Article

Cs-Doped WO3 with Enhanced Conduction Band for Efficient

Photocatalytic Oxygen Evolution Reaction Driven by
Long-Wavelength Visible Light
Dong Li 1,2,*, Siyu Tian 1, Qiuhua Qian 1, Caiyun Gao 3, Hongfang Shen 1,2 and Fei Han 1

1 School of Materials Science & Engineering, North Minzu University, Yinchuan 750021, China;
[email protected] (S.T.); [email protected] (Q.Q.); [email protected] (H.S.);
[email protected] (F.H.)
2 National and Local Joint Engineering Research Center of Advanced Carbon-Based Ceramics Preparation

Technology, Yinchuan 750021, China

3 Chemical Science and Engineering College, North Minzu University, Yinchuan 750021, China;

[email protected]
* Correspondence: [email protected]

Abstract: Cesium doped WO3 (Cs-WO3) photocatalyst with high and stable oxidation activity was
successfully synthesized by a one-step hydrothermal method using Cs2CO3 as the doped metal ion
source and tungstic acid (H2WO4) as the tungsten source. A series of analytical characterization tools
and oxygen precipitation activity tests were used to compare the effects of different additions of
Cs2CO3 on the crystal structure and microscopic morphologies. The UV–visible diffuse reflectance
spectra (DRS) of Cs-doped material exhibited a significant red shift in the absorption edge with new
shoulders appearing at 440–520 nm. The formation of an oxygen vacancy was confirmed in Cs-WO3
by the EPR signal, which can effectively regulate the electronic structure of the catalyst surface and
contribute to improving the activity of the oxygen evolution reaction (OER). The photocatalytic OER
results showed that the Cs-WO3-0.1 exhibited the optimal oxygen precipitation activity, reaching
58.28 µmol at 6 h, which was greater than six times higher than that of WO3-0 (9.76 µmol). It can be
Citation: Li, D.; Tian, S.; Qian, Q.; attributed to the synergistic effect of the increase in the conduction band position of Cs-WO3-0.1
Gao, C.; Shen, H.; Han, F. (0.11 V) and oxygen vacancies compared to WO3-0, which accelerate the electron conduction rate
Cs-Doped WO3 with Enhanced and slow down the rapid compounding of photogenerated electrons–holes, improving the water-
Conduction Band for Efficient catalytic oxygen precipitation activity of WO3.
Photocatalytic Oxygen Evolution
Reaction Driven by Keywords: Cs-doped; tungsten trioxide; oxygen vacancy; band energy; oxygen evolution reaction
Long-Wavelength Visible Light.
Molecules 2024, 29, 3126. https://
doi.org/10.3390/molecules29133126

Academic Editor: Shengjie Wang 1. Introduction

Received: 29 May 2024 Hydrogen energy converted from abundant solar energy is believed to be a sustain-
Revised: 19 June 2024 able green fuel to replace traditional fossil fuel due to its being pollution-free and low-
Accepted: 26 June 2024 cost [1]. Hydrogen production and oxygen production can be generated simultaneously
Published: 30 June 2024 by photocatalytic water splitting, which results from a hydrogen evolution reaction (HER)
and OER [2]. Compared with the HER, the OER, as a four-electron transfer reaction, re-
quires higher photon energy to overcome the reaction kinetic barriers and it is considered
Copyright: © 2024 by the authors. Li- to be the rate-determining step in the entire water splitting process [3,4]. Currently, IrO2
censee MDPI, Basel, Switzerland. and RuO2 have been widely used as photocatalysts for the OER due to their high catalytic
This article is an open access article activities [5,6]. However, these noble metals are scarce and costly, limiting their large-
distributed under the terms and con- scale application for water splitting. Therefore, the development of an advanced photo-
ditions of the Creative Commons At- catalyst based on low-cost and earth-abundant materials with highly efficient acceleration
tribution (CC BY) license (https://cre- of the reaction dynamic and lowering of the energy barrier of OER is core issue for pho-
ativecommons.org/licenses/by/4.0/). tocatalytic water splitting.

