Journal of Alloys and Compounds 947 (2023) 169480

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Journal of Alloys and Compounds

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

Boosting photoelectrochemical chlorine and hydrogen production with

oxygen vacancy rich TiO2 photoanodes ]]
]]]]]]
]]

Yuanchang Ye a, Bin Liao a, Miao Li a, Manfang Mai c, Li Zhang a, Lianke Ma a, Donghai Lin e,
⁎ ⁎⁎
Jishi Zhao d, , Dongchu Chen a,b, Xinzhou Ma a,b,
a
School of Materials Science and Hydrogen Energy, Foshan University, Foshan 528000, PR China
b
Guangdong Key Laboratory for Hydrogen Energy Technologies, Foshan 528000, PR China
c
School of Physics and Optoelectronic Engineering, Foshan University, Foshan 528000, PR China
d
Foshan Institute of Environment and Energy Technology, Foshan 528000, PR China
e
Shanghai Engineering Research Center of Advanced Thermal Functional Materials and School of Energy and Materials, Shanghai Polytechnic University, Shanghai
201209, PR China

a r t i cl e i nfo a bstr ac t

Article history: Photoelectrochemical chlorine (Cl2) evolution as the anodic reaction of solar hydrogen production is helpful
Received 5 December 2022 for increasing the additional value of hydrogen and reducing production cost. In this work, chemically stable
Received in revised form 16 February 2023 TiO2 nanotubes are used as the photoanodes for photoelectrochemical chlorine and hydrogen production.
Accepted 27 February 2023
Oxygen vacancies (VO) are introduced by post-annealing in H2/N2 atmosphere. By controlling the post-
Available online 28 February 2023
annealing temperature, concentration of oxygen vacancies is tuned efficiently. Systematic photoelec­
trochemical measurements reveal that the oxygen vacancies significantly enhance the PEC performance for
Keywords:
Solar hydrogen production Cl2 production with respect to the pristine TiO2. The sample post-annealed at 450 °C in H2/N2 achieves the
Oxygen vacancy highest Cl2 production rate of 37.12 μmol h−1 cm−2 with a Faradaic efficiency of 73.2% that resulted in fast
Chlorine evolution degradation of methyl orange at a speed of 5.73 mg h−1 cm−2. Furthermore, photocurrent of the two-
Methyl orange degradation electrode cell constructed with the VO-rich TiO2 is strongly increased by 250%, demonstrating that in­
Wastewater treatment troducing oxygen vacancies is a promising way for promoting the photoelectrochemical performance for Cl2
and H2 production. By careful measuring the Faradaic efficiency of various photoanodes, it is revealed that
the strongly boosted up Cl2 production is owing to enhancing utilization of photogenerated holes via the
oxygen vacancies.
© 2023 Elsevier B.V. All rights reserved.

1. Introduction evolution reaction (OER) at the (photo)anode, respectively. Photo­

Converting the abundant but discontinuous sunlight to chemical
fuels is considered as a promising way to deal with the issues of
global energy shortage and environmental pollution [1]. Hydrogen
with high energy density is one of ideal solar fuel candidates [2].
Photoelectrochemical (PEC) water splitting as an attractive route for
producing hydrogen has been widely studied to increase the con­
version efficiency and reduce the cost of hydrogen [3]. Generally, PEC
water splitting includes two separated half reactions of hydrogen
evolution reaction (HER) at the (photo)cathode and oxygen
⁎
Corresponding author.
⁎⁎
Corresponding author at: School of Materials Science and Hydrogen Energy,
Foshan University, Foshan 528000, PR China.
E-mail addresses: zhaojishi0219@163.com (J. Zhao),
xinzhou.ma@hotmail.com (X. Ma).
electrochemical hydrogen conversion efficiency is mainly hindered
by the kinetically slow OER [4]. On the other hand, producing low
commercially valuable oxygen (O2) is not helpful for increasing the
additional value of the photoelectrochemical produced hydrogen [5].
Recently, some efforts have been conducted to break these limita­
tions by substituting OER with other fast photoanodic reactions that
can produce high-value-added chemicals [6–8], such as H2O2 [9],
S2O8- [10], Dihydroxyacetone [11], Chlorocyclohexane [12] and so on.
Chlorine (Cl2) as an important chemical is widely used for was­
tewater treatment, polymer production and other industries, which
is more commercially valuable than O2 with a price of about $240
per ton [5]. 75 million tons Cl2 are produced annually via electrolysis
of NaCl that require huge amount of electric energy [13]. Therefore,
producing H2 and Cl2 with abundant solar energy is very attractive.
On the other hand, the 2-electron chlorine evolution reaction (CER)
is kinetically more favorable than the 4-electron OER [14]. Thus, CER

https://doi.org/10.1016/j.jallcom.2023.169480
0925-8388/© 2023 Elsevier B.V. All rights reserved.
Y. Ye, B. Liao, M. Li et al.
is a promising alternative counter reaction of the PEC hydrogen
evolution that would also be helpful for adding the extra value of
solar hydrogen.
The standard potential of CER of 1.36 VNHE [15] requires the
photoanodes having very positive valance band position, which can
be satisfied by some oxide semiconductors such as BiVO4 [16,17],
WO3 [8,18,19] and TiO2 [20,21]. Since Zou’s work on using the RhO2
modified Mo-doped BiVO4 photoanodes for producing Cl2 from
seawater [22], BiVO4-based photoanodes have attracted some at­
tentions for photoelectrochemical chloride oxidation [17,23,24].
However, inhibiting photo-corrosion of the BiVO4 is still needed to
deal with for long-term application [25]. In comparison with BiVO4,
WO3 and TiO2 are relatively stable against photo-corrosion. Recently,
Augustrynski et. al. achieved efficient photoelectrochemical CER
with porous WO3 [8]. However, the high surface recombination of
the photogenerated charge carriers at WO3 resulted in a very posi­
tive onset potential of photocurrent that seriously limited the energy
efficiency [26]. Alternatively, TiO2 as a representative semiconductor
is frequently used as photoanode, but most of efforts are con­
centrated on PEC water oxidation [27,28]. Up to now, only a few
studies have focused on PEC chloride oxidation that requires further
explored [19–21].
