Electrochimica Acta 331 (2020) 135441

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical oxidation of sulfadiazine with titanium suboxide

mesh anode
Jie Teng, Guoshuai Liu, Jiabin Liang, Shijie You*
State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin, 150090, PR China

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

Article history: Pharmaceutical wastewater needs to be treated properly before it can be discharged due to the presence
Received 24 September 2019 of high-concentration antibiotic pollutants. Electrochemical oxidation is a promising process for
Received in revised form decentralized treatment of pharmaceutical wastewater. In this study, electrochemical oxidation of a
3 December 2019
typical antibiotic, i. e. sulfadiazine (SDZ), was investigated by using titanium suboxide mesh (TiSOM)
Accepted 4 December 2019
anode. The results showed that the 60 min electrolysis could achieve almost 100% removal of SDZ based
Available online 5 December 2019
on 0.05 mol L
1 Na2SO4, pH ¼ 6.33, and current density of 10 mA cm
2. Under these conditions, the
abatement of SDZ proceeded through indirect OH-mediated oxidation rather than direct electron
Keywords:
Titanium suboxide mesh anode
transfer reaction, indicated by cyclic voltammetry (CV) and electron spin resonance (ESR) measurement.
Electrochemical oxidation The TiSOM anode exhibited a high oxygen evolution potential (2.2 V vs standard hydrogen electrode,
Sulfadiazine SHE) for OH formation and long-term stability in treatment of real pharmaceutical wastewater. The
Pharmaceutical wastewater mesh structure of TiSOM anode enabled a large electrochemically active surface area (ECSA, 2517.3 cm2)
derived from electrochemical impedance spectroscopy (EIS) measurement, and an improved mass
transfer from bulk electrolyte to the anode under flow-through operation. This makes the TiSOM anode
more advantageous than flat-plate anode. The degradation pathway of SDZ was underlined on a quali-
tative basis by using ion chromatography, ultra performance liquid chromatography-mass spectrometry/
mass spectrometry (UPLC-MS/MS) and density functional theory (DFT) calculation. This study provides
an effective manner for electrochemical treatment of pharmaceutical wastewater by using a mesh-
structured TiSO anode material.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction small-scale de-centralized wastewater treatment [1,2]. For

Pharmaceuticals are used at an increased rate globally, and they
end up in the effluent of wastewater. These pharmaceuticals,
especially antibiotics, will exert a crucial influence to water envi-
ronment, aquatic life in their habitats as well human health. The
major concern is associated with the development of antibiotic
resistance in the environment. Security of water resource creates a
demand for efficient treatment of pharmaceutical wastewater as
part of water management. In comparison with other advanced
oxidation processes like Fenton and photocatalysis, electrochemical
advanced oxidation process (EAOP) has several unique advantages
in terms of high efficiency, ease of automation, no need for chem-
ical agents and solid/liquid separation, as well as suitability for
* Corresponding author. P. O. Box 2603#, No. 73, Huanghe Road, Nangang District,
Harbin, 150090, China.
E-mail address: sjyou@hit.edu.cn (S. You).
example, a number of prior studies reported the electrochemical
removal of amoxicillin trihydrate on Ti/RuO2 anode [3], 4-
chlorophenol on boron-doped diamond (BDD) anode [4], cipro-
floxacin on PbO2 anode [5], and naphthenic acids on graphite anode
[6]. However, these anode materials may be problematic for scale-
up application because of low oxygen evolution potential (OEP),
instability and high cost.
Recently, titanium suboxides (TiSOs) have attracted a growing
interest as a novel anode material in wastewater treatment by
virtue of high conductivity, good stability, high OEP (2.5 V vs SHE),
and low cost [7e9]. In particular, the high OEP allows water
oxidation to produce highly oxidative species such as hydroxyl
radicals (OH) that can oxidize many kinds of organic compounds
unselectively [10,11]. Based on reduction of rutile TiO2 at high
temperature [12,13], the TiSOs electrode can be fabricated to ver-
satile forms such as powders, rods and tubes, plates and composites
[14e16].

