data. Fig. S1(b)
and (c) show that all residuals are randomly scattered within the stan­
dard deviation range, which approves that none of the experiments need
to be repeated [66].
The final model equation for predicting the system response was
presented in Eq. (12). To optimize the BPA removal in 3DER system with
the GA technique, Eq. (12) was used as input fitness function and in­
dependent variables were defined in their ± α values [25].
BPA removal (%) =12.122+2.162 (A)+289.316 (B)+ 0.542 (C)
+1.048 (D) +0.409 (E)− 0.016 (AD)
+0.004 (AE) − 1.395 (BC) +0.883 (BE)
( ) (12)
+0.002 (CE) +0.001 (DE)− 0.230 A2
( 2) ( 2) ( )
− 2073.43 B − 0.004 C − 0.010 D2
( 2)
− 0.0009 E
Here, A, B, C, D, and E are the five independent variables in this study
that are defined in Table 1. Fig. 6(a) shows a gradual decrease in the best
fitness and mean fitness versus generation. As observed, the process
optimization process has reached the best possible solution after 30
repetitions. Optimal points for BPA removal in the 3DER system were
presented in Fig. 6(b). Accordingly, the optimal points for pH, Na2SO4
concentration, current density, GAC amount, and reaction time were
4.6, 0.074 mol L− 1, 37.5 mA cm− 2, 25 g, and 80 min, respectively. Under
these conditions, the maximum predicted removal efficiency was
98.06%. An experiment was performed under optimal conditions with
three repetitions to check the accuracy of the model prediction. Under
optimal conditions, the maximum efficiency of experimental removal
was about 98.8%, which indicates the high accuracy of the GA method
for predicting system response. Contour response surface and one-factor
plots were used to show the interaction and linear effects of independent
variables on system response under optimal conditions, respectively.
Figs. 7 and S2 show the interaction and linear effects of independent
variables on BPA removal efficiency under optimal conditions, respec­
tively. As it seemed, the prediction of the system response under optimal
conditions by GA is completely consistent with the response predicted
by the CCD (98.06%).
3.4. Electrocatalytic synergy in the 3DER system
The electrocatalytic synergy of β-PbO2 film and GAC particle elec­
trodes in improving the performance of the 3DER system was deter­
mined by comparing the removal efficiency of BPA in hybrid and
separate systems. Fig. 8(a) shows the BPA removal efficiency in different
removal systems. As can be seen, the removal efficiency of BPA in the
separate application of pre-exposed GAC and graphite/β-PbO2 anode at
the end of 80 min is 9.75% and 70.2%, respectively. However, under
similar operating conditions the performance of the 3DER system
equipped with graphite/β-PbO2 and graphite anodes in BPA removal
was 98.8% and 75.5%, respectively. The kinetic coefficients of BPA

Table 3
ANOVA results for modeling BPA degradation in 3DER system.
Source Sum of squares df Mean square F-value p-value Source

Model 3773.54 16 235.85 2001.26 < 0.0001 significant

Aa 89.1 1 89.1 756.07 < 0.0001
B 38.22 1 38.22 324.32 < 0.0001
C 261.63 1 261.63 2220.07 < 0.0001
D 475.41 1 475.41 4034.07 < 0.0001
E 2854.41 1 2854.41 24,220.94 < 0.0001
AD 0.6328 1 0.6328 5.37 0.02680
AE 0.6903 1 0.6903 5.86 0.02120
BC 1.4 1 1.4 11.9 0.00160
BE 3.06 1 3.06 25.99 < 0.0001
CE 3.06 1 3.06 25.99 < 0.0001
DE 0.5253 1 0.5253 4.46 0.04240
A2 15.88 1 15.88 134.72 < 0.0001
B2 22.01 1 22.01 186.78 < 0.0001
C2 2.5 1 2.5 21.19 < 0.0001
D2 2.28 1 2.28 19.34 0.00010
E2 2.73 1 2.73 23.13 < 0.0001
Residual 3.89 33 0.1178
Lack of Fit 2.73 26 0.105 0.6344 0.81330 not significant
Pure Error 1.16 7 0.1655
Cor Total 3777.43 49
a
A, B, C, D, and E represent the independent variables defined in Table 1.