Molecules 2024, 29, 3126. https://doi.org/10.3390/molecules29133126 www.mdpi.com/journal/molecules

Molecules 2024, 29, 3126 2 of 13

In recent years, some nanostructured semiconductor photocatalysts with lower OER

overpotentials, including WO3, Fe2O3, BiVO4, TaON, BaZrO3-BaTaO2N and so on, have
been explored [7–11]. Among these compounds, WO3 has attracted immense attention
owning to its suitable bandgap (2.4–2.8 eV) [12,13], earth abundance, good chemical sta-
bility in strongly acidic media and its thermodynamically suitable valence band positions
for OER. Nevertheless, WO3 suffers from limited visible-light response capability (λ < 460
nm), resulting in poor OER kinetics. Therefore, it is urgent to develop a WO3 photocatalyst
with efficient light absorption at longer wavelengths in the visible region. Nonmetal ele-
ment doping as one of the most effective strategies to improve the visible-light absorption
of WO3 has been confirmed due to the formation of an intermediate level between the
conduction band (CB) and valence band (VB) of WO3, resulting in the decrease in the band
gap [14,15]. Also, metal element doping has already been used as a strategy to promote
the visible-light absorption of WO3 because the conduction band position of WO3 can be
adjusted to narrow the bandgap [16].
At present, investigations on doped WO3 by metal doping (Ti, Fe, Co, Ni, Cu, Zn, Yb,
etc.) [17–22], rare earth metal doping [23] and nonmetal element doping (N, C, S, P) [24–
27] have reported mostly to improve not only light absorption at longer wavelengths but
also the photocatalytic performance for OER. Noted that cesium-doped WO3 has rarely
been reported yet, although photocatalysts containing alkali metal cesium ions (Cs+) such
as Cs0.3WO3, CsBi2Nb5O16, Cs3PW12O40, Cs2V4O11, Cs-doped α-Bi2O3 and Cs-doped TiO2
have been reported [28–33]. The reported results indicated that the photocatalytic activi-
ties could be enhanced by the introduction of Cs+ due to the low ionization energy of Cs
in the lattices.
Herein, we report the first synthesis of Cs-doped WO3 (Cs-WO3) photocatalysts with
Cs+ doping into the WO3 lattice through the hydrothermal method using cesium carbonate
(Cs2CO3) as the Cs ion source. The Cs-WO3 was responsive to visible light of λ ≤ 520 nm,
which give a red shift of 80 nm compared with that of pristine WO3 (440 nm). The photo-
catalytic activities of Cs-WO3 for OER were significantly enhanced compared with pristine
WO3, because the CB potential of WO3 is significantly increased through cesium doping,
while introducing more lattice defects and oxygen vacancies, thereby improving the con-
ductivity of the semiconductor. In particular, there is an extremely significant mutually
dependent relation between the addition of the Cs source and the photocatalytic activities
of Cs-WO3 for OER.

2. Results and Discussion

2.1. Characterization and Influencing Factors of Structure of Cs-WO3
The results of the influencing factors on the structure of Cs-WO3-0.1 are shown in
Figure 1. Figure 1A exhibits the XRD patterns of the samples prepared at different sol-
vothermal temperatures from 120 to 180 °C. The XRD pattern prepared at 120 °C agreed
with that of orthorhombic H2WO4 (JCPDS no. 01-084-0886). When the solvothermal tem-
perature was 150 °C, it can be clearly observed that the peaks at 2θ = 15.0°, 24.6°, 28.9°,
30.3°, 43.2° and 46.1° correspond to the (111), (210), (311), (222), (422) and (511) plane, re-
spectively, which can be assigned to a cubic WO3·0.5H2O crystalline phase (PDF # 01-084-
1851). The peaks intensities of the Cs-WO3-0.1 decreased when increasing the temperature
to 180 °C, and meanwhile the peaks at 27.2° and 27.8° assigned to the Cs2W6O19 compound
(PDF # 01-045-0522) were formed. The XRD patterns of Cs-WO3-0.1 prepared at 150 °C for
different reaction times of 12~36 h are exhibited in Figure 1B. The peak intensities of Cs-
WO3-0.1 increased with the reaction time from 12 to 24 h, and thereby decreased above 24
h due to the formation of the Cs2W6O19 compound. The XRD results suggest that the opti-
mum preparation conditions of Cs-WO3-0.1 are a solvothermal temperature of 150 °C and
a reaction time of 24 h, which were employed in our experiments. As shown in Figure 1C,
the XRD patterns of the WO3-0 and Cs-WO3 samples show the characteristic peaks of the
cubic WO3·0.5H2O crystalline phase (PDF # 01-084-1851). However, the peaks of the
Molecules 2024, 29, 3126 3 of 13