https://doi.org/10.1016/j.electacta.2019.135441
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
2 J. Teng et al. / Electrochimica Acta 331 (2020) 135441
A number of previous EAOPs studies were based upon flat-plate
shaped anodes (e. g. BDD anode and dimensionally stable anode
(DSA)) [17,18]. However, these electrodes have to be operated under
optimum hydrodynamic conditions to enable diffusion-controlled
reactions at limited current density; otherwise the limitation of
mass transfer will greatly decrease the oxidation efficiency [19].
This concern would be addressed by reactive electrochemical
membrane (REM) such as carbon nanotube membrane (CNM)
[20,21] and titanium suboxide membrane [22]. The mass transfer
can be enhanced substantially when the electrolyte is enforced to
be filtered through the porous channels of REM. Nevertheless, the
EAOPs generate oxygen concurrently with OH at the potential
higher than OEP. Oxygen bubbles evolving at anode surface may
lead to blockage of active sites within the micro- and nano-scale
pores of REM. This will not only reduce efficiency of organic
oxidation, but also decrease water flux due to increased operating
pressure during long-term operation. Therefore, to enable efficient
electrochemical oxidation of antibiotic contaminant, it is necessary
to modify the channel structure of TiSOs anode to more suitable
form such as macro mesh structure that allows flow-through
operation without blockage by oxygen bubbles and without loss
of sufficient mass transfer. Previous studies reported the decon-
tamination performance of mesh-structured anodes based on ti-
tanium [23], palladium/carbon nanotubes-nafion film [24] and
WO3/TiO2 nanotubes composite [25], but there is no literature on
recently developed TiSOs mesh anode for oxidation of antibiotics.
This study reports the fabrication of titanium-based mesh-
structured TiSOs-coating (TiSOM) anode and the electrochemical
oxidation of sulfadiazine (SDZ), a typical sulfa antibiotic drug that
has been detected at different concentration levels in environ-
mental mediums. Pharmaceutical industry is one of the most
important sources for release of SDZ, and thus the pharmaceutical
wastewater containing high-concentration SDZ needs de-
centralized treatment. Following characterization of morphology,
crystalline form, and chemical composition, the electrochemical
properties of TiSOM anode were investigated. Then, we examined
the performance of TiSOM anode for electrochemical oxidation of
SDZ contaminant and treatment of SDZ-containing pharmaceutical
wastewater. Last, the mechanisms of SDZ oxidation on TiSOM
anode were underlined and discussed by identifying intermediate
products based on density functional theory (DFT) calculation and
ultra performance liquid chromatography-mass spectrometry/
mass spectrometry (UPLC-MS/MS) measurement.
2. Materials and methods
2.1. Chemicals
SDZ in powder (99% purity) was purchased from Sigma-Aldrich
(China). Na2SO4, NaNO3 and NaClO4 of analytical grade were pur-
chased from Sinopharm Chemical Reagent Co., Ltd (Shanghai,
China) and used as background electrolytes. All the other chemicals
employed were of high performance liquid chromatography (HPLC)
grade and also purchased from Sigma-Aldrich (China). Synthetic
and analytical solutions were prepared with ultrapure water pro-
duced by PureLab Prima (ELGA LabWater, UK).
2.2. Preparation of TiSOM anode
The synthesis process of the TiSOM anode is shown in Fig. 1.
First, TiSOs powder was prepared by continuous reduction of rutile
TiO2 in H2 atmosphere at 1020  C for 120 min during which the
color of the powder turned from white to black. After pretreatment
by ultrasonic cleaning with methanol, ethanol and deionized water,
the titanium mesh was then uniformly coated with TiSOs powder
via plasma spray system [26]. The TiSOs flat-plate anode was
fabricated in the same way based on a titanium plate. The tubular
electrochemical reactor with a stainless steel cathode and a TiSOM
anode is shown in Fig. S1. The reactor has a length of 25 cm with an
inner diameter of 7.5 cm. The electrodes (20 cm  4 cm) are parallel
to the wastewater flow and placed face to face in the reactor with a
distance of 5 cm. 1 L of synthetic SDZ wastewater was circulated in
the electrochemical system by a peristaltic pump (WT600-2J,
LongerPump, Baoding, China). The temperature was controlled at
25 ± 1  C by the thermostatic bath (DC-0510, Scientz, Ningbo,
China).
2.3. Characterization
The morphology of the TiSOM anode was observed by scanning
electron microscope (SEM, Sigma 500, Zeiss, German). The crys-
talline phase of the powder was identified by X-ray diffraction
(XRD, D8 ADVANCE, Ka radiation, Bruker, Germany). The surface
composition and valence state before and after the reduction pro-
cess were determined by X-ray photoelectron spectroscopy (XPS,
ESCALAB 250 Xi, Al Ka radiation, Thermo Fisher Scientific, USA).
The electrochemical properties of TiSOM, BDD and carbon cloth
were determined through cyclic voltammetry (CV) and electro-
chemical impedance spectroscopy (EIS) in a standard three-
electrode cell using galvanostat (CHI750D, CH Instruments, Inc.,
USA) with TiSOM/BDD/carbon cloth as the working electrodes. A
stainless steel mesh was used as a counter electrode and the
reference electrode was Ag/AgCl (0.195 V vs SHE). The EIS spectra
were fitted by an equivalent circuit using ZSIMPWIN.
Electron spin resonance (ESR) spectra were employed to
investigate the production of OH near the surface of TiSOM anode
during EAOP. In the ESR experiments for OH detection, 50 mL DMPO
(5,5-dimethyl-1-pyrroline-N-oxide) was mixed with 1 L
0.05 mol L
1 Na2SO4 solution in the same electrochemical system,
circulated for 20 min, and then sampled by a 100 mL capillary tube,
which was immediately inserted into the ESR cavity (A200, Bruker,
Germany).
2.4. Mass transfer
In order to determine the effect of electrode configuration on
SDZ degradation, the reaction rate constant (ks,i) and mass transfer
rate constant (km,i) were calculated for both TiSOM and plate an-
odes. ks (min
1) was obtained by duplicate bulk oxidation experi-
ments. A straight line was obtained for the logarithm (ln) of SDZ
concentration plotted versus the degradation time, suggesting that
the degradation of SDZ via TiSOM and plate anodes followed the
pseudo first-order kinetic model, which can be represented by Eq.
(1) [27e29].


ln Ct=C ¼
ks;i t (1)
0
where C0 (mg L
1) and Ct (mg L
1) are the initial concentration of
SDZ and the concentration after a certain degradation time t (min),
respectively. km,i was calculated by using Koutecky-Levich equation
as [30,31].
2
=
km;i ¼ km;0 ðDi =D0 Þ 3
(2)
Ilim
km;0 ¼ (3)
nAFC
 J. Teng et al. / Electrochimica Acta 331 (2020) 135441
Fig. 1. Schematic diagram of TiSOM anode preparation.
1 nFVS DðTOCÞ
ðyMÞ =2T
Di ¼ 7:4  10
8
gV 0:6
m
where D0 (7.6  10
10 m2 s
1) and Di (m2 s
1) are diffusion co-
efficients for Fe(CN)64
and SDZ, respectively, Ilim (A) the limiting
current based on 5 mmol L
1 Fe(CN)64
and 10 mmol L
1 Fe(CN)3
6 (3600 s h  12000 mg of carbon mol
1) and m the number of
in a 1 mol L
1 KCl solution, A (160 cm2) the geometric area of TiSOM
anode, C (mmol L
1) the bulk concentration of Fe(CN)64
, y the
parameter associated with hydrogen bonds in solvents (2.6 for
water), M the solvent’s molecular weight, T (298 K) the absolute
temperature, g the solvent viscosity and Vm the molar volume
(64.62 cm3 mol
1 for SDZ). Di value was calculated to be
1.39  10
9 m2 s
1.
2.5. Analyses and calculations
Identification and analysis of compounds were performed by
UPLC-MS/MS (Waters Co., Milford, MA, USA). Chromatographic
separation was conducted with a Symmetry® C18 column (1.7 mm,
2.1 mm  50 mm, Waters, MA) and quantitative analysis was per-
formed using selected ion monitoring to achieve the maximum
sensitivity. The mobile phase (0.1% formic acid-acetonitrile, 70:30,
v/v) was used with a flow rate of 0.1 mL min
1 and an injection
volume of 2 mL. The target compounds were detected in a positive
electrospray ionization (ESI) mode and the MS data was obtained
by a full scan mass spectrum from 100 to 500 m/z. The simple