9
M.R. Samarghandi et al.
Fig. 6. GA optimization plots: (a) best and mean fitness; (b) current best individual.
removal in these systems are presented in Fig. 8(b). Accordingly, the
kinetic coefficients for the separate application of pre-exposed GAC and
the electrocatalytic degradation system with graphite/β-PbO2 anode
were obtained to be 0.0013 and 0.014 min− 1, respectively. For the 3DER
system with graphite/β-PbO2 and graphite anodes, the coefficients were
0.0481 and 0.0157 min− 1, respectively. By placing the coefficients in
Eq. (7), the electrocatalytic synergy of the 3DER system for BPA
degradation was calculated to be 35.5%.
In a study, García et al. performed electrochemical oxidation and
GAC hybrid system for greywater treatment. The synergetic removal of
COD and TOC were 21.1 ± 4.3% and 23.3 ± 6.6%, respectively [67].
Also, in a study conducted by Zhu et al. for the degradation of p-nitro­
phenol in a 3DER with GAC particles, the synergetic removal of COD was
determined in the range of 16–36% [14]. When GAC particles are
exposed to an electric field, a double layer of electricity forms on their
surface that can absorb charged organic pollutants, mineral ions, and
oxidizing species by electrosorption [68]. At the same time, GAC par­
ticles were polarized under the electric field and form a large number of
10
Journal of Environmental Chemical Engineering 9 (2021) 106072
microelectrodes with anode and cathode surfaces [69]. These micro­
electrodes are able to oxidize the adsorbed organic pollutants [70]. The
energy consumed during BPA degradation in three different electro­
chemical systems can be seen in Fig. 8(c). Accordingly, the energy
consumption in a separate electrocatalytic degradation system with the
graphite/β-PbO2 anode is 6.08 kW h g− 1 BPA. However, for the 3DER
system with graphite/β-PbO2 and graphite anodes, the energy con­
sumption is 4.3 and 5.67 kW h g− 1 BPA, respectively. This shows that
the presence of GAC particle electrodes reduces the energy consumption
of the system by about 41%. On the other hand, β-PbO2 electrocatalytic
film can reduce energy consumption by 32%. Shen et al. used a 3DER
with a GAC + glass bead particle electrode to degrade estriol. In their
study, energy consumption for the 3DER and separate electrochemical
degradation system were about 1.6 and 6 kW h g− 1 estriol, respectively
[30]. Also, Liu et al. used the Sn-Sb-Bi/γ-Al2O3 particle electrode in a
3DER to remove antipyrine. They reported that the energy consumption
of the separate electrochemical degradation system was about twice that
of the 3DER system. [71].
M.R. Samarghandi et al.
Fig. 7. Contour response surface plots to show the interaction effects in optimal conditions; (a) the interaction of pH and Na2SO4, (b) the interaction of reaction time
and GAC, (c) the interaction of Na2SO4 and current density.
3.5. The role of HO• radicals in the indirect electrochemical oxidation of
BPA
In order to prove the role of HO• radicals in the indirect electro­
chemical degradation of BPA in the 3DER system with the graphite/
β-PbO2 anode, tert-butyl alcohol (TBA) (kHO• = 6.0 × 108 M− 1 S− 1) was
used as a specific scavenger [72,73]. A series of trapping experiments
were performed with different concentrations of TBA in the range of
0–50 mM, the results of which can be seen in Fig. 8(d). As can be seen, in
the presence of 5 mM TBA after 80 min reaction, the BPA removal ef­
ficiency decreases from 98.8% (No scavenger) to 75.2%. Under similar
conditions in the presence of 10 mM and 15 mM TBA, BPA removal
efficiency decreased to 59.4% and 47.3%, respectively. However, in the
presence of high concentrations of TBA at 25 and 50 mM, the system
performance in the removal of BPA was 26.3% and 22.6%, respectively.
This indicates that increasing the TBA concentration in the range of
25–50 mM does not have a significant effect on reducing system
11
Journal of Environmental Chemical Engineering 9 (2021) 106072
performance for BPA degradation. In other words, excess amounts of
TBA can completely inhibit the effect of HO• radicals on BPA degrada­
tion. However, it is observed that in the presence of 50 mM TBA, the
removal efficiency of BPA is still 22.6%, which can be attributed to the
direct oxidation (electron transfer pathway) of BPA or other electro­
catalytic degradation mechanisms expect HO• radicals [64,74].
3.6. Mineralization of BPA and degradation pathways
BPA mineralization rates were investigated under optimal conditions
for oxidative systems including 3DER with graphite/β-PbO2 anode,
3DER with graphite anode and separate electrocatalytic degradation
process with graphite/β-PbO2 anode. As observed in Fig. 8(e), the
reduction ratio of [TOC]t /[TOC]0 in the 3DER system with graphite/
β-PbO2 anode after 10 and 80 min of reaction was 0.92 and 0.02,
respectively. For the 3DER system with graphite anode and the separate
electrocatalytic degradation system with graphite/β-PbO2 anode, the
M.R. Samarghandi et al. Journal of Environmental Chemical Engineering 9 (2021) 106072

