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Visible-light photoelectrocatalysis/H2O2
Cite this: RSC Adv., 2022, 12, 30577
synergistic degradation of organic pollutants by
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a magnetic Fe3O4@SiO2@mesoporous TiO2

catalyst-loaded photoelectrode†
Bo Zhang, Xuemei Li, * Yongshan Ma, Tianyi Jiang, Yanyan Zhu and Huixue Ren

In this paper, we describe a method for photoelectrocatalysis (PEC)/H2O2 synergistic degradation of

organic pollutants with a magnetic Fe3O4@SiO2@mesoporous TiO2 (FST) photocatalyst-loaded
electrode. At optimal conditions of pH 3.0, 2.25% H2O2, working electrode (fixed FST 30 mg) potential
+0.6 V (vs. SCE), and 10 mg L−1 of all experimental pollutants, the FST PEC/H2O2 synergistic system
exhibited high activity and stability for the removal of various organic pollutants under visible light with
comparable degradation efficiencies, including MB (98.8%), rhodamine B (Rh B, 96.7%), methyl orange
(MO, 97.7%), amoxicillin (AMX, 83.9%). Moreover, this system obtained TOC removal ratios of 83.5% (MB),
77.9% (Rh B), 80.2% (MO), 65.5% (AMX) within 8 min. The kinetic rate constants of the PEC/H2O2
synergistic system were nearly 53 and 1436 times higher than that of the PEC process and H2O2
Received 18th August 2022
Accepted 21st October 2022
photolysis under visible light, respectively. Furthermore, the main reactive oxidant species (cOH, cO2−)
were studied and enhanced mechanisms of the photocatalytic-electro-H2O2 coupling system were
DOI: 10.1039/d2ra05183d
proposed. This work brings new insights to efficiently purify organic pollutants by PEC coupled with
rsc.li/rsc-advances peroxide under solar light illumination.

such as heterogeneous catalysis,2 photoelectrocatalysis (PEC),3

1. Introduction photocatalysis,4 Fenton5 and Fenton-like,6 electro-Fenton and
With advances in industrialization and rapid population photoelectro-Fenton,7 electrochemical oxidation,8 etc. can be
growth, organic pollutants are frequently detected in water used for wastewater treatment. The PEC technology combines
environments. They continue to be enriched in food chains and photocatalysis and electrochemical methods, which is an effi-
food webs, endangering ecological environments and human cient process to remove recalcitrant organic pollutants from
health.1 These organic pollutants cannot be completely elimi- water.9 Biasing the semiconductor photoanode with a voltage
nated by wastewater treatment processes, resulting in residues under illumination, photogenerated h+–e− pairs can be effec-
in groundwater and surface water. Therefore, it is necessary to tively inhibited by an external electric eld, resulting in
develop suitable technological approaches for the decomposi- improved photocatalytic activities.10 A lot of research has been
tion and mineralization of refractory organic pollutants and done on the photoanode materials, reaction mechanisms and
removal of refractory organic pollutants from water kinetics of PEC,11 which shows that it is a promising wastewater
environments. treatment technology.
Refractory organic pollutants cannot be effectively degraded TiO2 is considered as a promising photocatalyst for waste-
and mineralized by using the conventional biological, physical water treatment12 due to its unique photoelectric performance
and chemical wastewater treatment methods. Compared to and high photochemical stability, and it has been widely
these traditional technologies, advanced oxidation processes exploited as photoanode material in PEC systems.13 However,
(AOPs) have many advantages with regards to degrading due to the large forbidden bandwidth of TiO2 (3.2 eV for anatase
refractory organic pollutants, which include complete miner- type), it can only absorb ultraviolet light (l # 387 nm), which
alization and oxidation of refractory organic pollutants, low limits its photocatalytic activity under visible light.14 In addi-
secondary pollution outcomes, and small working area. AOPs tion, photogenerated hole–electron pairs (h+–e−) of TiO2 can
rapidly recombine, resulting in low catalytic efficiency.15 So
there have been many attempts to modify titanium dioxide (e.g.
School of Municipal and Environmental Engineering, Shandong Jianzhu University, dye sensitization, metal/non-metal doping, morphology
Jinan 250101, Shandong, China. E-mail: ch1889l@sdjzu.edu.cn control, and composite photocatalysts) to overcome aforesaid
† Electronic supplementary information (ESI) available. See DOI: challenges.16 Among the composite photocatalysts, magnetic
https://doi.org/10.1039/d2ra05183d