Cs2W6O19 compound began to be seen in the Cs-WO3-0.5 alongside the main peaks of the
cubic phase WO3·0.5H2O while overdoping with Cs+ ions. In Figure 1B,C, obvious shifts
of XRD peaks are observed, which are ascribed to the existence of structural strain [34].
Additionally, compared with the WO3-0, the crystallinity of the Cs-WO3 samples de-
creased with increasing the doping concentration of Cs ions. This may be due to the dis-
ruption of the crystal structure of WO3, when the Cs ions with larger ionic radii (1.67 Å)
are doped into the WO3 lattice, resulting in the formation of a distorted structure.

Figure 1. The XRD patterns of Cs-WO3-0.1 samples prepared at (A) different temperatures and (B)
different reaction times. (C) The XRD patterns of the pure WO3 and Cs-WO3 samples prepared with
different doping concentrations of Cs+ ions.

The average crystal grain size was calculated from the (311) peak (2θ = 28.9˚) of cubic
WO3·0.5H2O according to Scherrer’s equation [35], as shown in Table 1. The crystallite di-
ameter of the WO3-0 (23.6 nm) was larger than those of Cs-WO3-0.1 (22.6 nm), Cs-WO3-0.3
(20.9 nm) and Cs-WO3-0.5 (19.1 nm). The calculated lattice parameters and average crys-
talline size of WO3 were decreased (Table 1) by Cs doping. The results indicate that Cs-
doped WO3 has a strong restraining function with the increase in crystal size owning to
the dopant cations Cs+ preventing the growth of crystal grains in the nanoparticles [36].

Table 1. Summary of physicochemical properties of different WO3 samples.

Crystallite Lattice Parameters

Molar Ratio of Surface Area (c)
Samples Diameter (b)
Cs/W (a) a (Å) b (Å) c (Å) (m2 g−1)
(nm)
WO3-0 0:1 27.5 7.3125 7.5384 7.5964 9.2
Cs-WO3-0.1 0.12:1 25.2 7.2997 7.5009 7.5625 16.1
Cs-WO3-0.3 0.15:1 20.9 7.2453 7.4813 7.4953 10.6
Cs-WO3-0.5 0.17:1 19.1 7.2046 7.4364 7.4678 8.9
The content of Cs+ was analyzed according to the approach we reported previously. (b) The crys-
(a)

tallite diameters were calculated from XRD data according to the Scherrer equation and expressed
as average values calculated based on the (311) peak. (c) The surface areas were provided from N2
sorption isotherms.

As shown in Figure 2a, the elliptical-like WO3-0 is composed of nanosheets and na-
noparticles with a major axis of about 55 µm and a semimajor axis of 40 µm. Notably, the
Cs-WO3-0.1 is made up of a microsphere of about 41 µm in diameter which mainly con-
sists of nanoparticles and nanorods (Figure 2b). The diameter of the microsphere (43 µm)
Molecules 2024, 29, 3126 4 of 13

increased and the amount of nanorods gradually decreased with the increasing doping
amount of Cs+ (Figure 2c). A smooth microsphere with a diameter of 45 µm was formed
for the Cs-WO3-0.5 (Figure 2d), suggesting that the formation of micrometer spheres
mainly relies on self-assembly effects. As shown in Table 1, it was found that the specific
surface area of the sample strongly depends on its morphology. The Cs-WO3-0.1 pos-
sessed a higher specific surface area (16.1 m2/g) relative to those of WO3-0 (9.2 m2/g) and
Cs-WO3-0.3 (10.6 m2/g) owing to the formation of nanorods on the surface of the micro-
sphere, which is beneficial to form more accessible active sites for the OER.