Fig. 8. (a) BPA removal efficiency, and (b) its kinetic constants under different removal systems at optimal conditions. (c) Energy consumption in various elec­
trochemical systems under optimal conditions. (d) Removal of BPA under optimal conditions in the presence of different concentrations of TBA. (e) TOC reduction
rate and (f) MCE (%) under optimal conditions for oxidative systems.

12
M.R. Samarghandi et al.
reduction ratio of [TOC]t /[TOC]0 after 80 min of reaction were 0.2 and
0.24, respectively. This confirms that the performance of the 3DER
system with graphite/β-PbO2 anode for BPA mineralization is signifi­
cantly better than the other two oxidative systems. Nevertheless, at the
end of 80 min of the reaction, the ratio of [TOC]t /[TOC]0 is not zero,
indicating that intermediates other than H2O and CO2 are formed during
BPA degradation.
Eq. (13) was used to calculate mineralization current efficiency
(MCE) during BPA mineralization.
∆(TOC)exp
MCE = × 100% (13)
∆(TOC)theor
where ∆(TOC)exp and ∆(TOC)theor are the experimental and theoretical
removal of TOC (mg L− 1) at reaction time t (s),
respectively. ∆(TOC)theor can be calculated by Eq. (14).
It
nC M × 103
∆(TOC)theor = nc F (14)
V
In Eq. (14), I and t are the applied current (A) and the electro­
chemical degradation time (s), respectively. F represents the Faraday
constant (96,485 C mol− 1 electrons). V is also the volume of the solution
being treated (mL). M shows the atomic weight of C (12 g mol− 1). nC is
the number of carbons in the structure of the organic pollutant and ne is
the number of electron transfers during contaminant mineralization
[75].
According to Fig. 8(f), the highest MCE is observed in the 3DER
system with graphite/β-PbO2 anode, which confirms that the highest
electrocatalytic activity belongs to this system. It is also observed that
for all electrochemical degradation systems, MCE has the highest value
in the initial time of 10 min and then gradually decreases. This indicates
that the main BPA degradation reactions take place at the beginning of
the process and then degradation intermediates are produced that are
Table 4
Intermediates detected during BPA degradation based on positive mass spectrum.
13
Journal of Environmental Chemical Engineering 9 (2021) 106072
resistant to degradation. Intermediate compounds induced by BPA
degradation in the 3DER system with graphite/β-PbO2 anode were
studied by LC-MS analysis. All LC-MS chromatograms related to the BPA
degradation intermediates are shown in Fig. S3. Based on the mass
spectra, the chemical name, the molecular structure and m/z of the in­
termediates identified were listed in Table 4. BPA is degraded in both
proposed pathways by HO• radicals at the anode surface [76]. As shown
in Fig. 9, BPA first produces 4-(2-hydroxypropan-2-yl) phenol
(m/z = 152 Da) under the influence of HO• radicals through cleavage of
isopropylidene group. This compound is oxidized to H2O and CO2 from
pathways I and II. In pathway I, the compound of 4-(2-hydrox­
ypropan-2-yl)phenol is converted to 4-isopropylphenol (m/z = 136 Da)
with loss of the OH functional group [77]. Subsequently, under the in­
fluence of HO• radicals and ring opening reactions, intermediate of
adipic acid (m/z = 146 Da) and then malonic acid (m/z = 104 Da) are
produced [78]. Acetic acid (m/z = 60 Da) and ethane-1,2-diol
(m/z = 62 Da) are produced by continuing the degradation reactions.
In path II, the compound of 4-(2-hydroxypropan-2-yl) phenol is first
oxidized to benzoic acid (m/z = 122 Da) and then to adipic acid
(m/z = 146 Da) under a ring opening reaction. Finally, as the oxidation
process continues, H2O and CO2 can be considered as the final in­
termediates of BPA degradation.
3.7. Monitoring the BPA degradation by cyclic voltammetry technique
Electrocatalytic degradation of BPA was evaluated by cyclic vol­
tammetry technique. Fig. 10(a) shows the cyclic voltammograms of BPA
degradation in 3DER system. As can be seen, complete degradation of
BPA in the 3DER system occurs within 80 min. During the electro­
catalytic degradation process, the peak of A1 decreases and new peaks
C0 and A0 are formed. Decreasing peak of A1 indicates the consumption
of BPA and the appearance and increasing new peaks of C0 and A0 re­
veals the formation of relatively stable intermediates during the
M.R. Samarghandi et al. Journal of Environmental Chemical Engineering 9 (2021) 106072