organic acids and inorganic salt ions such as SO2

4 , NO3 , and NO2
generated during SDZ degradation by EAOP were measured by ion
chromatography (ICS-3000, Dionex, USA). NHþ 4 was determined by
colorimetric method using Nessler Reagent. The energy consump-
tion (kWh kg
1) of SDZ degradation was determined as:
1000UIt
EC ¼
ðC0
Ct ÞVs
where U (V) is the applied voltage, I the applied current (A), t (h) the
degradation time, and Vs (L) the volume of the solution. The
mineralization rate was determined according to TOC values using
a TOC analyzer (TOC-VCPN, Shimadzu, Japan). The TOC removal
percentage TOCremoved (%) was calculated according to the following
equation:
TOC0
TOCt
TOCremoved ð%Þ ¼  100
TOC0
where TOC0 (mg L
1) is the initial value before treatment and TOCt
is the TOC value after t. The mineralization current efficiency (MCE,
%) for each treated solution was then calculated from TOC values
using the following equation [3]:
3
MCEð%Þ ¼  100 (7)
(4) 4:32  107 mIt
where n is the number of electrons consumed per molecule of SDZ
for complete mineralization, F the Faraday constant
(96487C mol
1), 4.32  107 a conversion factor

1
carbon atoms of SDZ:
C10 H10 N4 O2 S þ 34H2 O/10CO2 þ 4NO
2
þ
3 þ SO4 þ 78H þ 72e


(8)
2.6. Theoretical calculations
The computational calculation based on density functional
theory (DFT) was performed on a Gaussian 09 package. Geometry
optimization was executed using the hybrid b3lyp method at
6e31g(d) basis set level. The results of electrochemical experi-
ments and ESR have indicated that OH is the primary attacking
species, thus the regioselectivity during SDZ degradation can be
analyzed by the condensed Fukui function (Text S1).
3. Results and discussion
3.1. Characterizations of TiSOM anode
SEM images show that the TiSOs powder has approximately
spherical shape with an average diameter about 1.76 mm (Fig. 2A
and B). The size distribution was in the range of 0.73e5.2 mm
(Fig. 2C). The elemental composition of the TiSOM anode was
confirmed by using energy dispersive spectroscopy (EDS) and
mapping images, showing the composition of Ti, O and Au (sub-
strate) element (Figs. S2A and S2B). The TiSOs powder coated onto
the Ti mesh substrate provides a large surface area and more active
sites for electrochemical reactions.
(5)
XRD and XPS characterizations were also performed to
demonstrate the crystallographic structure and phase composition
of the TiSOM anode. The XRD pattern (Fig. 2D) illustrated the
characteristic peaks of TiSOs powder (2q ¼ 20.80 , 26.38 , 29.62 ,
35.58 , 47.50 and 53.34 ; JCPDS No.500787) with negligible dif-
ference in the profiles before and after spraying treatment. Com-
parison of XRD pattern between precursor rutile TiO2 (Fig. S2C) and
TiSOM anode demonstrates the reduction of rutile TiO2 to TiSOs. To
gain further insight into the chemical composition on the surface of
TiO2 and TiSOs, high-resolution XPS spectra were shown in Fig. 2E
(6)
and F. There was observation of two characteristic peaks located at
binding energy of 455.8 eV and 461.7 eV for rutile TiO2 assigned to
Ti4þ 2p3/2 and Ti4þ 2p1/2. In comparison, except for Ti4þ peaks, two
other peaks of Ti3þ 2p3/2 and Ti3þ 2p1/2 could be observed at
binding energy of 453.5 eV and 460.7 eV for TiSOs. This indicated
the existence of both Ti4þ and Ti3þ species resulting from lattice
4 J. Teng et al. / Electrochimica Acta 331 (2020) 135441

Fig. 2. (A, B) SEM images of the TiSOM anode, (C) size frequency distribution histogram for TiSOs powder on the anode surface, (D) XRD patterns of TiSOs powder and TiSOM anode,
XPS spectra of (E) TiO2 and (F) TiSOs powder.

mismatch in TiSOs sample [9].