Chemically and optically stable TiO2 nanotube arrays have very
high specific surface area and open channel structure that are ben­
eficial for decreasing transport length of charge carriers and in­
creasing light absorption efficiency [29,30]. In this work, TiO2
nanotube arrays are used as the photoanodes to construct photo­
electrochemical cells for chlorine and hydrogen production. Never­
theless, the wide band gap and high recombination of the charge
carriers still limit the PEC performance of the TiO2-based photo­
anodes. Various methods have been developed to improve the PEC
performance of the TiO2-based photoanodes [30,31]. For example,
introducing oxygen vacancies is one of efficient methods for im­
proving the PEC performance of the TiO2 [32–36] and other oxide
photoanodes [37,38]. In this work, oxygen vacancy (VO) rich TiO2
photoanodes were obtained by post-annealing of the nanotube ar­
rays in N2 and H2/N2 atmosphere at different temperatures. Sys­
tematic photoelectrochemical measurements illustrated that all the
VO-rich TiO2 photoanodes had boosted up performance for Cl2 and
H2 production with respect to the pristine TiO2 photoanode. The
highest Cl2 production rate of 37.12 μmol h−1 cm−2 with a Faradaic
efficiency of 73.2% was achieved by the VO-rich TiO2 post-annealed
at 450 °C in H2/N2. Potential application of the produced Cl2 for
wastewater treatment has also been demonstrated by the rapid
degradation of methyl orange at a rate of 5.73 mg h−1 cm−2. By
careful study on the Faradaic efficiency of Cl2 production of various
TiO2, the dominate mechanism of the boosted performance for Cl2
production is attributed to the enhanced utilization of the photo­
generated charge carriers rather than upon improving selectivity of
Cl- oxidation. This work would be very constructive for developing
VO-rich TiO2 photoanodes for high-performance solar Cl2 and H2
production as well as for degradation of organic pollution.
2. Experimental
2.1. Preparation of VO-rich TiO2 photoanodes
Similar to the method reported by Yu [39], the TiO2 nanotube
photoanodes were fabricated with electrochemical anodization fol­
lowed by calcination. Firstly, amorphous TiO2 nanotubes were pre­
pared by electrochemical anodization of a mechanically polished Ti
foil using a DC voltage of 30 V for 3 h in the mixture solution of
glycerol and H2O (50:50 vol%) containing 1 wt% NH4F electrolyte.
After electrochemical anodization, the as-prepared amorphous TiO2
nanotubes were then calcined at 600 °C for 2 h in air at a heating rate
of 5 °C min−1 to improve their crystallization. 600 °C was the optimal
2
Journal of Alloys and Compounds 947 (2023) 169480
calcination temperature determined by studying the effect of calci­
nation temperature on PEC performance of the TiO2 photoanodes
with linear sweep voltammetry (Fig. S1). To obtain VO-rich TiO2
photoanodes, the pristine TiO2 photoanodes were then post-an­
nealed respectively in pure N2 and H2/N2 (10%/90%) atmosphere
(flowing 40 sccm H2 and 400 sccm N2) at different temperature of
300, 350, 400, 450, 500, 550 °C for 2 h at a heating rate of 5 °C min−1.
Herein, the post-annealed TiO2 photoanodes are denoted as TiO2-N-
450 (in pure N2 atmosphere), TiO2-H-300, TiO2-H-350, TiO2-H-400,
TiO2-H-450, TiO2-H-500 and TiO2-H-550 (in H2/N2 atmosphere),
respectively.
2.2. Characterization of TiO2 photoanodes
Morphology of the TiO2 photoanodes was imaged with a Hitachi
S4800 scanning electron microscope (SEM). Crystallization and
phase composition of the TiO2 were characterized by a X′Pert PRO X-
ray diffractometer using Cu Kα (λ = 0.154 nm) radiation. X-ray pho­
toelectron spectra of the TiO2 were recorded with a Thermo Fisher
Scientific ESCALAB 250 XI, irradiated with Al Kα (hν=1486.60 eV) at a
500 µm diameter spot. The XPS results were calibrated with the
binding energy of C 1 s photoelectrons of 284.8 eV. Raman spectra of
the TiO2 were recorded by a Horiba LabRam HR Evolution Raman
microscope with a 532 nm laser as the excitation light. The relative
diffuse reflectance spectra of the TiO2 photoanodes in the range from
200 nm to 800 nm were measured with a Shimadzu UV-3600 Plus
UV–VIS–NIR spectrophotometer.
2.3. Photoelectrochemical characterizations
Photoelectrochemical performance of the TiO2 photoanodes was
investigated with an electrochemical workstation of CH Instruments
660D. As sketched in Fig. 1, all the photoelectrochemical measure­
ments were conducted with a two-compartment H-cell (Foshan Aoshi
Operanalysis, Fig. S2) with its two chambers separated by a cation
exchange membrane (Fumasep FKS-50). The TiO2 photoanode with
exposed area of 0.45 cm2 as the working electrode and an Ag/AgCl
(sat. KCl) as the reference electrode were sealed to the anodic
chamber, where 60 mL 1 M NaCl electrolyte with the pH adjusted to 1
by HCl was filled. A Pt wire counter electrode (ca. 2 cm2) was
mounted to the cathodic chamber which was filled with 35 mL 0.5 M
Na2SO4 with the pH adjusted to 1 using H2SO4. Before measurement,
the Na2SO4 was bubbled with Ar (99.99%) for 30 min to eliminate the
dissolved oxygen and air inside the sealed cathodic chamber. A 300 W
Xenon lamp (Perfect light PLS-SXE300D) was used as the light source
for all the PEC measurements. Periodic illumination was generated by
an electronic shutter. The optical power of illumination was measured
with an optical power meter (FieldBest) to be 500 mW cm−2. For
linear sweep voltammetry measurements, the potential of the TiO2
photoanodes was scanned positively from − 0.215–1.25 VAg/AgCl at a
rate of 5 mV s−1 under periodic illumination. The Mott-Schottky plots
under dark were obtained by sweeping the potential from
− 0.1–1.2 VAg/AgCl with a step of 0.01 V while superimposing a sinu­
soidal wave of 1 kHz, 10 mV. In the figures, the presented potential is
either referred to reversible hydrogen electrode (RHE) converted with
the relation of VRHE = (VAg/AgCl+0.197 +0.059 pH) V, or to the potential
of the standard chloride electrode (SClE) converted with the relation
of VSClE= (VAg/AgCl-1.163) V.
Photoelectrochemical Cl2 evolution performance of various TiO2
photoanodes at different potentials was measured by cycling the gas
inside the sealed anodic chamber to 200 mL indicative solution of
0.36 M Kl, 0.025 M NaOH and 0.049 M C8H5KO4, which would gra­
dually turn yellow upon the formation of I3- by Cl2 (see Fig. S8), si­
milar to the method described by Boyle [20]. The amount of Cl2 was
quantitatively obtained by measuring the absorbance of the I3-
peaking at 351 nm with a UV–vis spectrometer (UV-5200, Shanghai
Y. Ye, B. Liao, M. Li et al.
Fig. 1. Schematic of the two-compartment H-cell for photoelectrochemical measurements of the TiO2 photoanodes for Cl2 and H2 production and methyl orange degradation.
Metash). The standard curve between absorbance and the amount of
Cl2 is shown in Fig. S3. To further demonstrate the application for
degradation of organic pollution of methyl orange (MO), the pro­
ducing Cl2 was cycling into 250 mL H2O containing 2.5 mg MO
(10 mg L−1). The degradation rate of MO was obtained by measuring
the absorbance of the sampling solution each 0.5 h. The above used
three-electrode PEC cell can only study the PEC performance of the
TiO2 photoanode individually. Two-electrode configured PEC cells
are more practical for actual application. Therefore, the PEC perfor­
mance of the two-electrode cells constructed with the TiO2 photo­
anodes and a Pt wire dark cathode at different cell voltages was also
investigated. The produced H2 was measured with the thermal
conductivity detector of a gas chromatography (GC-7900, Zhongjiao
Jinyuan).