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TiO2 is not only to be separated and recovered from reaction radicals and improve the degradation efficiency in PEC
mixtures easily, but also contains some magnetic nanoparticles systems.39,40
that have good visible-light absorption and excellent optical/ In this study, a PEC/H2O2 coupling system with magnetic
electrical properties, further improving the degradation FST-loaded photoanode was constructed to discuss the syner-
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kinetics of pollutants.17 Due to its low toxicity, biocompatibility, gistic degradation of organic pollutants. The FST PEC/H2O2
and superparamagnetism, magnetite (Fe3O4) has become one of system was effective for the degradation of methylene blue,
the most widely used magnetic nanoparticles18,19 in the fabri- rhodamine B, methyl Orange, and amoxicillin under visible
cation of magnetic TiO2 photocatalysts. Previous studies have light. With the addition of 2.25% H2O2, the reaction kinetic rate
shown that direct contact of the magnetic core with photo- constant of the PEC/H2O2 synergistic system was nearly 53
catalysts leads to photodissolution of Fe3O4,20 as well as times that of individual PEC. In the PEC/H2O2 process, cO2− and
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increases recombination of photogenerated charge carriers, cOH were generated to degrade pollutants, and at the same
thereby reducing the catalytic activity.21 It has been reported time, the photogenerated e− could be captured by a sufficient
that the SiO2 interlayer between TiO2 and the magnetic core amount of H2O2 to generate cOH, which increased the amounts
can effectively prevent the chemical- and photo-dissolution of of strong oxidizing substances and promoted the separation of
Fe3O4 22,23 and can improve the photocatalytic activity of photogenerated h+–e−. The formed photocatalytic-electro-H2O2
TiO2.24 And because of silica's well-known special character- coupling system improved the degradation efficiency of diverse
istics, such as low cost, thermal and mechanical stability, organic pollutants, and maintained the high degradation effi-
surface chemical and adsorption capacity, and optical trans- ciency within 8 degradation cycles.
parency in the wavelength region where TiO2 absorbs,25
previous studies have shown that the core–shell SiO2@TiO2
has excellent photocatalytic efficiency for the pollutant 2. Experimental section
degradation than pure TiO2.26 In recent years, the research on
2.1. Materials and reagents
magnetic TiO2 composite photocatalysts based on Fe3O4 has
mostly focused on the application of Fe3O4@SiO2@TiO2 in Indium tin oxide (ITO) coated glass slides (25 mm × 25 mm ×
photocatalysis.27–33 The role of Fe3O4 in these studies is 1.1 mm, 8–12 U sq−1) were purchased from Sigma-Aldrich
primarily in the area of magnetic separation, but less attention (Shanghai Warehouse). Methylene blue (MB, C16H18ClN3S,
is paid to how to improve TiO2 photocatalytic activity. Mean- $98%), rhodamine B (Rh B, C28H31ClN2O3, $99%), methyl
while, less research has been conducted on Fe3O4@SiO2@TiO2 orange (MO, C14H14N3NaO3S, 98%), amoxicillin (AMX, C16H19-
in photoelectrocatalysis,34 and few studies have comprehen- N3O5S$3H2O, 98%), titanium butoxide (C16H36O4Ti, AR), poly(-
sively discussed the issues of expanding the light absorption propylene glycol) (PPG 1000, H[OCH(CH3)CH2]nOH, average Mn
range, increasing the photoelectrocatalytic activity, effective ∼ 1000), tetraethyl orthosilicate (TEOS, C8H20O4Si, >99%),
charge separation performance, and stable recyclability.35 ethanol (CH3CH2OH, $99.5%) were purchased from Macklin
Therefore, it is necessary to further study the effect of Fe3O4 on Inc. (Shanghai, China). FeCl3$6H2O (AR), FeSO4$7H2O (AR),
the band gap and optical absorption of Fe3O4@SiO2@TiO2 NH3 H2O (AR, 28%), HCl (AR, 36%), glacial acetic acid (CH3-
composites, and on the optical and electrical properties of COOH, AR), and other inorganic metal salts were purchased
composite photoanodes. We successfully prepared a novel from Sinopharm Chemical Reagent Co., Ltd (Shanghai, China).
composite photoelectrocatalytic material (Fe3O4@SiO2@- All solutions were prepared using ultrapure water from a Milli-Q
mesoporous TiO2, FST), encapsulated by layers of Fe3O4, SiO2 water purication system (resistivity > 16 MU cm at 25 °C).
and mesoporous TiO2 particles with a unique core–shell
structure. The dense SiO2 layer prevents the magnetic core
from interacting with TiO2, reducing the electron–hole 2.2. Fabrication of photoelectrode
recombination rate, and preventing photo-dissolution of The detailed synthesis of FST and TiO2 can be found from ESI.†
Fe3O4 (ref. 36) and dissolution under acidic conditions. Fe3O4 FST-loaded photoelectrode: 30 mg FST was sonicated in 1 mL
can lower the band gap of FST and enhance the visible-light ethanol to obtain a 30 mg mL−1 FST suspension. The ITO coated
absorption. Due to the mesoporous structure and anatase glass slides, which have been cleaned via ultrasonic waves in
TiO2 particles, FST has a high specic surface area and acetone, ethanol and distilled water, were connected to
exceptional catalytic performance. a section of electrode wires with conductive silver glue. The
Because of mass transfer limitations and the low number epoxy resin glue was used to seal the connection between ITO
of active radicals generated in the heterogeneous PEC and the electrode wire. Then, 30 mg mL−1 FST suspension was
systems, the efficiency of photoelectrocatalytic oxidation for applied on the ITO work surface and dried at 25 °C. During the
pollutant removal should be increased. UV/H2O2 systems PEC/H2O2 synergistic degradation experiment, the Nd–Fe–B (25
have been applied to the degradation of various pollutants.37 mm × 25 mm × 5 mm) magnet was coated with a layer of
The addition of H2O2 to other AOPs can improve the degra- polyvinyl chloride lm to avoid the contact of the Nd–Fe–B
dation efficiency of organic pollutants by strengthening magnet with the reaction solution, and glued to the back of the
the generation of radicals in a wider spectral range.38 It has ITO work surface.31
been reported that H2O2 can enhance the generation of TiO2-loaded photoelectrode: 30 mg TiO2 was sonicated in
1 mL ethanol to obtain a 30 mg mL−1 TiO2 suspension. Add the