0 11=
The Ti mesh had a macro open structure and framework with 4
T
the area of 0.1 cm2 for each hollow. The geometric area of electrode Cdl ¼ @h i1
4 A (9)
was 160 cm2, a value being much smaller than electrochemically R
1
s þ R
1
p
active surface area (ECSA) due to a high roughness of TiSOs parti-
cles. Thus, the ECSA of TiSOM was determined by using EIS tech-
nology at potential of 0.76 V vs open-circuit voltage with a ECSA¼ Cdl =Cdl;0 (10)
frequency range of 10
2 to 105 Hz [31,32]. Fig. 3A revealed the EIS
data collected at potential of 0.76 V and the fitted equivalent circuit where T (0.14108 F s4
1) is a constant associated with the CPE1, 4,
using ZSIMPWIN, in which Rp and Rs represented interfacial charge- according to the angle of rotation on the complex plane plots, is
transfer resistance and ohmic resistance, respectively. The values of equal to epp/2 (p ¼ 0.30927, the value associated with the CPE1). Cdl
Rp and Rs were 15.85 U and 12.32 U for TiSOM anode, indicating a is calculated to be 0.15104 F. Value obtained for double-layer
relatively low charge-transfer resistance and small ohmic resis- capacitance (Cdl,0) of the metal oxide surface is assumed to be
tance (i. e. good conductivity of TiSOs). The Warburg impedance 60 mF cm
2 [32]. The average ECSA of TiSOM anode was then
(Wo) was related to diffusion-limited process. The double layer estimated to be 2517.3 cm2.
constant phase element (CPE) reflected the interfacial capacitive
behavior of electrode/electrolyte, and compensated for the non-
3.2. Mass transfer of TiSOM anode
homogeneity. According to Fig. 3B and C, 1e1000 Hz represents the
active layer of the anode, so the corresponding CPE1 was used for
As a key factor that exerts the influence on the efficiency of
the subsequent calculation. The ECSA can be derived quantitatively
electrochemical reaction, mass transfer is mainly controlled by the
from the values collected for double-layer capacitances (Cdl, F)) as
hydrodynamic nature nearby the anode surface. Compared with
flat-plate electrode, the macro mesh structure can induce
 J. Teng et al. / Electrochimica Acta 331 (2020) 135441 5

Fig. 3. (A) EIS data collected at 0.76 V with fitted curve, (B) Bode phase plots and (C) the equivalent circuit.

turbulence near the anode when electrolytes pass through the open
grid of mesh, which enhances the mass transfer and minimizes the
“dead zone”. This could be confirmed by enhanced SDZ oxidation of
TiSOM anode (k ¼ 0.0912 min
1) in comparison with TiSOs flat-
plate anode (k ¼ 0.0329 min
1) at the same flow rate of
180 L h
1 (Figs. 4A and S3). Since the two electrodes are composed
of the same chemical composition, the enhanced performance
should result from the difference in diffusion process. Fig. 4B gave
the km,i values for TiSOs anodes under different flow rates. The km,i
increased with the flow rate for both anodes, and a significantly
higher km,i values were observed for TiSOM anode. This provided
the most likely explanation to the enhanced SDZ oxidation
observed for TiSOM anode.
3.3. Impact of operating factors on electrochemical oxidation of SDZ
To examine the impact of operating parameters, batch experi-
ments were carried out to investigate electrochemical oxidation of
SDZ as a function of electrolyte, pH values, current density and
energy consumption. It is known that the electrochemical reactions
require supporting electrolyte to facilitate ionic conduction. Since
real wastewater contains various inorganic salts with concentration
in a wide range, Na2SO4 (0.05 mol L
1), NaNO3 (0.05 mol L
1) and
NaClO4 (0.05 mol L
1) were examined as electrolyte to simulate real
wastewater [33,34]. As shown in Fig. 5A, almost 100% removal of
SDZ could be achieved within 60 min for Na2SO4 electrolyte,
whereas the removal efficiency was only 92% and 88% for NaNO3
and NaClO4. The better degradation efficiency obtained for Na2SO4
should result from higher conductivity of Na2SO4 (9.858 mS cm
1)
than that of NaNO3 (5.319 mS cm
1) and NaClO4 (4.713 mS cm
1).
Besides, under the same current density (10 mA cm
2), Na2SO4
accounted for the lowest applied cell voltage (10.09 V).
The effect of solution pH on SDZ degradation was investigated
and the results were exhibited in Figs. 5B and S4B. According to the
pKa values (pKa1 ¼ 2.01, pKa2 ¼ 6.50), SDZ are mostly in non-
protonated form under alkaline condition (pH ¼ 9.91) which ten-
ded to be adsorbed to the anode and favored the SDZ oxidation by

OH (90% removal efficiency with a k of 0.0374 min
1). However,
the degradation efficiency of SDZ was found higher in acidic con-
dition (pH ¼ 2.64, 100% removal with a k of 0.0983 min
1) than that
in alkaline condition. Since oxygen evolution reaction competes
with OH production under high anode potential, more OH could
be generated under acidic condition due to the inhibition of oxygen
evolution (Eq. (11)). Besides, the oxidation capacity of OH is higher
under acidic condition. The maximal SDZ degradation obtained at
pH ¼ 2.64 herein was consistent with prior reports of higher
oxidation capacity of OH under acidic conditions [35,36].

Fig. 4. Comparisons of (A) SDZ removal and (B) mass transfer rate constant (km) between TiSOM and TiSO-plate. Operating conditions: 0.05 mol L
1 Na2SO4, pH 6.33, current density
10 mA cm
2 and initial SDZ concentration 50 mg L
1.
6 J. Teng et al. / Electrochimica Acta 331 (2020) 135441

Fig. 5. Effects of (A) electrolyte type, (B) pH, and (C) current density on SDZ degradation, (D) energy consumption (EC) with respect to SDZ removal and current density, (E) TOC and
SDZ degradation efficiency with time, and (F) MCE evolution of TiSOM anode, PbO2 and Pt. In each figure, apart from the operating parameter being tested, other operating pa-
rameters are selected according to the basic values. Basic operating conditions: 0.05 mol L
1 Na2SO4, pH 6.33, current density 10 mA cm
2 and initial SDZ concentration 50 mg L
1.