3. Results and discussion
3.1. Morphology, structure, optical properties of the TiO2 photoanodes
Fig. 2a shows the SEM image of the top-view morphology of the
pristine TiO2 nanotube array. The TiO2 nanotubes are highly ordered.
The average pore diameter of the nanotube is around 180–200 nm
and the thickness of the wall is about 20 nm. As revealed by Fig. S4,
the post-annealing treatment did not change the morphology of the
TiO2 photoanodes. The crystalline and phase composition of the
pristine TiO2 and the TiO2-N-450 and TiO2-H-450 were character­
ized with X-ray diffraction that are shown in Fig. 2b (XRD patterns of
other photoanodes can be seen in Fig. S5). In addition to the in­
tensive diffraction peaks from the Ti substrate, diffraction peaks of
the anatase phase and rutile phase are also observed, demonstrating
that the TiO2 nanotubes mixed with these two phases [40,41]. It is
believed that the heterojunctions between the two phases are
helpful for minimizing the recombination rate of the photo­
generated charge carriers and the ratio of the two phases on PEC
performance has been comprehensively studied [42–44]. The posi­
tion and width of the diffraction peaks are almost the same, in­
dicating that the post-annealing treatment did not significantly
change the crystalline and phase composition of the TiO2.
Fig. 2c and d show the Raman spectra of the TiO2 photoanodes.
The most intense peak at 143 cm−1 and the less intense peak at
196 cm−1 can be attributed to the Eg modes of the anatase phase [45].
The peaks at 395 cm−1, 514 cm−1 and 636 cm−1 correspond to the B1 g,
A1 g+B1 g and Eg modes of the anatase phase, respectively [46]. The
presence of the rutile phase is confirmed by its Eg mode at 445 cm−1
and the A1 g mode at 612 cm−1 [45]. XRD results and Raman spectra
3
Journal of Alloys and Compounds 947 (2023) 169480
confirm that the TiO2 photoanodes contained the mixed phases of
anatase and rutile and the post-annealing treatment did not change
the crystalline and phase composition of the TiO2 photoanodes.
The light harvest properties of the TiO2 photoanodes were eval­
uated by the diffuse reflectance UV–vis spectra in Fig. 2e. With re­
spect to the pristine TiO2, the characteristic absorption edge of the
post-annealed TiO2 photoanodes just slightly red-shifted to around
390 nm and the adsorption intensity slightly increased as well. Ac­
cording to the Kubelka-Munk function:
( h )n (hv Eg)
where α is absorption efficiency, hν is energy of light, Eg is the band
gap of the semiconductor, n is 0.5 for indirect bandgap semiconductor
and is 2 for direct bandgap semiconductor, the band gap of the TiO2
photoanodes can be determined [47]. Fig. 2f shows the Tauc plots
derived from the diffuse reflectance UV–vis spectra via the Kubelka-
Munk function. The Eg of the TiO2 photoanodes was obtained by the
intercept the linear portion of the Tauc plots with the hv-axis, as
shown in Fig. S6. It can be seen from the inset in Fig. 2f that the Eg of
the pristine TiO2 is 3.13 eV and the Eg of the VO-rich TiO2 was just
slightly reduced with the biggest variation of 0.07 eV. The VO-rich TiO2
photoanodes show considerably enhanced visible light absorption
capability upon the light trapping effect of the nanotube structure and
the transitions between the VO level and the energy bands of the TiO2
[48]. With respect to the pristine TiO2, light harvesting capability of
the VO-rich TiO2 was slightly improved. However, it needs to point out
that the small enhancement on light harvesting should not be the
dominated reason for the strongly boosted up PEC performance
achieved by the VO-rich TiO2 photoanodes.
Impact of the post-annealing temperature and atmosphere on
the surface chemical composition and oxygen vacancy content was
explored with high resolution XPS spectra of Ti 2p and O 1 s Fig. 3a
shows the Ti 2p XPS spectra of the pristine TiO2 and VO-rich TiO2
photoanodes. There are four binding energy (BE) peaks of Ti 2p
observed for all the photoanodes. The BE peaks of 458.7 eV and
464.4 eV of the pristine TiO2 are corresponding to the Ti 2p3/2 and Ti
2p1/2 of Ti4+, respectively [33]. Separation of the two BE peaks is
5.7 eV, which is typical for the Ti4+-O bonds in TiO2 [48]. There are
two small peaks centered at low binding energy of 458.4 eV and
463.6 eV are assigned to 2p3/2 and 2p1/2 of Ti3+, demonstrating the
existence of Ti3+ on the surface of the pristine TiO2 [48]. The surface
VO content of the pristine TiO2 is calculated to be 6.34% with the XPS
peak areas of Ti 2p (see Table S1) [48]. The BE peak positions of Ti 2p
of the TiO2-N-450 did not shift with respect to the pristine TiO2,
while the surface VO content increased to 8.10%. Post-annealing with
Y. Ye, B. Liao, M. Li et al.
Fig. 2. (a) SEM image of the pristine TiO2 nanotubes; (b) XRD patterns of the pristine TiO2, the TiO2-N-450 and the TiO2-H-450 photoanodes; (c) Raman spectra and (d) Zoom-in
Raman spectra of the TiO2 photoanodes; (e) diffuse reflectance UV–vis spectra of the TiO2 photoanodes; (f) the derived Tauc Plots and the Eg of the TiO2 photoanodes.
the present of 10% H2 increased the VO content to 9.72% at 450 °C.
Surprisingly, the surface VO content was not further increased by
post-annealing at 500 °C and 550 °C. It might because that lattice
oxygen in bulk had sufficient energy to diffuse to surface and re­
sulted in the formation of oxygen vacancies in depth that could not
be analyzed with XPS. This suggestion is supported by the Mott-
Schottky results in Fig. 4(b), which demonstrate that the donor
concentration related to oxygen vacancy content in bulk indeed in­
creased with the increasing post-annealing temperature.
Since the missed oxygen atoms do not generate any X-ray pho­
toelectron, oxygen vacancies cannot be directly measured with XPS
of oxygen. However, upon exposure to ambient for certain time,
surface hydroxyls (absorbed -OH group) would be formed by dis­
sociation of water at oxygen vacancies [49]. Therefore, the existence
of the oxygen vacancies were evidenced by the XPS signal of the
absorbed -OH group [32]. Fig. 3b shows the high resolution XPS
spectra of O 1 s that were deconvoluted into three peaks of 529.8 eV,
330.7 eV and 532.5 eV, corresponding to the lattice oxygen (OL), the
surface absorbed oxygen (OA) and the oxygen of the absorbed -OH
group (OOH) [50], respectively. Obviously, the surface of all the TiO2
photoanodes contained Ti3+ and VO. With respect to the pristine
TiO2, the content of Ti3+ and VO was increased by post-annealing
treatment. Generally, the BE peak positions of Ti 2p and O 1 s were
just slightly shifted. The largest shifts were observed for the TiO2-H-
350 that the Ti4+ 2p1/2 shifted positively by 0.2 eV and the Ti4+ 2p3/2
shifted positively by 0.1 eV. Meanwhile the O 1 s peak of OL shifted
positively by 0.15 eV. The positively shifted BE peak positions in­
dicate the shorten of the Ti4+-O bond length.