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TiO2 suspension dropwise to the cleaned ITO conductive 3. Results and discussion
surface and dry at 25 °C.
3.1. Morphology and structural analysis of catalysts
2.3. Characterization of FST The FST microspheres were characterized by scanning trans-
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mission electron microscopy (STEM). The high-angle annular

Sample microscopic morphologies were investigated by eld
dark-eld (HAADF) image in Fig. 1a exhibited an overlay of
emission transmission electron microscopy (JEM-2100F, JEOL,
Fe3O4 core and TiO2 shell with a clear separation. A clear
Japan). The X-ray diffraction (XRD) pattern was measured by
contrast difference was also observed in EDS mappings
a BrukerX-ray diffractometer (D8 advance, Germany). X-ray
(Fig. 1b), conrming the core–shell structure of FST. The
photoelectron spectroscopy (XPS, ThermoEscalab 250Xi,
diameter of Fe3O4 core was about 580 nm, while thickness of the
Thermo sher, USA) was performed to assess surface properties
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SiO2 intermediate layer and TiO2 shell layer was about 45 nm

and composition. The UV-vis diffuse reectance spectrum was
and 50 nm, respectively.
determined by UV-visible-near infrared light spectrophotometry
FST, Fe3O4@SiO2 and Fe3O4 nanoparticles were analyzed by
(Cary 5000, Agilent, USA). Mesoporous structures of catalysts
X-ray diffraction (XRD) (Fig. 2). Fe3O4 nanoparticles exhibited
were measured using the surface area and pore size analyzer
characteristic peaks at 2q = 30.1°, 35.44°, 43.2°, 53.56°, 57.1°
(Autosorb-iQ, Quantachrome, USA). Magnetic data was ob-
and 62.6°, in agreement with previously reported XRD patterns
tained by an MPMS magnetic measurement system (MPMS-
of Fe3O4.41 The obtained material was Fe3O4 crystal with anre-
VSM, Quantum Design, USA).
gular octahedral inverse spinel structure. Fe3O4@SiO2 particles
exhibited comparable XRD patterns to Fe3O4, indicating that
2.4. The PEC/H2O2 synergistic degradation experiment
the Fe3O4 crystal structure was well maintained. Characteristic
Experiments were conducted in a quartz photoelectric reactor peaks at 25.4°, 37.8°, 48.1°, 54.1°, 55.2°, 62.8° and 68.8° of FST
with the volume of 60 mL, and the light source was a xenon can be attributed to anatase TiO2 (101), (004), (200), (105), (211),
light source (H8X-F300, Beijing Newbit Technology Co., Ltd.). (204) and (116), respectively. The high crystallinity of nano-TiO2
Potentiostat experiments were performed using a three elec- can reduce the migration distance of photogenerated charges,
trode system consisting of a working electrode (W.E., FST + and accordingly reduce the recombination rate.42
ITO photoelectrode, anode), a counter electrode (C.E., Pt The characterization data and analysis details of meso-
electrode, cathode), and a reference electrode (R.E., saturated porous structure, magnetic response and XPS spectrum were
calomel electrode, recorded as SCE), which were controlled described in the ESI.†
using a CHI electrochemical analyzer (CHI 760E, CH Instru-
ments, Inc., USA). The distance between the working elec-
trode and the light source was 10 cm. To enhance 3.2. Photo-electric performance
conductivity, 0.05 mol per L Na2SO4 was added to the The UV-vis diffuse reectance spectra (DRS) of Fe3O4, Fe3O4@-
pollutants solution (the concentration was 10 mg L−1) as the SiO2, TiO2 nanoparticles and FST were shown in Fig. 3a. TiO2
supporting electrolyte. exhibited a lower optical absorption response from 400–
The UV-vis spectrophotometer (UV-5800, Shanghai) was used 1000 nm. Comparing the optical absorption responses of Fe3O4,
to determine pollutant concentrations (lmax,MB = 664 nm, Fe3O4@SiO2 and FST at 400–1000 nm, Fe3O4 has the strongest
lmax,Rh B = 554 nm, lmax,MO = 463 nm, lmax,AMX = 198 nm). The light absorption, while FST has a weaker light absorption due to
total organic carbon (TOC) was determined using a TOC the encapsulation of SiO2 and TiO2. However, the visible-NIR
analyzer (Elementer, vario TOC). absorption of FST is still signicantly enhanced compared