OH þ H2O/O2þ3Hþþ3e


(11) TiSOM anode (79%) than other commercially available anodes of Pt
(63%) and PbO2 (43%) due to high OEP of TiSOM anode. Besides, the
In the EAOPs with TiSOM anode, the degradation of SDZ was interaction between TiSOM anode and OH is relatively low [7],
found to be accelerated by increasing the current density from leading to higher activity of OH reacting with SDZ. Fig. 5F
3 mA cm
2 to 20 mA cm
2, which followed the order of k ¼ 0.1344
min
1 (20 mA cm
2)>k ¼ 0.0912 min
1 (10 mA cm
2)>k ¼ 0.0039
min
1 (3 mA cm
2) (Fig. S4C). It appears most likely that higher
current density produced higher amount of OH available for
electrochemical degradation of SDZ. As shown in Fig. 5C and D,
increasing current density from 3 mA cm
2 to 10 mA cm
2 caused
the increase in overall energy consumption from 9.62 kWh kg
1
(20% degraded) to 34.09 kWh kg
1 (100% degraded). However, only
slight increase of oxidation efficiency was observed when current
density was further increased to 20 mA cm
2 with a dramatic in-
crease of energy consumption to 116.31 kWh kg
1 (100% degraded).
Under diffusion-controlled condition, the SDZ oxidation was no
longer controlled by current density and more electric energy was
consumed by side reactions (e. g. oxygen evolution) as well as by
dissipation in the form of heat to the surroundings [37].
The TOC abatement was further investigated at initial SDZ
concentration of 50 mg L
1 (TOC of 24 mg L
1). As shown in Fig. 5E,
after 60-min electrolysis at current density of 10 mA cm
2, there Fig. 6. Cyclic voltammetry results with TiSOM anode (with and without SDZ), BDD and
was an observation of higher TOC removal efficiency attained for carbon cloth. Operating conditions: 0.05 mol L
1 Na2SO4, pH 6.33 and scan rate
0.001 V s
1.
 J. Teng et al. / Electrochimica Acta 331 (2020) 135441 7

illustrates a high MCE value obtained for TiSOM anode (57%) due to
its strong ability to produce OH for high mineralization rate at a
relatively low current density. In addition, slow decline of MCE
values should be associated with the formation of less easily
degradable intermediates like short-chain carboxylic acids [28].
3.4. Mechanism and pathways for electrochemical oxidation of SDZ
To investigate if SDZ oxidation proceeded via direct electron
transfer (DET) reaction at TiSOM anode, CV scan was recorded in
the potential range of
1.5-3.2 V vs SHE. When SDZ (50 mg L
1) was
added into the Na2SO4 electrolyte, no oxidative current was found

Fig. 7. (A) ESR spectra of DMPO-OH obtained in TiSOM/EAOP system (E ¼ 2.0 V and E ¼ 3.0 V), (B) SDZ chemical structure and (C) main reaction pathways proposed for SDZ
degradation in the TiSOM/EAOP system.
8 J. Teng et al. / Electrochimica Acta 331 (2020) 135441
Fig. 8. (A) Decomposition of SDZ in EAOP and concentration evolution of degradation intermediates, and (B) concentration change of SO2

Fig. 9. (A) COD removal of real pharmaceutical wastewater using TiSOM anode and (B) COD removal in 20 cycles. Operating condition: current density 10 mA cm
2.
in comparison with the CV curve attained in SDZ-free electrolyte,
indicating electrochemical inactivity of SDZ within the potential
window (Fig. 6). Alternatively, it appeared most likely for SDZ to be
oxidized indirectly by OH produced from water oxidation at high
anode potential. The ability of OH production by TiSOM anode
could be confirmed by a relatively high OEP (2.2 V vs SHE) being
comparable to BDD anode (2.3 V vs SHE) (Fig. 6).
ESR measurement was carried out to identify the existence of

OH in the TiSOM anode system on a qualitative basis. As shown in
Fig. 7A, there was no characteristic signal in the ESR spectra during
electrolysis conducted at anode potential of 2.0 V vs SHE. The ESR
signals representing DMPO-OH adduct were observed at anode
potential of 3.0 V vs SHE, indicating dominant role of OH in
oxidation of SDZ in EAOP. This was in good consistence with elec-
trochemical oxidation of amoxicillin, trichloroethylene and para-
cetamol compounds by OH produced on TiSOs anodes reported in
prior studies [7,33,38].
The mechanism and pathways for oxidation of SDZ mediated by

OH produced on TiSOM anode, were underlined and discussed by
using UPLC-MS/MS measurement and DFT calculations. The inter-
mediate products during SDZ degradation in EAOP are complicated
[39]. As shown in Table S1 and Fig. S5, SDZ oxidation produced a
variety of degradation intermediates such as sulfanilamide, pyr-
imidin-2-amine and 2-amine-4,6-dihydroxypyrimidine. Addition-
ally, we performed natural population analysis of charge
distribution and Fukui index representing radical attack (f0A) of the
atoms on SDZ molecule to identify degradation pathways. Fig. 7B
and Table S2 reveal that 11(N), 21(C) and 27(N) with higher f0A
values are the most likely active sites subject to OH attacking
[40,41]. Combining DFT calculations with detected intermediates,
four steps could be inferred in the initial stage of SDZ degradation


4 and NO3 .
as illustrated schematically in Fig. 7C. (i) Among the atoms of 11(N),
21(C) and 27(N), the 11(N) has the greatest f0A value (0.074502),
indicating that the amino group in SDZ molecule tends to be more
easily oxidized to hydroxyamino (I1). Further reaction of OH with
hydroxyamino group leads to nitro-substitution (I2). (ii) 21(C) atom
with the second highest f0A value (0.065605) can also be attacked by
OH, resulting in the formation of 4-amino-N-(6-oxo-1,6-
dihydropyrimidin-2-yl)benzenesulfonamide (I3). (iii) The mono-
hydroxylated SDZ (I4) was the main product of OH attacking
benzene ring in sulfonamide part. (iv) The S-N bond in SDZ mole-
cule is a preferred position for hydrolysis leading to bond breakage,
producing sulfanilic acid (I5) and pyrimidin-2-amine (I6)
[39,42,43].
The time profile for concentration of important intermediates is
shown in Fig. 8A and the results reveal the presence of various
short-chain carboxylic acids released through C-N bond breakage,
ring opening and hydroxylation along with SDZ degradation. The
oxidation intermediates were decomposed to small molecules or
mineralized to CO2 and H2O with the release of NO
3 and SO4
2


under sustained OH attacking [44]. Fig. 8B illustrated the formation
and evolution of NO
2