3.2. Photoelectrochemical performance of the TiO2 photoanodes
Firstly, the photoelectrochemical performance of the pristine TiO2
and the VO-rich TiO2 photoanodes in 1 M NaCl (pH=1) was studied
with linear sweep voltammetry (LSV). Fig. 4a shows the LSV curves of
the TiO2 photoanodes under periodic light illumination. Considerable
photocurrent was produced even when the potential was as low as
0.08 VRHE for all the photoanodes, pointing to the low onset potential
of PEC reactions. Though relatively high photocurrent at the low
4
Journal of Alloys and Compounds 947 (2023) 169480
potential region (< 0.3 VRHE) was produced, the obvious cathodic
spikes soon after illumination off indicate serious surface combina­
tion loss, since the measured cathodic spikes related to the electron
flux moving to combine with the holes on surface. Photocurrent of the
pristine TiO2 rapidly increased with the positively increasing potential
to a plateau of about 1.88 mA cm−2. In comparison with the pristine
TiO2, all the VO-rich TiO2 photoanodes generated significantly boosted
up photocurrent, demonstrating the strong enhance effect of the
oxygen vacancies on PEC performance. The photocurrent of the TiO2-
N-450 reached to 2.2 mA cm−2 at 1.23 VRHE, enhanced by a factor of
1.17. The TiO2-H-300, TiO2-H-350 and TiO2-H-400 had comparable
PEC performance and their photocurrent was increased by a factor of
1.42 to around 2.68 mA cm−2 at 1.23 VRHE. The TiO2-H-450 photoanode
achieved the highest photocurrent of 3.21 mA cm−2 with an enhance
factor of 1.71. After that, the PEC performance was not further im­
proved with the increasing post-annealing temperature. The photo­
current of the TiO2-H-500 and TiO2-H-550 was slightly lower with
respect to that of the TiO2-H-450.
To elucidate the enhance effect of the oxygen vacancies on the
photocurrent, interfacial properties of the TiO2 photoanodes were
studied with Mott-Schottky plots, as shown in Fig. 4b. Obviously, the
slope of the linear portion of the Mott-Schottky plots is strongly
dependent on the post-annealing conditions. Concentration of donor
ND and the flat band potential φFB of the TiO2 photoanodes can be
determined from the Mott-Schottky plots [51] with Eq. (1):
1 2 kT
2
= FB
CSC e o r ND e (1)
in which CSC is capacitance of semiconductor electrode, φ is the
applied electrode potential, φFB is flat band potential, k is Boltzmann
constant; T is absolute temperature, e is electron charge, εo is di­
electric constant in vacuum, εr is relative dielectric constant which is
55 for TiO2 [52] and ND is donor concentration. The obtained ND of
the photoanodes is presented on Fig. 4b. ND of the pristine TiO2 is
6.24 × 1017 cm−3. ND of the TiO2-H-300, TiO2-H-350 and TiO2-H-400
is around 2.20 × 1018 cm−3 that is consistent with their comparable
photocurrent. ND of the TiO2-H-450 rapidly increased to 8.80 × 1018
cm−3, 3.24 times of that of the TiO2-N-450, revealing that oxygen
Y. Ye, B. Liao, M. Li et al.
Fig. 3. XPS spectra of the pristine TiO2, the TiO2-N-450, TiO2-H-300, TiO2-H-350, TiO2-H-400, TiO2-H-450, TiO2-H-500 and TiO2-H-550, (a) Ti 2p and (b) O 1s.
vacancies were introduced more easily by the present of hydrogen in
the post-annealing atmosphere. The TiO2-H-550 has the highest ND
of 8.58 × 1020 cm−3 which is 3 orders of magnitude higher with re­
spect to the pristine TiO2.
As indicated by Fig. 4b, not only the ND was strongly increased by
post-annealing, the φFB of the VO-rich TiO2 shifted positively to
around 0.4 VRHE with respect to the φFB of the pristine TiO2 of
0.136 VRHE. In fact, the positively shifted φFB is not helpful for en­
hancing photocurrent since the potential drop across the depletion
layer would be decreased. The band bending Φsc can be predicted by
Eqs. (2) and (3),
sc = FB H (2)
CH
sc
= TiO2 was highest, the lowest ND of 6.24 × 1017 cm−3 made the
H Csc (3)
where ΦH is the potential drop across the Helmholtz layer and CH is
the capacitance of the Helmholtz layer [51]. Fig. 4c shows the Φsc as a
5
Journal of Alloys and Compounds 947 (2023) 169480
function of the applied electrode potential that was calculated with
the CH of 200 μF cm−2 deduced from the Mott-Schottky plots in the
section where the interfacial capacitance was dominated by the CH.
Apparently, the Φsc of the pristine TiO2 was largest. However, this
result seems contradictory with the photocurrent in Fig. 4a.
Separation efficiency of the photo-generated charge carriers is
not only determined by the Φsc but also by the thickness and the
electric field of the depletion layer. According to Eq. (4),
20 r kT
w= sc
eND e (4)
the depletion layer thicknesses w of the TiO2 photoanodes were
calculated [53] and shown in Fig. 4d. Although the Φsc of the pristine
thickness of depletion layer largest that resulted in the weakest
strength of the electric field (see Fig. S7). This is the main reason for
the lowest photocurrent generated by pristine TiO2 photoanode.
Y. Ye, B. Liao, M. Li et al.
Fig. 4. (a) LSV curves of various TiO2 photoanodes under periodic illumination; (b) Mott-Schottky plots of the TiO2 photoanodes measured under dark; (c) the calculated potential
drop across the depletion layer as a function of the applied potential; (d) the calculated thickness of the depletion layer of the TiO2 photoanodes as a function of the applied
potential.
As shown in Fig. 4d, the depletion layer thicknesses decreased
with the increasing post-annealing temperature. The depletion layer
thicknesses of the TiO2-H-300, TiO2-H-350 and TiO2-H-400 were
around 40 nm, twice of the nanotube wall thickness. The higher
electric field upon the thinner depletion layer enhanced the charge
separation efficiency and can be attributed to the increased photo­
current with respect to the pristine TiO2. The highest photocurrent
achieved by the TiO2-H-450 can also be explained by this point of
view. The depletion layer thickness of the TiO2-H-450 was around
20 nm that was close to the wall thickness of the TiO2 nanotubes,
indicating that the wall of the TiO2-H-450 was completely depleted
with the highest electric field horizontally for efficient charge carrier
separation. On the other hand, the existed oxygen vacancies in the
depletion layer could extract the holes for prolonging their lifetime
[34]. Long lifetime of the photogenerated holes inside the com­
pletely depleted nanotubes were very helpful for electrochemical
reaction in timescale of ms to s [54]. Though the higher ND made the
TiO2-H-500 and the TiO2-H-550 obtained stronger electric field upon
the much thinner depletion layer, the wall of the nanotubes could
not be completely depleted in these cases, and the charge carriers
generated in the middle of the wall needed to diffuse to the deple­
tion layer for separation. Therefore, photocurrent of the TiO2-H-500
and TiO2-H-550 did not further increase with the increasing ND.