Figure 2. The SEM images of (a) WO3-0, (b) Cs-WO3-0.1, (c) Cs-WO3-0.3, (d) Cs-WO3-0.5.

The elemental maps of the EDX for the Cs-WO3-0.1 are shown in Figure 3. The map-
ping signals of the W and O (Figure 3c,d) and of the Cs (Figure 3e) were detected. The
results showed a uniform distribution of Cs, O and W, in good chemical agreement with
Cs-WO3.

Figure 3. The SEM_EDX element distribution mapping images of the (a) Cs-WO3-0.1; (b) layered W,
O and Cs; (c) W; (d) O; (e) Cs.

The chemical composition and valence states of Cs-WO3 samples were investigated
by XPS. The spectra were calibrated with the C 1s peak as reference. As shown in Figure
4A, the XPS survey spectrum of WO3-0 (a) depicts that no other impurity phases were
detected except W and O elements. W, O and Cs elements were co-present in the Cs-WO3-
0.1 (b) and Cs-WO3-0.3 (c). In Figure 4B, the high-resolution XPS spectrum of W 4f exhibits
two peaks at 37.7 eV and 35.5 eV that are, respectively, ascribed to the spin–orbit doublet
Molecules 2024, 29, 3126 5 of 13

of W 4f5/2 and W 4f7/2, respectively, for a W6+ state in WO3 [37]. The XPS spectra of W 4f for
Cs-WO3-0.1 and Cs-WO3-0.3 (Figure 3b) exhibit two characteristic peaks at 38.1 eV and
35.9 eV, corresponding to 4f5/2 and W 4f7/2 of the WO3 lattice, respectively. As shown in
Figure 3c, the binding energy at 531.5 eV and 530.4 eV in the XPS spectrum of O 1s for the
WO3-0 can be assigned to the H2O and lattice oxygen, respectively [38]. The main peaks in
the high-resolution O 2p spectra for the Cs-WO3-0.1 and Cs-WO3-0.3 located at 530.8 eV
can be assigned to the lattice oxygen of the W-O bond in the crystalline WO3. The banding
energies at 531.9 eV correspond to the adsorbed oxygen ions and hydroxyl groups on the
surface, respectively. The ratios of adsorbed O increased to 12.7% and 13.5% in Cs-WO3-
0.1 and Cs-WO3-0.3 due to the surface oxygen vacancies, while it was 10.3% in WO3. This
can serve as indirect evidence for the presence of oxygen vacancies. The high-resolution
XPS spectra of the Cs element for both Cs-WO3-0.1 and Cs-WO3-0.3 (Figure 3d) exhibited
two peaks at 738.4 eV and 724.7 eV, which are assigned to the spin orbits of Cs 3d3/2 and
Cs 3d5/2, respectively [32,39]. Notably, the positive shifts of 0.4 eV and 0.8 eV in W 4f and
O 1s for Cs-WO3 can be seen after Cs+ doping. This is due to the occurrence of ion exchange
on the WO3 surface, which also confirmed that the Cs was successfully introduced into
the lattice of WO3 and formed W-Cs bonds in the doped samples The positive shifts im-
prove the PEC performance of WO3. Furthermore, it can be seen that the peak intensities
of W 4f and O 1s for Cs-WO3 decreased with increasing the doped contents of Cs element
because of the replacement of W6+ by Cs+ leading to the contamination of oxygen. Gener-
ally, the larger the ionic radius is, the more difficult it is for doping to occur due to the
requirement of high formation energy. Therefore, the replacement of W6+ by Cs+ is more
favorable than replacing O2- with Cs+.