3 and SO4 , whose concentration tended to
increase gradually with reaction time. According to the initial
concentration of SDZ, the maximum theoretical concentration of

1
SO2
2

4 is 19.2 mg L . The concentration of SO4 measured experi-
mentally herein accounted for approximately 71% of the theoretical
value, and this was also consistent with TOC abatement (80%) un-
der the same conditions.
3.5. Treatment of pharmaceutical wastewater by TiSOM anode
To further evaluate the feasibility of TiSOM anode for engineered
 J. Teng et al. / Electrochimica Acta 331 (2020) 135441
application, we tested the treatment of real SDZ-containing phar-
maceutical wastewater (COD of 533 mg L
1, pH 5.8, conductivity of
15.8 mS cm
1 and SDZ concentration of 48 mg L
1) collected from
the effluent of secondary clarifier in a pharmaceutical factory.
Implementing 4.0-h electrolysis resulted in reduction of COD from
533 mg L
1 to 67 mg L
1 (removed by 87%; Fig. 9A), a value that
meets the discharge standard of pollutants for pharmaceutical in-
dustry bio-pharmaceutical category (100 mg L
1; National Stan-
dards of the People’s Republic of China; GB 21907-2008). Owing to
interference caused by complex components produced, the energy
consumption (152.32 kWh kg
1) for real wastewater was much
higher than that for synthetic SDZ wastewater. The stability of
TiSOM anode was also tested upon the treatment of pharmaceutical
wastewater over 20 cycles (Fig. 9B). Slight decrease was observed
for COD removal and it declined to 80% at the 20th cycle most likely
due to electrode fouling since the quality of real wastewater is very
complicated. Therefore, the feasibility of TiSOM anode in treating
real wastewater requires further evaluation and electrode fouling
needs to be prevented by proper approach.
4. Conclusions
Based on the above results, main conclusions could be drawn as
follows. The mesh structured TiSO anode enabled a large ECSA and
improved mass transfer from bulk electrolyte to the anode under
flow-through operation. The TiSOM anode could achieve almost
100% removal of SDZ based on 0.05 mol L
1 Na2SO4, pH ¼ 6.33, and
current density of 10 mA cm
2. The abatement of SDZ proceeded
mainly through indirect oxidation mediated by OH produced from
water oxidation on TiSOM anode with a high oxygen evolution
potential. The TiSOM anode demonstrated a good performance to
treat real pharmaceutical wastewater. This study provides an
effective manner for electrochemical treatment of pharmaceutical
wastewater by using a mesh-structured TiSO anode material.
Author Contribution Statement
Jie Teng: Conceptualization, Methodology, Investigation, Formal
analysis, Writing - Original Draft. Guoshuai Liu: Conceptualization.
Jiabin Liang: Software. Shijie You: Term, Conceptualization,
Methodology, Writing - Review & Editing, Funding acquisition.
Declaration of competing interest
None.
Acknowledgments
Project supported by the National Natural Science Foundation of
China (Grant No. 51822806, 51678184, 51761145031) and “Funda-
mental Research Funds for the Central Universities” (Grant No.
HIT.BRETIV.201905).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.135441.
References
[1] A. Goncalves, J. Orfao, M. Pereira, Catalytic ozonation of sulphamethoxazole in
the presence of carbon materials: catalytic performance and reaction path-
ways, J. Hazard Mater. 239e240 (2012) 167e174, https://doi.org/10.1016/
j.jhazmat.2012.08.057.
[2] A. Trovo, R. Nogueira, A. Aguera, A. Fernandez-Alba, C. Sirtori, S. Malato,
Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical
9
and toxicological evaluation, Water Res. 43 (2009) 3922e3931, https://
doi.org/10.1016/j.watres.2009.04.006.
[3] R. Kaur, J. Kushwaha, N. Singh, Electro-oxidation of amoxicillin trihydrate in
continuous reactor by Ti/RuO2 anode, Sci. Total Environ. 677 (2019) 84e97,
https://doi.org/10.1016/j.scitotenv.2019.04.339.
[4] Y. Shin, H. Yoo, Y. Ahn, M. Kim, K. Lee, S. Yu, C. Lee, K. Cho, H. Kim, J. Lee,
Electrochemical oxidation of organics in sulfate solutions on boron-doped
diamond electrode: multiple pathways for sulfate radical generation, Appl.
Catal. B Environ. 254 (2019) 156e165, https://doi.org/10.1016/
j.apcatb.2019.04.060.
[5] N. Wachter, J. Aquino, M. Denadai, J. Barreiro, A. Silva, Q. Cass, R. Rocha-Filho,
N. Bocchi, Optimization of the electrochemical degradation process of the
antibiotic ciprofloxacin using a double-sided b-PbO2 anode in a flow reactor:
kinetics, identification of oxidation intermediates and toxicity evaluation,
Environ. Sci. Pollut. Res. Int. 26 (2019) 4438e4449, https://doi.org/10.1007/
s11356-018-2349-8.
[6] A. Abdalrhman, S. Ganiyu, M. Gamal El-Din, Degradation kinetics and
structure-reactivity relation of naphthenic acids during anodic oxidation on
graphite electrodes, Chem. Eng. J. 370 (2019) 997e1007, https://doi.org/