It is interesting to observed that considerable photocurrent was
generated in the potential region more negative than the φFB in
Fig. 4a, especially for the VO-rich TiO2 photoanodes. The explanation
for this observation is because the applied potential was mainly
6
Journal of Alloys and Compounds 947 (2023) 169480
distributed across the Helmholtz layer in this potential region that
only resulted in a small upward band bending across the accumu­
lation layer. The very positive valance band position of the TiO2 still
would allow portion of the photo-generated holes transport to sur­
face for taking part in anodic reactions.
Fig. 5a-f show the j-t curves of the TiO2 photoanodes at different
potentials under periodic illumination. Herein, the presented po­
tential is referred to the standard potential of chloride electrode
(VSClE). The j-t results are consistent with the LSV results that sig­
nificantly enhanced photocurrent was obtained by the VO-rich TiO2
photoanodes. As shown in Fig. 5a, even at − 1.0 VSClE, photocurrent of
1.5 mA cm−2 was produced by the TiO2-H-450 photoanode, in­
dicating a large photovoltage was provided for PEC Cl2 evolution,
benefit from the very positive valance band position of the TiO2. As
expected, the photocurrent of all the photoanodes was increased
with the increasing potential. At − 0.3 VSClE, the highest photocurrent
of 3.0 mA cm−2 was generated by the TiO2-H-450, which was in­
creased by a factor of 1.71 with respect to the pristine TiO2.
The produced Cl2 of the TiO2 photoanodes at different applied
potentials was measured by cycling the gas inside the anodic
chamber into the indicative solution of KI which was gradually
turning to yellow (see Fig. S8). The amount of Cl2 was calculated
with the absorbance peak at 351 nm. Fig. 5i shows the corresponding
produced amount and Faradaic efficiency (FE) of Cl2 in 2 h with ef­
fective illumination time of 1 h. The photocurrent in full timescale of
2 h can be found in Fig. S9. At − 0.4 VSClE, the TiO2-H-450 produced
the highest amount of Cl2 of 37.12 μmol cm−2 with a FECl2 of 73.92%,
Y. Ye, B. Liao, M. Li et al. Journal of Alloys and Compounds 947 (2023) 169480

Fig. 5. Photocurrent of the TiO2 photoanodes at different potentials of (a) − 1.0 VSClE, (b) − 0.9 VSClE, (c) − 0.8 VSClE, (d) − 0.7 VSClE, (e) − 0.6 VSClE, (f) − 0.5 VSClE, (g) − 0.4 VSClE, (h)
− 0.3 VSClE; (i) the corresponding amount and Faradaic efficiency of Cl2.

Fig. 6. (a) Long-term photocurrent of the TiO2-H-450 at −0.4 VSClE; (b) degradation of methyl orange, production of H2 and the corresponding amount of the passed charge.

which was 1.56 times of that of the pristine TiO2 of 23.76 μmol cm−2.
However, though the Cl2 production was significantly enhanced by
the VO-rich TiO2, as indicated by the FECl2, the tendency of FECl2
generally decreased with the increasing post-annealing temperature
and was not consistent with the tendency of surface vacancy content
(listed in Table S1). Therefore, this reveals that the selectivity of Cl-
oxidation was not improved by the surface oxygen vacancies, the
enhanced Cl2 production of the VO-rich TiO2 was mainly because of
the more efficient utilization of the photogenerated charge carriers.
The non-catalysis effect of the surface vacancies on Cl- oxidation
would be understood by the self-healing of the surface oxygen va­
cancies in aqueous solutions [49]. On the other hand, the FECl2
steeply decreased with the increasing potential. For example, FECl2 of
the TiO2-H-450 decreased from 85.6% to 52.9% as the potential in­
creased from − 1.0 VSClE to − 0.3 VSClE, revealing that the kinetically
slow oxygen evolution was more favorable at relatively positive
potential. But in general, the FECl2 of the VO-rich TiO2 is higher than
that reported FECl2 [8].
Fig. 6a shows long-term photocurrent of the TiO2-H-450 at
− 0.4 VSClE. The photocurrent steeply decreased about 15% in the first

7
Y. Ye, B. Liao, M. Li et al.
Fig. 7. (a) Scheme of the two-electrode cell for PEC production of H2 and Cl2; (b) LSV curves of the two-electrode cells constructed with the pristine TiO2 and the TiO2-H-450 as
the photoanode, respectively; (c) long-term photocurrent of the two-electrode cell with the TiO2-H-450 under different cell voltages; (d) the corresponding production rate of H2,
Cl2 and its Faradaic efficiency.
3 h and then trended to stable at around 2.5 mA cm−2. One possible
reason for the decreased photocurrent would be the dilution effect
of Cl- inside the nanotube. Blockage effect of the generated gas
bubbles attached on TiO2 surface was another possible reason for the
decreased photocurrent. As shown by Fig. 6b, the amount of passed
charge almost linearly increased with time, demonstrating the high
stability of the TiO2-H-450. In order to demonstrate the application
of the produced Cl2 for wastewater treatment, e.g., degradation of
organic pollution, the gas inside the anodic chamber was cycling into
250 mL H2O containing 2.5 mg simulated organic dye of methyl or­
ange (MO). The degradation of the MO was measured each 0.5 h with
a UV–vis spectrometer. The corresponding absorbance spectra are
shown in Fig. S10. As shown by the point-line curves in Fig. 6b,
2.5 mg MO was almost completely degraded in 2 h. After that, an­
other 2.5 mg MO was injected into the 250 mL H2O for the second-
round measurement. Totally 12.5 mg MO was injected in 10 h. The
degradation rate of the MO by the PEC producing Cl2 was about
5.73 mg h−1 cm−2 (calculated with the effective illumination time),
which is comparable with the reported results [55–57]. Meanwhile
the produced H2 at the Pt dark electrode was collected in the sealed
cathodic chamber and the evolution rate was determined to be 53.64
μmol h−1 cm−2, which is much higher than the production rate of 2.1
μmol h−1 cm−2 obtained with the AgIn5Se8 sensitized TiO2 nanotubes
[58]. The Faradaic efficiency of the H2 was close to 100%. The above
studies demonstrate that the highly stable VO-rich TiO2 photoanodes
8
Journal of Alloys and Compounds 947 (2023) 169480
can be used for long-term Cl2 and H2 production as well as organic
pollution degradation.
3.3. PEC performance of the two-electrode cells for H2 and Cl2
production
In above studies, the PEC performance of the TiO2 photoanodes
was individually studied in the three-electrode configured cell. The
effect of the dark cathode on the overall PEC performance could not
be figured out with the three-electrode system [59]. Furthermore,
the three-electrode PEC cell is relatively complicate for practical
application. In contrast, two-electrode configured PEC cells are more
practical for actual application. Therefore, in this work, two-elec­
trode PEC cells were also constructed with a Pt wire as the dark
cathode and the pristine TiO2 and the VO-rich TiO2 as the photo­
anode, respectively, as sketched in Fig. 7a. Effect of the cell voltage
on the performance of H2 and Cl2 production was studied. Ther­
modynamically, the equilibrium cell voltage for Cl2 and H2 evolution
is 1.419 V, which means that H2 and Cl2 would not be produced
under dark if the cell voltage was less than 1.419 V.