Fig. 1 Scanning transmission electron microscopy (STEM) of FST: (a) HAADF image, (b) EDS mappings of Fe3O4, SiO2, and TiO2.

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wavelength has shown the capability to potentially utilize

natural solar light as activation source.29 Compared with other
materials (WO3, ZnO, CdS, etc.) with low Eg and activity in
visible light, FST has lower Eg, and has the characteristics of
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nontoxicity, biochemical inertness, low cost of TiO2.

To investigate the charge transfer of interface between pho-
tocatalysts and reaction solutions, Electrochemical Impedance
Spectroscopy (EIS) was conducted. The EIS Nyquist plots were
shown in Fig. 4a. The circular radius of ITO + FST was smaller
than the pristine ITO and ITO + TiO2. A smaller impedance arc
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radius at low frequencies signies a lower charge transfer

resistance (Rct),44 thus, h+–e− pairs are efficiently separated. In
this regard, ITO + FST possessed faster charge transfer rate and
more efficient separation of h+–e− pairs than ITO and ITO +
TiO2 at the solid–liquid interface.
The photocurrent of W.E. at +0.6 V (vs. SCE) was measured to
Fig. 2 X-ray diffraction (XRD) pattern. test the separation efficiency of photogenerated charge by
several on/off cycles of visible-light. Photocurrent response
curves of pristine ITO, ITO + TiO2 and ITO + FST were shown in
with that of TiO2. Since FST is very sensitive to visible light, it Fig. 4b. The photocurrents generated by ITO + FST, ITO and ITO
enhances the performance of visible-light driven photo- + TiO2 photoelectrodes were 0.17, 0.10, and 0.07 mA, respec-
electrocatalytic systems. Using the Tauc equation (eqn (1)) and tively. The photocurrent of the ITO + FST electrode was about
the Kubelka–Munk function (eqn (2)), band gaps of Fe3O4, 1.7-fold that of ITO electrode, and 2.4-fold that of ITO + TiO2
Fe3O4@SiO2, TiO2 and FST were calculated as previously electrode, respectively. The photocurrent enhancement of ITO +
reported.43 FST induced by visible light indicates that the photogenerated
h+–e− pairs at the interface have higher separation efficiency
[F(R)hʋ]0.5 = A(hʋ − Eg) (1) and less recombination. The high separation rate of h+–e− pairs
can promote the movement and subsequent reaction of elec-
F(R)=(1 − R)2/2R (2) trons. However, TiO2 had lower conductivity than ITO, and
absorbed less visible-light, so the photocurrent of the ITO +
TiO2 was lower than that of the pristine ITO.
Fig. 3b shows that the effective Eg values of samples were
calculated by plotting [F(R)hʋ]0.5 versus hʋ. The indirect Eg
3.3. Control experiments for different degradation methods
values of catalysts can be determined by extrapolating the linear
part at [F(R)hʋ]0.5 = 0. The Eg values for Fe3O4, Fe3O4@SiO2, FST Taking MB as the model pollutant, the effects of direct
and TiO2 were 1.49, 1.77, 1.88 and 3.19 eV, respectively. The photolysis (PO), photocatalysis (PC), electrocatalysis (EC), pho-
addition of Fe3O4 and SiO2 reduced the forbidden bandwidth of toelectrocatalysis (PEC), and PEC/H2O2 synergistic system on
TiO2, so that the light absorption of FST extended to the visible MB degradation were compared (Fig. 5). In the PO, PC, PEC, and
light region. The higher photocatalytic performance at higher PEC/H2O2 synergistic system, illumination was the visible light
provided by the xenon lamp light source. In the EC, PEC, and