Fig. 9. Proposed pathway for degradation of BPA.

Fig. 10. CVs of BPA in Na2SO4 electrolyte (Temperature = 25 ± 1 ◦ C, Scan rate 100 mV s− 1) at glassy carbon electrode. (b) CVs of A: Primary substance B: Na2SO4
electrolyte and C: after electrolysis solution at glassy carbon electrode during constant-current electrolysis using 3DER system.

electrolysis process. The electrolysis process of peaks of C0 and A0 also
begins to decrease until the current of these peaks is completely elimi­
nated. In Fig. 10(b), CVs of A, B, and C are related to the BPA, electrolyte
and solution after the degradation process in the 3DER system,
respectively.
4. Conclusion
The aim of this study was to evaluate the electrocatalytic efficiency
of the 3DER system with graphite/β-PbO2 anode and GAC particle
electrode in BPA degradation and mineralization. The results of FESEM,
XRD and EDX-mapping confirmed the deposition of β-PbO2 film on the
graphite substrate. The prepared graphite/β-PbO2 anode had a high
stability (90 h) and oxygen evolution potential (2 V). A quadratic
mathematical model (p-value < 0.0001 and R2 > 0.99) was developed
by the OCCD to predict BPA removal efficiency. Accordingly, the per­
formance of the optimized 3DER system for BPA removal was 98.8%.
The electrocatalytic synergy of β-PbO2 film and GAC particle electrodes
for BPA degradation was 35.5%. In addition, the GAC particle electrodes
and β-PbO2 film reduced the energy consumption in the 3DER system by
about 41% and 32%, respectively. The final intermediates resulting from
the degradation of BPA were short-chain acids such as oxalic acid, acetic
acid, and formic acid. The results of this study showed that the 3DER
oxidation system with graphite/β-PbO2 anode and GAC particle elec­
trode can be used with high efficiency and low energy consumption for
BPA degradation and mineralization. However, the performance of
electrocatalytic degradation systems is undoubtedly influenced by some
operational variables that were not studied in this study. Therefore, it is

14
M.R. Samarghandi et al.
suggested that in future studies, the effect of some variables such as
solution temperature, distance, and the number of electrodes, type of
supporting electrolyte on the performance of 3DER systems should be
considered. On the other hand, to judge the overall performance of a
degradation system for the removal of organic matter, the efficiency of
the system must be examined in real environments such as polluted
water and wastewater. In real samples, the effect of various organic and
inorganic interventions on the performance of the system can be studied,
and finally, a suitable design for the new treatment system can be
reached.
CRediT authorship contribution statement
Mohammad Reza Samarghandi: Resources, Supervision, Project
administration. Amin Ansari: Formal analysis. Abdollah Dargahi:
Methodology, Investigation. Amir Shabanloo: Methodology, Investi­
gation, Writing – review & editing. Davood Nematollahi: Data cura­
tion, Supervision. Mohammad Khazaei: Formal analysis. Hassan
Zolghadr Nasab: Investigation. Yaser Vaziri: Validation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the Hamadan University of Medical
Sciences [Grant number 9705022625].
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jece.2021.106072.
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