Under illumination electrons and holes were generated that could
make the quasi-Fermi level of the holes much more positive than the
equilibrium potential of chlorine evolution, and PEC production of H2
and Cl2 could be driven with a cell voltage less than 1.419 V.
Considerable photocurrent was observed in the LSV curves in Fig. 7b
Y. Ye, B. Liao, M. Li et al.
even when the cell voltage was as low as 0 V. Photocurrent of the two-
electrode cell using the TiO2-H-450 as the photoanode generated
3.5 mA cm−2 at 1.419 V, enhanced by 250% with respect to its coun­
terpart of the pristine TiO2, indicating that the overall performance of
the cell was dominated by the photoanode. As mentioned above, the
strongly boosted up photocurrent was resulted from the introduced
oxygen vacancies in the TiO2-H-450, which increased the strength of
the electric field in the depletion layer and acted as the trapping
centers for the photogenerated holes to prolong their lifetime for
promoting oxidation of Cl-, as sketched in Fig. 7a.
Fig. 7b shows the long-term photocurrent of the PEC cell with the
TiO2-H-450 as the photoanode under various cell voltages and the
corresponding production rates of H2 and Cl2 were shown in Fig. 7c.
The photocurrent was almost constant at low cell voltage of 0.619 V,
0.719 V and 0.819 V. Steep decay of the photocurrent was observed
when the cell voltage was higher than 0.919 V. As expected, the
evolution rate of H2 increased from 26.2 μmol h−1 cm−2 to 52.0 μmol
h−1 cm−2 with the increasing cell voltage. The FE of Cl2 varied be­
tween 52% and 65% with the cell voltage. The highest FE of Cl2 of 65%
was obtained at 1.119 V that resulted in the highest Cl2 production
rate of 28.7 μmol h−1 cm−2.
4. Conclusions
In this work, VO-rich TiO2 photoanodes fabricated by post-an­
nealing treatment in H2/N2 atmosphere at different temperatures
were used as photoanodes for photoelectrochemical chlorine and
hydrogen production. With respect to the pristine TiO2 photoanode,
all the VO-rich TiO2 gained boosted up performance for H2 and Cl2
production. Among them, the TiO2-H-450 photoanode exhibited the
best performance, which achieved the highest Cl2 production of
37.12 μmol cm−2 h−1 with an FE of 73.9% at − 0.4 VSClE. By system­
atically studied the FE of Cl2 of the various TiO2 photoanodes, it is
revealed that the increased Cl2 production was not due to increasing
selectivity of Cl- oxidation but upon the enhanced utilization of
photogenerated holes by the oxygen vacancies that minimized the
recombination loss. As demonstrated by the rapid degradation of
methyl orange at a rate of 5.73 mg h−1 cm−2, the PEC production of
Cl2 showed a great potential application for organic dye degradation
and wastewater treatment. Finally, the two-electrode PEC cell con­
structed with TiO2-H-450 achieved H2 production rate of 49.2 μmol
cm−2 h−1 and the highest Cl2 production rate of 28.7 μmol cm−2 h−1
with the highest EF of 65% at the cell voltage of 1.119 V. This work is
constructive for guiding the fabrication of the high-performance VO-
rich TiO2 photoanodes and provides a deep insight into the me­
chanism of oxygen vacancy enhanced PEC Cl2 and H2 production.
CRediT authorship contribution statement
Yuanchang Ye: Methodology, Investigation, Conceptualization.
Bin Liao: Methodology, Investigation. Miao
Li: Investigation. Manfang Mai: Resources. Li Zhang: Data
curation. Lianke Ma: Resources. Donghai Lin: Data curation. Jishi
Zhao: Writing – original draft. Dongchu Chen: Writing – original
draft. Xinzhou Ma: Conceptualization, Methodology, Supervision.
Data availability
No data was used for the research described in the article.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
9
Journal of Alloys and Compounds 947 (2023) 169480
Acknowledgments
This work was financially supported the National Natural Science
Foundation of China (No. 11504242); the Project of Guangdong
Provincial Education (No. 2020KTSCX131); Guangdong Basic and
Applied Basic Research Foundation (Nos. 2020B1515120006 and
2020B1515120097); the Innovation Team of Universities of
Guangdong Province (Nos. 2020KCXTD011 and 2022KCXTD030); the
Guangdong Key Laboratory for Hydrogen Energy Technologies (No.
2018B030322005).
Appendix A. Supplementary material
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.jallcom.2023.169480.
References
[1] Y. Liu, F. Wang, Z. Jiao, S. Bai, H. Qiu, L. Guo, Photochemical systems for solar-to-
fuel production, Electrochem. Energy Rev. 5 (2022) 5.
[2] N. Pirrone, F. Bella, S. Hernández, Solar H2 production systems: current status
and prospective applications, Green Chem. 24 (2022) 5379–5402.
[3] A. Thakur, D. Ghosh, P. Devi, K.H. Kim, P. Kumar, Current progress and challenges
in photoelectrode materials for the production of hydrogen, Chem. Eng. J. 397
(2020) 125415.
[4] J. Zhang, J. Cui, S. Eslava, Oxygen evolution catalysts at transition metal oxide
photoanodes: their differing roles for solar water splitting, Adv. Energy Mater. 11
(2021) 2003111.
[5] K. Sayama, Production of high-value-added chemicals on oxide semiconductor
photoanodes under visible light for solar chemical-conversion processes, ACS
Energy Lett. 3 (2018) 1093–1101.
[6] K. Fuku, N. Wang, Y. Miseki, T. Funaki, K. Sayama, Photoelectrochemical reaction
for the efficient production of hydrogen and high-value-added oxidation re­
agents, ChemSusChem 8 (2015) 1593–1600.
[7] M. Natali, A. Sartorel, A. Ruggi, Beyond water oxidation: hybrid, molecular-based
photoanodes for the production of value-added organics, Front. Chem. 10 (2022)
907510.
[8] M. Jadwiszczak, K. Jakubow-Piotrowska, P. Kedzierzawski, K. Bienkowski,
J. Augustynski, Highly efficient sunlight-driven seawater splitting in a photo­
electrochemical cell with chlorine evolved at nanostructured WO3 photoanode
and hydrogen stored as hydride within metallic cathode, Adv. Energy Mater. 10
(2020) 1903213.
[9] K. Zhang, J. Liu, L. Wang, B. Jin, X. Yang, S. Zhang, J.H. Park, Near-complete
suppression of oxygen evolution for photoelectrochemical H2O oxidative H2O2
synthesis, J. Am. Chem. Soc. 142 (2020) 8641–8648.