Fig. 3 (a) UV-vis diffuse reflectance spectrum (DRS), (b) Tauc plot of DRS.

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Fig. 4 (a) EIS responses of ITO, ITO + TiO2 and ITO + FST, (b) surface photocurrent curves.

H2O2 signicantly improved MB degradation when they coex-

isted, the degradation efficiency was close to 100% aer 5 min.
Therefore, FST PEC has good synergistic effects with H2O2 PO
and can quickly remove pollutants.
The synergy factor (S) obtained from eqn (3) 45 elucidates on
the synergy between PEC and H2O2 photolysis in the PEC/H2O2
degradation system, and demonstrates the priority of the
combined process.

S = K12/(K1 + K2) (3)

where, K1, K2, and K12 are kinetic constants for H2O2 PO, PEC
process, and PEC/H2O2 synergistic system, respectively. Exper-
imental data was tted with the Langmuir–Hinshelwood model,
and kinetic constants (Table 1) of the different degradation
methods presented by the different curves (a, g, i) in Fig. 5 were
calculated. Since the concentration of MB was low, it was
assumed that the reaction would take place with a pseudo-rst-
Fig. 5 MB degradation by photolysis (PO), photocatalysis (PC), elec-
order equation. The correlation coefficient (R2) for all processes
trocatalysis (EC), photoelectrocatalysis (PEC), and PEC/H2O2 syner-
gistic system. was above 0.95, indicating that the assumption was reasonable.
Based on Table 1, the kinetic constant K of the FST PEC/H2O2
synergic system (1.2924 min−1) was found to be about 1436 and
PEC/H2O2 synergistic system, anode potential was +0.6 V (vs. 53 times higher than that of the H2O2 PO (0.0009 min−1) and
SCE). As shown in curve (a), the MB solution showed less than FST PEC (0.0244 min−1), respectively. Substituting K1, K2 and
1.9% degradation when irradiated with visible light in the H2O2 K12 into eqn (3), the value of S was 51.08 (much greater than 1),
PO for 40 min. Curve (b) showed that the degradation efficiency indicating that the composite process was not a simple addition
was slightly increased up to about 25% by visible-light PC aer of PEC and H2O2 photolysis.
adding FST to the MB solution. Curve (c) represented the PC in
the presence of H2O2, the degradation efficiency was signi- 3.4. Optimization of FST PEC/H2O2 synergistic system
cantly improved, and 31.1% of the MB was removed aer Using methylene blue (MB) as the model pollutant, the experi-
40 min. Curve (d–f) showed the experimental results under EC mental conditions and degradation performance of the PEC/
conditions. MB exhibited stability, whether H2O2 (curve (d)) or H2O2 synergistic system was studied.
FST (curve (e)) are added alone. Aer adding H2O2 and FST at Effects of pH. To study the effects of the pH on MB degra-
the same time (curve (f)), the removal rate slightly increased, dation efficiency, the initial pH of the reaction solution,
while the degradation efficiency was less than 10% aer 40 min. including 10 mg L−1 MB, 0.05 mol per L Na2SO4, and 2.25%
Curves (g) and (h) represented experimental results in PEC. H2O2, was adjusted to 1.0, 2.0, 3.0, 4.0, and 5.0, respectively, and
Under these conditions, the removal rate of MB reached 61.5% the ITO + FST working electrode (xed FST 30 mg) was applied
aer adding only FST for 40 min, the removal rate of MB at +0.6 V (vs. SCE) potential, aer which degradation was per-
reached 96.1% aer adding only H2O2 for 10 min, and was close formed by visible-light irradiation. MB degradation rates under
to 100% aer 20 min. Curve (i) showed the experimental results different degradation times in each group were compared and
under PEC/H2O2 synergistic degradation conditions. FST and analyzed (Fig. 6a). When pH was in the range of 1.0–5.0, the

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Table 1 Kinetic constants and correlation coefficients (R2) of MB degradation