Figure 4. (A) The XPS survey spectra of (a) WO3-0, (b) Cs-WO3-0.1 and (c) Cs-WO3-0.3; (B) W 4f; (C)
O 2p; and (D) Cs 3d regions.

In situ electron paramagnetic resonance (EPR) measurements were carried out to fur-
ther prove the existence of surface oxygen vacancies and investigate their properties. No
signal was detected for the WO3-0; however, Cs-WO3 samples exhibited relatively stronger
EPR peaks intensity at g ≈ 2.002 under the same conditions, as shown in Figure 5. The
higher the doped amounts of Cs, the stronger the signal intensity. These results agreed
with results reported previously, confirming the presence of surface oxygen vacancies on
Cs-WO3 samples [40,41]. The oxygen vacancies may be beneficial to improve the photo-
catalytic performance of Cs-WO3.
Molecules 2024, 29, 3126 6 of 13

Figure 5. The EPR spectra of (a) WO3-0, (b) Cs-WO3-0.1 and (c) Cs-WO3-0.3 at 103 K in liquid N2.

2.2. The Optical Properties of Cs-WO3

Figure 6 shows the UV–visible DRS spectra in the range from 300 to 700 nm and Tauc
plots of WO3-0 and Cs-WO3 samples, respectively. As shown in Figure 6A, WO3-0 can only
absorb light below 440 nm. However, a significant red shift in the absorption edge with
new shoulders appearing at 440–520 nm can be seen for Cs-WO3 samples. Absorption
above 600 nm was observed for Cs-WO3 samples because of the formation of an oxygen
defect caused by doping [42], in contrast to negligible absorption for neat WO3, which is
consist with the results of XPS and EPR. Furthermore, Figure 6B shows the Tauc plots
based on DRS data, in which two different slopes are observed for the Tauc plots of Cs-
WO3 samples due to the appearance of the new shoulders. Therefore, these estimated val-
ues of band energies for Cs-WO3-0.1 (2.38 eV) and Cs-WO3-0.3 (2.47 eV) were obtained
from the slopes, which decreased by 0.43 eV and 0.34 eV, respectively, compared to 2.81
eV of WO3-0.

Figure 6. (A) UV–visible DRS and (B) Tacu plots based on UV–visible DRS of (black) WO3-0, (red)
Cs-WO3-0.1 and (blue) Cs-WO3-0.3.
Molecules 2024, 29, 3126 7 of 13

2.3. Photocatalytic Activity

The photocatalytic O2 evolution activities over WO3-0, Cs-WO3-0.1 and Cs-WO3-0.3
were carried out under visible-light irradiation in Fe2(SO4)3 solution; the results are shown
in Figure 7. In Figure 7A, the WO3-0 generates only 9.76 µmol of O2 evolution due to the
high recombination rate of photogenerated carriers. It is noted that the activities for O2
evolution are drastically improved after Cs doping. The Cs-WO3-0.1 shows a higher
amount of O2 evolution (58.28 µmol), which is an increase of about 6 times and 1.2 times
(47.68 µmol) compared with WO3-0 and Cs-WO3-0.3. It can be explained by the formation
of oxygen vacancies, leading to the acceleration of electron and hole transport rates caused
by Cs doping. However, the photocatalytic activity decreased with further increases in
doping concentration, demonstrating that a higher Cs doping content could also form the
recombination centers for the photogenerated carriers caused by excessive dopants. As
shown in Figure 7B, the stability test of photocatalytic O2 evolution activity for Cs-WO3-
0.1 was performed repeatedly for four cycles. The results suggest that the Cs-WO3-0.1 can
be used as an efficient and stable visible-light excited photocatalyst for photocatalytic O2
evolution. The small decrease in the O2 production rate during the recycling reaction is
mainly attributing to the small loss of catalysts during the photocatalytic process at a low
dosage of the catalysts, and the powdered catalyst in aqueous solution can be dispersed
easily to be taken away from the photocatalytic system during the real-time sampling pro-
cedure.