[10] W. Xie, Z. Huang, R. Wang, C. Wen, Y. Zhou, Metallic Pt and PtOx dual-cocatalyst-
loaded WO3 for photocatalytic production of peroxydisulfate and hydrogen
peroxide, J. Mater. Sci. 55 (2020) 11829–11840.
[11] H. Tateno, S.-Y. Chen, Y. Miseki, T. Nakajima, T. Mochizuki, K. Sayama,
Photoelectrochemical oxidation of glycerol to dihydroxyacetone over an acid-
resistant Ta:BiVO4 photoanode, ACS Sustain. Chem. Eng. 10 (2022) 7586–7594.
[12] Z. Li, L. Luo, M. Li, W. Chen, Y. Liu, J. Yang, S.M. Xu, H. Zhou, L. Ma, M. Xu, X. Kong,
H. Duan, Photoelectrocatalytic C-H halogenation over an oxygen vacancy-rich
TiO2 photoanode, Nat. Commun. 12 (2021) 6698.
[13] H. Wang, Z. Han, Y. Zhou, X. Liu, D. Zeng, W. Wang, D. Sarker, L. Zhang, W. Wang,
Efficient photocatalytic chlorine production on bismuth oxychloride in chloride
solution, Appl. Catal. B 297 (2021) 120436.
[14] R.K.B. Karlsson, A. Cornell, Selectivity between oxygen and chlorine evolution in
the chlor-alkali and chlorate processes, Chem. Rev. 116 (2016) 2982–3028.
[15] K.S. Exner, Controlling stability and selectivity in the competing chlorine and
oxygen evolution reaction over transition metal oxide electrodes,
ChemElectroChem 6 (2019) 3401–3409.
[16] L. Ma, T. Chen, Q. Li, M. Mai, X. Ye, J. Mai, C. Liu, J. Zhang, D. Lin, X. Ma, Yb3+, Er3+
co-doped NaGdF4/BiVO4 embedded Cu2O photocathodes for photoelec­
trochemical water reduction with near infrared light, Appl. Surf. Sci. 585 (2022)
152650.
[17] A.M. Rassoolkhani, W. Cheng, J. Lee, A. McKee, J. Koonce, J. Coffel, A.H. Ghanim,
G.A. Aurand, C. Soo Kim, W. Ik Park, H. Jung, S. Mubeen, Nanostructured bismuth
vanadate/tungsten oxide photoanode for chlorine production with hydrogen
generation at the dark cathode, Commun. Chem. 2 (2019) 57.
[18] R. Pang, Y. Miseki, S. Okunaka, K. Sayama, Photocatalytic production of hypo­
chlorous acid over Pt/WO3 under simulated solar light, ACS Sustain. Chem. Eng. 8
(2020) 8629–8637.
[19] X. Huang, Y. Zhang, J. Bai, J. Li, L. Li, T. Zhou, S. Chen, J. Wang, M. Rahim, X. Guan,
B. Zhou, Efficient degradation of N-containing organic wastewater via chlorine
oxide radical generated by a photoelectrochemical system, Chem. Eng. J. 392
(2020) 123695.
[20] C. Boyle, N. Skillen, H.Q.N. Gunaratne, P.K. Sharma, J.A. Byrne, P.K.J. Robertson,
The use of titanium dioxide nanotubes as photoanodes for chloride oxidation,
Mater. Sci. Semicond. Process. 109 (2020) 104930.
Y. Ye, B. Liao, M. Li et al.
[21] G. Chehade, N. Alrawahi, B. Yuzer, I. Dincer, A photoelectrochemical system for
hydrogen and chlorine production from industrial waste acids, Sci. Total Environ.
712 (2020) 136358.
[22] W. Luo, Z. Yang, Z. Li, J. Zhang, J. Liu, Z. Zhao, Z. Wang, S. Yan, T. Yu, Z. Zou, Solar
hydrogen generation from seawater with a modified BiVO4 photoanode, Energy
Environ. Sci. 4 (2011) 4046–4051.
[23] S. Iguchi, Y. Miseki, K. Sayama, Efficient hypochlorous acid (HClO) production via
photoelectrochemical solar energy conversion using a BiVO4-based photoanode,
Sustain. Energy Fuels 2 (2018) 155–162.
[24] Z. Zheng, Y.H. Ng, Y. Tang, Y. Li, W. Chen, J. Wang, X. Li, L. Li, Visible-light-driven
photoelectrocatalytic activation of chloride by nanoporous MoS2@BiVO4 pho­
toanode for enhanced degradation of bisphenol A, Chemosphere 263 (2021)
128279.
[25] D.K. Lee, K.-S. Choi, Enhancing long-term photostability of BiVO4 photoanodes for
solar water splitting by tuning electrolyte composition, Nat. Energy 3 (2018) 53–60.
[26] J. Juodkazytė, M. Petrulevičienė, M. Parvin, B. Šebeka, I. Savickaja, V. Pakštas,
A. Naujokaitis, J. Virkutis, A. Gegeckas, Activity of sol-gel derived nanocrystalline
WO3 films in photoelectrochemical generation of reactive chlorine species, J.
Electroanal. Chem. 871 (2020) 114277.
[27] X. Zhang, S. Zhang, X. Cui, W. Zhou, W. Cao, D. Cheng, Y. Sun, Recent advances in
TiO2-based photoanodes for photoelectrochemical water splitting, Chem. Asian
J. 17 (2022) e202200668.
[28] N.R. Reddy, P.M. Reddy, N. Jyothi, A.S. Kumar, J.H. Jung, S.W. Joo, Versatile TiO2
bandgap modification with metal, non-metal, noble metal, carbon material, and
semiconductor for the photoelectrochemical water splitting and photocatalytic
dye degradation performance, J. Alloy. Compd. 935 (2023) 167713.
[29] J. Lim, Y.U. Shin, A. Son, S.W. Hong, S. Hong, TiO2 nanotube electrode for organic
degradation coupled with flow-electrode capacitive deionization for brackish
water desalination, npj Clean Water 5 (2022) 7.
[30] K. Arifin, R.M. Yunus, L.J. Minggu, M.B. Kassim, Improvement of TiO2 nanotubes
for photoelectrochemical water splitting: review, Int. J. Hydrog. Energy 46
(2021) 4998–5024.
[31] T.S. Rajaraman, S.P. Parikh, V.G. Gandhi, Black TiO2: a review of its properties and
conflicting trends, Chem. Eng. J. 389 (2020) 123918.
[32] X. Huang, X. Gao, Q. Xue, C. Wang, R. Zhang, Y. Gao, Z. Han, Impact of oxygen
vacancies on TiO2 charge carrier transfer for photoelectrochemical water split­
ting, Dalton Trans. 49 (2020) 2184–2189.
[33] X. Liang, Q. He, J. Zhang, X. Ding, Y. Gao, W. Chen, K.H.L. Zhang, C.Y. Haw,
Enhanced photo-carrier transportation at semiconductor/electrolyte interface of
TiO2 photoanode by oxygen vacancy engineering, Appl. Surf. Sci. 597 (2022)
153744.