Curve in Fig. 5 Degradation system Kinetic constant (min−1) R2

a H2O2 PO 0.0009 (K1) 0.9620

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g FST PEC 0.0244 (K2) 0.9979

i FST + H2O2 PEC/H2O2 synergistic system 1.2924 (K12) 0.9562
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Fig. 6 PEC/H2O2 synergistic degradation of MB. (a) pH values, (b) H2O2 concentration, (c) anodic potential, (d) FST fixation amount, (e) initial
mass concentration of MB, (f) recycling test of FST.

degradation efficiency of MB reached 99% aer 6 min. At the pH than 2.25%, the degradation efficiency of MB didn't continue to
range of 1.0–3.0, the degradation efficiency was more than 80% increase (2.55% H2O2), but decreased (2.85% H2O2). Excess
aer 1 min, and reduced to less than 80% at the pH range of H2O2 consumes cOH, the main active species for degrading MB,
4.0–5.0, indicating that lower pH value is more conducive for and H2O2 reacts with cOH to generate cHO2 or cO2− with much
improving photocatalytic activities.46 The degradation efficiency less reactivity,48 which reduces the catalytic reaction rate and is
was largest at pH 1.0, but its advantages relative to pH 2.0–3.0 unfavorable for MB degradation. Therefore, the optimal
were not marked. Therefore, pH 3.0 was selected as the optimal concentration of H2O2 in this system is 2.25%.
reaction pH value. Effects of applied anodic potential. To examine the effects of
Effects of H2O2 concentrations. To determine the impact of various W.E. anodic potentials on degradation of MB, 10 mg L−1
H2O2 concentrations on PEC/H2O2 synergistic degradation, the MB, 0.05 mol per L Na2SO4, and 2.25% H2O2 were added to the
ITO + FST working electrode (xed FST 30 mg) was applied at photoelectric reaction cell, the solution pH was adjusted to 3.0,
a bias voltage of +0.6 V (vs. SCE). The solution in the photocell and ITO + FST W.E. (xed FST 30 mg) was applied at potentials
contained 10 mg L−1 MB, 0.05 mol per L Na2SO4, and H2O2 with of +0.4 V, +0.6 V, +0.8 V, +1.0 V, and +1.2 V (vs. SCE). As shown in
concentrations of 0.00%, 1.65%, 1.95%, 2.25%, 2.55% and Fig. 6c, MB rapidly degraded with increasing potential at the
2.85%, respectively. Finally, the solution was adjusted to pH potential range of +0.4–+0.6 V (vs. SCE). At the potential of
value of 3.0. Degradation efficiency of MB at different degra- +0.6 V (vs. SCE), the degradation efficiency of MB was 98.25%
dation times under each group were compared and analyzed within 2 min. The bias voltage applied on W.E. makes the
(Fig. 6b). The amount of H2O2 was established to be an visible-light photogenerated electrons to ow to the C.E. along
important factor in MB degradation. When H2O2 concentration the external circuit, thereby reacting with H2O2 to generate
was 2.25%, degradation efficiency was highest within 1 to cOH.49 However, as the potential continued to rise, degradation
3 min. H2O2 is benecial for photocatalytic reaction by trapping efficiency of MB decreased, because too high potential caused
the conduction band e− in order to generate more cOH radi- the electropolymerization of MB50 and the oxidation of H2O2.
cals.47 However, when the concentration of H2O2 was higher H2O2 had an oxidation peak at +0.6 V (vs. SCE) (Fig. S4†). If the

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potential exceeded + 0.6 V, the H2O2 added in the system was

consumed by oxidation, which reduced the MB's degradation
efficiency. Thus, anode potential +0.6 V (vs. SCE) is the optimal
potential of the system.
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Effects of FST loading amounts. The xed amount of FST