10.1016/j.cej.2019.03.281.
[7] S. Ganiyu, N. Oturan, S. Raffy, M. Cretin, R. Esmilaire, E. van Hullebusch,
G. Esposito, M. Oturan, Sub-stoichiometric titanium oxide (Ti4O7) as a suitable
ceramic anode for electrooxidation of organic pollutants: a case study of ki-
netics, mineralization and toxicity assessment of amoxicillin, Water Res. 106
(2016) 171e182, https://doi.org/10.1016/j.watres.2016.09.056.
[8] S. You, B. Liu, Y. Gao, Y. Wang, C. Tang, Y. Huang, N. Ren, Monolithic porous
magne li-phase Ti4O7 for electro-oxidation treatment of industrial wastewater,
Electrochim. Acta 214 (2016) 326e335, https://doi.org/10.1016/
j.electacta.2016.08.037.
[9] B. Xu, H. Sohn, Y. Mohassab, Y. Lan, Structures, preparation and applications of
titanium suboxides, RSC Adv. 6 (2016) 79706e79722, https://doi.org/10.1039/
c6ra14507h.
[10] A. Fabianska, A. Bialk-Bielinska, P. Stepnowski, S. Stolte, E. Siedlecka, Elec-
trochemical degradation of sulfonamides at BDD electrode: kinetics, reaction
pathway and eco-toxicity evaluation, J. Hazard Mater. 280 (2014) 579e587,
https://doi.org/10.1016/j.jhazmat.2014.08.050.
[11] D. Bejan, E. Guinea, N. Bunce, On the nature of the hydroxyl radicals produced
at boron-doped diamond and Ebonex® anodes, Electrochim. Acta 69 (2012)
275e281, https://doi.org/10.1016/j.electacta.2012.02.097.
[12] X. Zhang, Y. Liu, J. Ye, R. Zhu, Fabrication of Ti4O7 electrodes by spark plasma
sintering, Mater. Lett. 114 (2014) 34e36, https://doi.org/10.1016/
j.matlet.2013.09.101.
[13] C. Tang, D. Zhou, Q. Zhang, Synthesis and characterization of Magneli phases:
reduction of TiO2 in a decomposed NH3 atmosphere, Mater. Lett. 79 (2012)
42e44, https://doi.org/10.1016/j.matlet.2012.03.095.
[14] F. Walsh, R. Wills, The continuing development of Magne li phase titanium
sub-oxides and Ebonex® electrodes, Electrochim. Acta 55 (2010) 6342e6351,
https://doi.org/10.1016/j.electacta.2010.05.011.
[15] A. Pedersen, J. Rønsbo, Oxygen deficient Ti oxides (natural magne li phases)
from mudstone xenoliths with native iron from Disko, central West
Greenland, Contrib. Mineral. Petrol. 96 (1987) 35e46, https://doi.org/10.1007/
bf00375523.
[16] M. Toyoda, T. Yano, B. Tryba, S. Mozia, T. Tsumura, M. Inagaki, Preparation of
carbon-coated Magneli phases TinO2n-1 and their photocatalytic activity under
visible light, Appl. Catal. B Environ. 88 (2009) 160e164, https://doi.org/
10.1016/j.apcatb.2008.09.009.
[17] S. Vasilie, F. Manea, A. Baciu, A. Pop, Dual use of boron-doped diamond
electrode in antibiotics-containing water treatment and process control,
Process Saf. Environ. 117 (2018) 446e453, https://doi.org/10.1016/
j.psep.2018.05.024.
[18] R. Kaur, J. Kushwaha, N. Singh, Electro-oxidation of Ofloxacin antibiotic by
dimensionally stable Ti/RuO2 anode: evaluation and mechanistic approach,
Chemosphere 193 (2018) 685e694, https://doi.org/10.1016/
j.chemosphere.2017.11.065.
[19] H. Liu, C. Vecitis, Reactive transport mechanism for organic oxidation during
electrochemical filtration: mass-transfer, physical adsorption, and electron-
transfer, J. Phys. Chem. C 116 (2011) 374e383, https://doi.org/10.1021/
jp209390b.
[20] C. Vecitis, G. Gao, H. Liu, Electrochemical carbon nanotube filter for adsorp-
tion, desorption, and oxidation of aqueous dyes and anions, J. Phys. Chem. C
115 (2011) 3621e3629, https://doi.org/10.1021/jp111844j.
[21] Q. Zhang, S. Bolisetty, Y. Cao, S. Handschin, J. Adamcik, Q. Peng, R. Mezzenga,
Selective and efficient removal of fluoride from water: in situ engineered
amyloid fibril/ZrO2 hybrid membranes, Angew. Chem. Int. Ed. 58 (2019)
6012e6016, https://doi.org/10.1002/anie.201901596.
[22] A. Zaky, B. Chaplin, Mechanism of p-substituted phenol oxidation at a Ti4O7
reactive electrochemical membrane, Environ. Sci. Technol. 48 (2014)
5857e5867, https://doi.org/10.1021/es5010472.
[23] Y. Liu, Z. Yan, R. Chen, Y. Yu, X. Chen, X. Zheng, X. Huang, 2,4-Dichlorophenol
removal from water using an electrochemical method improved by a com-
posite molecularly imprinted membrane/bipolar membrane, J. Hazard Mater.
377 (2019) 259e266, https://doi.org/10.1016/j.jhazmat.2019.05.064.
[24] Z. Sun, X. Ma, X. Hu, Electrocatalytic dechlorination of 2,3,5-trichlorophenol
on palladium/carbon nanotubes-nafion film/titanium mesh electrode, Envi-
ron. Sci. Pollut. Res. Int. 24 (2017) 14355e14364, https://doi.org/10.1007/
10 J. Teng et al. / Electrochimica Acta 331 (2020) 135441
s11356-017-9004-7.
[25] M. Zhong, G. Zhang, X. Yang, Preparation of Ti mesh supported WO3/TiO2
nanotubes composite and its application for photocatalytic degradation under
visible light, Mater. Lett. 145 (2015) 216e218, https://doi.org/10.1016/
j.matlet.2015.01.091.
[26] J. Wang, D. Zhi, H. Zhou, X. He, D. Zhang, Evaluating tetracycline degradation
pathway and intermediate toxicity during the electrochemical oxidation over