[34] K.H. Kim, C.W. Choi, S. Choung, Y. Cho, S. Kim, C. Oh, K.S. Lee, C.L. Lee, K. Zhang,
J.W. Han, S.Y. Choi, J.H. Park, Continuous oxygen vacancy gradient in TiO2 pho­
toelectrodes by a photoelectrochemical-driven “self-purification” process, Adv.
Energy Mater. 12 (2022) 2103495.
[35] J. Wu, Y. Tao, C. Zhang, Q. Zhu, D. Zhang, G. Li, Activation of chloride by oxygen
vacancies-enriched TiO2 photoanode for efficient photoelectrochemical treat­
ment of persistent organic pollutants and simultaneous H2 generation, J. Hazard.
Mater. 443 (2023) 130363.
[36] Q. Zhang, D. Chen, Q. Song, C. Zhou, D. Li, D. Tian, D. Jiang, Holey defected TiO2
nanosheets with oxygen vacancies for efficient photocatalytic hydrogen pro­
duction from water splitting, Surf. Interfaces 23 (2021) 100979.
[37] R. Fernández-Climent, S. Giménez, M. García-Tecedor, The role of oxygen vacancies
in water splitting photoanodes, Sustain. Energy Fuels 4 (2020) 5916–5926.
[38] Y. Wang, J. Zhang, M.S. Balogun, Y. Tong, Y. Huang, Oxygen vacancy-based metal
oxides photoanodes in photoelectrochemical water splitting, Mater. Today
Sustain. 18 (2022) 100118.
[39] J. Yu, B. Wang, Effect of calcination temperature on morphology and photo­
electrochemical properties of anodized titanium dioxide nanotube arrays, Appl.
Catal. B 94 (2010) 295–302.
10
Journal of Alloys and Compounds 947 (2023) 169480
[40] K.M. Chahrour, F.K. Yam, A.M. Eid, A.A. Nazeer, Enhanced photoelectrochemical
properties of hierarchical black TiO2−x nanolaces for Cr (VI) photocatalytic re­
duction, Int. J. Hydrog. Energy 45 (2020) 22674–22690.
[41] J.M. Macak, H. Tsuchiya, A. Ghicov, K. Yasuda, R. Hahn, S. Bauer, P. Schmuki, TiO2
nanotubes: self-organized electrochemical formation, properties and applica­
tions, Curr. Opin. Solid State Mater. Sci. 11 (2007) 3–18.
[42] X. Yu, B. Kim, Y.K. Kim, Highly enhanced photoactivity of anatase TiO2 nano­
crystals by controlled hydrogenation-induced surface defects, ACS Catal. 3
(2013) 2479–2486.
[43] F. Cao, J. Xiong, F. Wu, Q. Liu, Z. Shi, Y. Yu, X. Wang, L. Li, Enhanced photoelec­
trochemical performance from rationally designed anatase/rutile TiO2 hetero­
structures, ACS Appl. Mater. Interfaces 8 (2016) 12239–12245.
[44] K.L. Schulte, P.A. DeSario, K.A. Gray, Effect of crystal phase composition on the
reductive and oxidative abilities of TiO2 nanotubes under UV and visible light,
Appl. Catal. B 97 (2010) 354–360.
[45] P. Bamola, A. Bhoumik, C. Dwivedi, V. Kaushik, H. Sharma, Enhanced photo­
catalytic activity in TiO2 mixed phase nanostructures, Mater. Today Proc. 28
(2020) 32–36.
[46] T. Gakhar, A. Hazra, Oxygen vacancy modulation of titania nanotubes by
cathodic polarization and chemical reduction routes for efficient detection of
volatile organic compounds, Nanoscale 12 (2020) 9082–9093.
[47] H. Huang, X. Hou, J. Xiao, L. Zhao, Q. Huang, H. Chen, Y. Li, Effect of annealing
atmosphere on the performance of TiO2 nanorod arrays in photoelectrochemical
water splitting, Catal. Today 330 (2019) 189–194.
[48] X. Bi, G. Du, A. Kalam, D. Sun, Y. Yu, Q. Su, B. Xu, A.G. Al-Sehemi, Tuning oxygen
vacancy content in TiO2 nanoparticles to enhance the photocatalytic perfor­
mance, Chem. Eng. Sci. 234 (2021) 116440.
[49] H. Idriss, On the wrong assignment of the XPS O1s signal at 531–532 eV at­
tributed to oxygen vacancies in photo- and electro-catalysts for water splitting
and other materials applications, Surf. Sci. 712 (2021) 121894.
[50] C. Fan, C. Chen, J. Wang, X. Fu, Z. Ren, G. Qian, Z. Wang, Black hydroxylated
titanium dioxide prepared via ultrasonication with enhanced photocatalytic
activity, Sci. Rep. 5 (2015) 11712.
[51] A. Hankin, F.E. Bedoya-Lora, J.C. Alexander, A. Regoutz, G.H. Kelsall, Flat band
potential determination: avoiding the pitfalls, J. Mater. Chem. A 7 (2019)
26162–26176.
[52] X. Ma, X. Li, M. Mai, D. Lin, H. Zhou, L. Zhang, J. Li, Q. Li, D. Chen, Observation of
suppressed photocurrent of plasmonic Au on TiO2 by a double light beam
method, Int. J. Hydrog. Energy 46 (2021) 5045–5052.
[53] R.Van de Krol, M. Graetzel, Photoelectrochemical Hydrogen Production,
Springer, New York, 2012.
[54] S. Corby, R.R. Rao, L. Steier, J.R. Durrant, The kinetics of metal oxide photoanodes
from charge generation to catalysis, Nat. Rev. Mater. 6 (2021) 1136–1155.
[55] J. You, L. Zhang, L. He, B. Zhang, Photocatalytic degradation of methyl orange on
ZnO-TiO2/SO42- heterojunction composites, Opt. Mater. 131 (2022) 112737.
[56] V.Q. Hieu, T.K. Phung, T.Q. Nguyen, A. Khan, V.D. Doan, V.A. Tran, V.T. Le,
Photocatalytic degradation of methyl orange dye by Ti3C2-TiO heterojunction
under solar light, Chemosphere 276 (2021) 130154.
[57] J.C. Wang, H.H. Lou, Z.H. Xu, C.X. Cui, Z.J. Li, K. Jiang, Y.P. Zhang, L.B. Qu, W. Shi,
Natural sunlight driven highly efficient photocatalysis for simultaneous de­
gradation of rhodamine B and methyl orange using I/C codoped TiO2 photo­
catalyst, J. Hazard. Mater. 360 (2018) 356–363.
[58] D.A.P. Velásquez, F.L.N. Sousa, T.A.S. Soares, A.J. Caires, D.V. Freitas, M. Navarro,
G. Machado, Boosting the performance of TiO2 nanotubes with ecofriendly
AgIn5Se8 quantum dots for photoelectrochemical hydrogen generation, J. Power
Sources 506 (2021) 230165.
[59] X. Ma, M. Mai, H. Lin, L. Zeng, J. Zhang, H. Zhou, D. Chen, A novel electrochemical
method for simultaneous measurement of real-time potentials and photo­
current of various photoelectrochemical systems, J. Power Sources 415 (2019)
99–104.