catalyst on the working electrode directly affects the degrada-
tion efficiency of MB. As displayed in Fig. 6d, the effects of FST
loading amounts on MB degradation, where the conditions
included 10 mg L−1 MB, 0.05 mol per L Na2SO4, 2.25% H2O2, pH
3.0, +0.6 V (vs. SCE) to the W.E. and different FST xed quan-
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tities (10, 20, 30, 40, and 50 mg). When the xed amounts of FST
were 10–30 mg, the degradation efficiency of MB increased with
increasing xed amounts of catalysts. When the xed amount of
catalysts was 30 mg, the MB degradation efficiency was Fig. 7 Degradation efficiency and TOC removal rate of MB, Rh B, MO,
maximum, while the degradation efficiency of MB gradually and AMX.
decreased at >30 mg. Too much catalysts negatively affect the
degradation efficiency, while agglomeration between catalyst
particles reduces the number of active sites.51 Besides, too much respectively. Moreover, this system obtained TOC removal rate
FST increases the thickness of the catalyst layer on the surface of 83.5% (MB), 77.9% (Rh B), 80.2% (MO), and 65.5% (AMX),
of ITO, which affects photoanode conductivity and visible light indicating the incomplete mineralization of MB, Rh B, MO, and
transmittance. Thus, the optimal xed amount of FST is AMX in the PEC/H2O2 system within 8 min and the presence of
determined to be 30 mg. intermediate products. In general, the FST PEC/H2O2 syner-
Effects of MB initial mass concentrations. The effects of MB gistic degradation system showed excellent oxidative degrada-
initial mass concentrations (1, 5, 10, 15, 20 mg L−1) on degra- tion and mineralization abilities for MB, Rh B, MO, and AMX,
dation rates were evaluated. The system contained 0.05 mol per indicating the wide applicability of PEC/H2O2 coupling system
L Na2SO4, 2.25% H2O2, pH 3.0, the W.E. (xed FST 30 mg) for organic pollutants wastewater treatment.
applied at the potential of +0.6 V (vs. SCE). The effects of initial
mass concentration of MB solution on degradation were shown
in Fig. 6e. The degradation efficiencies of ve different 3.6. Degradation mechanism
concentrations of MB by FST PEC/H2O2 system were above 90%,
with 10 mg L−1 exhibiting the best degradation effect. The possible reaction mechanism of the FST PEC/H2O2 syner-
Recyclability performance of FST. The PEC/H2O2 degrada- gistic degradation system is shown in Fig. 8. When visible light
tion experiment was performed at optimal conditions of 10 mg irradiates FST, the energy (hn) of the incident photon is higher
L−1 MB, 0.05 mol per L Na2SO4, 2.25% H2O2, pH 3.0, and +0.6 V than the semiconductor band gap (Eg), and the electrons in the
(vs. SCE) potential to the W.E. (xed FST 30 mg). Aer W.E. was valence band (VB) are excited to transition into the conduction
vacuum-dried at 80 °C, the above degradation experiment was band (CB) to become highly active photogenerated electrons
repeated 8 times, and then the degradation efficiency of MB (e−); photogenerated positively charged holes (h+) stay in the
measured each time. As can be seen from Fig. 6f, the MB VB, generating photogenerated h+–e− pairs. Upon separation,
degradation efficiency were above 98% within 5 recycled and the e− and h+ move to the surface of the semiconductor. The h+
reused experiments, and the degradation efficiency only showed in the VB reacts with H2O to generate hydroxyl radicals (eqn (4));
a slight decrease in 6–8 degradation cycles, demonstrating that the e− in the CB moves to the platinum counter electrode
FST catalysts were recyclable and stable. Comparable ndings through an external circuit under the action of a bias voltage.
have been reported, where such magnetically attached FST Photogenerated e− reacts with adsorbed or dissolved O2 on the
working electrode had the desired stability.33 The magnetic FST electrode surface to form cO2− (eqn (5)). In an acidic environ-
was loaded on the surface of ITO working electrode by attractive ment of the system, e− reacts with O2 to form H2O2 (eqn (6)),52,53
forces of the magnet, the FST was rmly xed and had a good aer which H2O2 reacts with cO2− to produce more cOH (eqn
stability. (7)).54 By adding H2O2 to the system, e− can directly activate
H2O2 to generate a large number of cOH (eqn (8)).49 The cOH and
cO2− in the system are involved in oxidative degradation of
3.5. PEC/H2O2 synergistic degradation of pollutants pollutants.
To further discussion the versatility of PEC/H2O2 synergistic
h+ + H2O / cOH + H+ (4)
system for the treatment of different organic pollutants, the
degradation experiments of four kinds of pollutants (MB, Rh B, e− + O2 / cO2− (5)
MO, AMX) were carried out. As displayed in Fig. 7, the
maximum degradation efficiencies of MB, Rh B, MO, and AMX e− + O2 + 2H+ / H2O2 (6)
in the FST PEC/H2O2 synergistic system could reach up to
98.8%, 96.7%, 97.7% and 83.9% aer 8 min illumination, H2O2 + cO2− / cOH + OH− + O2 (7)

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Fig. 8 Reaction mechanism of FST PEC/H2O2 synergistic degradation system.