a Ti/Ti4O7 anode, Water Res. 137 (2018) 324e334, https://doi.org/10.1016/
j.watres.2018.03.030.
[27] L. Wojna rovits, T. To
 th, E. Taka
cs, Critical evaluation of rate coefficients for
hydroxyl radical reactions with antibiotics: a review, Crit. Rev. Environ. Sci.
Technol. 48 (2018) 575e613, https://doi.org/10.1080/
10643389.2018.1463066.
[28] Y. Ji, J. Lu, L. Wang, M. Jiang, Y. Yang, P. Yang, L. Zhou, C. Ferronato, J. Chovelon,
Non-activated peroxymonosulfate oxidation of sulfonamide antibiotics in
water: kinetics, mechanisms, and implications for water treatment, Water
Res. 147 (2018) 82e90, https://doi.org/10.1016/j.watres.2018.09.037.
[29] T. Zhang, X. Li, Q. Zhao, Y. Rao, Control of a novel synthetical index for the local
indoor air quality by the artificial neural network and genetic algorithm,
Sustain. Cities Soc. 51 (2019) 101714, https://doi.org/10.1016/
j.scs.2019.101714.
[30] C. Brinzila, M. Pacheco, L. Ciríaco, R. Ciobanu, A. Lopes, Electrodegradation of
tetracycline on BDD anode, Chem. Eng. J. 209 (2012) 54e61, https://doi.org/
10.1016/j.cej.2012.07.112.
[31] A. Zaky, B. Chaplin, Porous substoichiometric TiO2 anodes as reactive elec-
trochemical membranes for water treatment, Environ. Sci. Technol. 47 (2013)
6554e6563, https://doi.org/10.1021/es401287e.
[32] Y. Jing, L. Guo, B. Chaplin, Electrochemical impedance spectroscopy study of
membrane fouling and electrochemical regeneration at a sub-stoichiometric
TiO2 reactive electrochemical membrane, J. Membr. Sci. 510 (2016)
510e523, https://doi.org/10.1016/j.memsci.2016.03.029.
[33] S. Ganiyu, N. Oturan, S. Raffy, M. Cretin, C. Causserand, M. Oturan, Efficiency of
plasma elaborated sub-stoichiometric titanium oxide (Ti4O7) ceramic elec-
trode for advanced electrochemical degradation of paracetamol in different
electrolyte media, Separ. Purif. Technol. 208 (2019) 142e152, https://doi.org/
10.1016/j.seppur.2018.03.076.
[34] A. Urtiaga, C. Fernandez-Gonzalez, S. Gomez-Lavin, I. Ortiz, Kinetics of the
electrochemical mineralization of perfluorooctanoic acid on ultra-
nanocrystalline boron doped conductive diamond electrodes, Chemosphere
129 (2015) 20e26, https://doi.org/10.1016/j.chemosphere.2014.05.090.
[35] P. Patil, P. Gogate, Degradation of methyl parathion using hydrodynamic
cavitation: effect of operating parameters and intensification using additives,
Separ. Purif. Technol. 95 (2012) 172e179, https://doi.org/10.1016/
j.seppur.2012.04.019.
[36] A. Pradhan, P. Gogate, Removal of p-nitrophenol using hydrodynamic cavi-
tation and Fenton chemistry at pilot scale operation, Chem. Eng. J. 156 (2010)
77e82, https://doi.org/10.1016/j.cej.2009.09.042.
[37] F. Moreira, J. Soler, A. Fonseca, I. Saraiva, R. Boaventura, E. Brillas, V. Vilar,
Incorporation of electrochemical advanced oxidation processes in a multi-
stage treatment system for sanitary landfill leachate, Water Res. 81 (2015)
375e387, https://doi.org/10.1016/j.watres.2015.05.036.
[38] G. Chen, E. Betterton, R. Arnold, Electrolytic oxidation of trichloroethylene
using a ceramic anode, J. Appl. Electrochem. 29 (1999) 961e970, https://
doi.org/10.1023/A:1003541706456.
[39] G. Ren, M. Zhou, P. Su, W. Yang, X. Lu, Y. Zhang, Simultaneous sulfadiazines
degradation and disinfection from municipal secondary effluent by a flow-
through electro-Fenton process with graphene-modified cathode, J. Hazard
Mater. 368 (2019) 830e839, https://doi.org/10.1016/j.jhazmat.2019.01.109.
[40] W. Liu, Y. Li, F. Liu, W. Jiang, D. Zhang, J. Liang, Visible-light-driven photo-
catalytic degradation of diclofenac by carbon quantum dots modified porous
g-C3N4: mechanisms, degradation pathway and DFT calculation, Water Res.
151 (2019) 8e19, https://doi.org/10.1016/j.watres.2018.11.084.
[41] K. Cheng, Z. Cai, J. Fu, X. Sun, W. Sun, L. Chen, D. Zhang, W. Liu, Synergistic
adsorption of Cu(II) and photocatalytic degradation of phenanthrene by a
jaboticaba-like TiO2/titanate nanotube composite: an experimental and
theoretical study, Chem. Eng. J. 358 (2019) 1155e1165, https://doi.org/
10.1016/j.cej.2018.10.114.
[42] Y. Song, J. Tian, S. Gao, P. Shao, J. Qi, F. Cui, Photodegradation of sulfonamides
by g-C3N4 under visible light irradiation: effectiveness, mechanism and
pathways, Appl. Catal. B Environ. 210 (2017) 88e96, https://doi.org/10.1016/
j.apcatb.2017.03.059.
[43] J. Yang, M. He, T. Wu, A. Hao, S. Zhang, Y. Chen, S. Zhou, L. Zhen, R. Wang,
Z. Yuan, L. Deng, Sulfadiazine oxidation by permanganate: kinetics, mecha-
nistic investigation and toxicity evaluation, Chem. Eng. J. 349 (2018) 56e65,
https://doi.org/10.1016/j.cej.2018.05.018.
[44] J. Murillo-Sierra, I. Sires, E. Brillas, E. Ruiz-Ruiz, A. Hernandez-Ramirez,
Advanced oxidation of real sulfamethoxazoleþtrimethoprim formulations
using different anodes and electrolytes, Chemosphere 192 (2018) 225e233,
https://doi.org/10.1016/j.chemosphere.2017.10.136.