H2O2 + e− / cOH + OH− (8) amount of active species. The addition of EDTA–2Na had no
signicant effects on MB degradation. Although EDTA–2Na
captures h+ and reduces the cOH generated in eqn (4), the
The free radical quenching experiment was performed to capture of h+ is more conducive to separating e− and h+, and the
verify the generation and degradation mechanisms of active eqn (5), (6), (7) and (8) caused by photogenerated e− can still
free radicals in the PEC/H2O2 synergistic degradation reaction. generate large amounts of hydroxyl radicals, which continue to
Tert-butanol (TBA), benzoquinone (BQ), ethylenediaminetetra- degrade pollutants. When AgNO3 was added as an e− scavenger,
acetic acid disodium salt (EDTA–2Na), and silver nitrate MB undergoed a certain degradation efficiency change, indi-
(AgNO3) were respectively added to the FST PEC/H2O2 degra- cating that e− played one signicant role in this system. Eqn (5),
dation system for MB as quenchers, to scavenge for related (6), (7) and (8) show that e− contributes to generation cO2− and
reactive species, including hydroxyl radicals (cOH), superoxide cOH. Based on the above ndings, the cOH generated by e− and
radicals (cO2−), photogenerated holes (h+) and photogenerated external H2O2 in eqn (8) are the most important active species in
electrons (e−).55,56 Fig. 9 displayed that addition of TBA, as the pollutant degradation process. In the FST PEC/H2O2
a scavenger for cOH, signicantly inhibited the MB degradation synergistic degradation system, electrons are generated by FST
reaction, indicating that cOH was the main species in this photocatalysis, and bias voltage promotes separation of h+ and
system. From the eqn (4), (5), (6), (7) and (8), cOH is the most e−. Due to reactions involving photogenerated h+ and e−, cOH
active substance produced by the system. The degradation and cO2− are formed, while electrons promote the formation of
efficiency of MB slightly decreased aer adding BQ, suggesting cOH from a large amount of H2O2 in the solution, forming the
that variations of cO2− had little effects on MB degradation. photocatalytic-electro-H2O2 synergistic system to promote the
cO2− was only generated by eqn (5), and accounted for a small rapid degradation of pollutants.

4. Conclusions
In summary, visible-light driven PEC/H2O2 coupling system was
developed for degradation of organic pollutants (MB, Rh B, MO,
AMX) by magnetic FST-loaded photoelectrode. Through char-
acterization by TEM, XRD, UV-vis DRS, BET, XPS and EIS, the
chemical and physical properties of the FST catalyst were
systematically analyzed. Taking advantage of the synergistic
effect of photoelectrocatalysis and H2O2 photolysis, the system
exhibited greatly enhanced performance. The FST PEC/H2O2
synergistic degradation system showed comparable degrada-
tion efficiencies for MB (98.8%), Rh B (96.7%), MO (97.7%), and
AMX (83.9%), indicating the wide applicability for various
organic pollutants wastewater treatment. In the PEC/H2O2
process, through applications of a bias voltage on the working
Fig. 9 Degradation efficiency of MB using different radical scavengers. electrode, photogenerated electrons were guided along the

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generate cOH, which increased the amounts of strong oxidizing R. M. Rodrı́guez and E. Brillas, Degradation of clobric
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Bo Zhang: investigation, methodology, writing – original dra.
10 S. Wu and Y. H. Hu, A comprehensive review on catalysts for
Xuemei Li: conceptualization, validation, resources, writing –
electrocatalytic and photoelectrocatalytic degradation of
review & editing, supervision, project administration, funding
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acquisition. Yongshan Ma: soware, visualization. Tianyi Jiang:
11 P. Alulema-Pullupaxi, P. J. Espinoza-Montero, C. Sigcha-
data curation. Yanyan Zhu: validation. Huixue Ren: supervision,
Pallo, R. Vargas and J. L. Paz, Fundamentals and
funding acquisition. All authors have approved the nal version
Applications of Photoelectrocatalysis as an Efficient
of the manuscript.
Process to Remove Pollutants from Water: A Review,
Chemosphere, 2021, 281, 130821.
Conflicts of interest 12 J. Schneider, M. Matsuoka, M. Takeuchi, J. Zhang,
Y. Horiuchi, M. Anpo and D. W. Bahnemann,
There are no conicts to declare. Understanding TiO2 photocatalysis: mechanisms and
materials, Chem. Rev., 2014, 114, 9919–9986.
13 Y. Z. Wang, M. Zu, X. S. Zhou, H. Lin, F. Peng and
Acknowledgements S. Q. Zhang, Designing efficient TiO2-based
photoelectrocatalysis systems for chemical engineering
This project was nancially supported by Natural Science
and sensing, Chem. Eng. J., 2020, 381, 122605.
Foundation of Shandong Province (No. ZR2020MD115,
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