Figure 7. (A) Photocatalytic O2 evolution over (black) WO3-0, (red) Cs-WO3-0.1 and (blue) Cs-WO3-
0.3 (10 mg of catalysts added into 30mL solution under visible-light irradiation.); (B) photocatalytic
O2 production stability of Cs-WO3-0.1.

2.4. Photoelectrocatalytic Properties

The linear sweep voltammograms (LSVs) for these electrodes were taken with
chopped visible-light irradiation to investigate their photoelectrocatalytic performances,
as shown in Figure 8. The photoanodic currents of these electrodes were observed above
0.1 V vs. Ag/AgCl based on water oxidation. For the WO3-0 electrode, the photocurrent of
0.06 mA cm−2 at 1.0 V was hard to observe; however, the PEC water oxidation performance
of Cs-WO3 electrodes was significantly enhanced. The highest photocurrent of 2.12 mA
cm−2 for Cs-WO3-0.1 was generated, which was about two times higher than that of Cs-
WO3-0.3 (1.1 mA cm−2).
Molecules 2024, 29, 3126 8 of 13

Figure 8. Linear sweep voltammograms (LSVs) of the (black) WO3-0, (red) Cs-WO3-0.1 and (blue)
Cs-WO3-0.3 electrodes with visible-light irradiation chopped in a 0.1 M phosphate-buffered solution
of pH 6.0 with visible-light irradiation (λ > 420 nm, 100 mW cm−2).

Mott–Schottky plots (Figure 9A) from alternating-current impedance measurements

were taken to reveal the relative positions of the valence band (VB) and conduction band
(CB) in WO3-0 and Cs-WO3. As a result, the flat band (EFB) potentials (vs. Ag/AgCl) of
WO3-0, Cs-WO3-0.1 and Cs-WO3-0.3 were 0.46 eV, 0.01 eV and 0.23 eV, corresponding to
0.66, 0.21, and 0.43 eV (vs. NHE), respectively. The CB potential of the semiconductor ma-
terial was 0.1–0.3 eV lower than that of the EFB (vs. NHE) [43], so the CB values of WO3-0,
Cs-WO3-0.1 and Cs-WO3-0.3 were calculated as 0.56, 0.11 and 0.33 eV (vs. NHE), respec-
tively. The VB values of WO3-0, Cs-WO3-0.1 and Cs-WO3-0.3 were estimated as 3.37 eV,
2.49 eV, and 2.8 eV, respectively, according to the formula of Eg = EVB-ECB [44]. Moreover,
the donor carrier densities (ND [cm−3]) were provided from the x-intercept and the slopes
of the straight line [45] (Table 2). The ND values of the Cs-WO3 were higher than those for
WO3-0. In particular, the highest ND value for Cs-WO3-0.1 (3.46 × 1019 cm−3) was calculated,
which was 1.5 and 1.1 times higher than those of WO3-0 (2.26 × 1019 cm−3) and Cs-WO3-0.3
(3.13 × 1019 cm−3). The negative shift in the EFB potential and the increase in the ND are
beneficial to enhance the photocatalytic activity and photoelectrocatalytic performance for
the OER.

Table 2. Summary of optical and electrochemical properties and energies of band structures of var-
ious WO3 samples.

Samples Absorption Energies EFB ND (1019 cm−3) ECB EVB

WO3-0 2.81 0.66 3.68 0.56 3.37
Cs-WO3-0.1 2.38 0.21 3.78 0.11 2.49
Cs-WO3-0.3 2.47 0.43 3.82 0.33 2.80

The Tafel plots are useful to investigate the reaction kinetics of the OER. As shown in
Figure 9B, the Tafel slopes of the Cs-WO3 prominently decrease compared with those of
WO3-0. Cs-WO3-0.1 possesses a lower Tafel slope of 16.46 mVdec−1 than Cs-WO3-0.3 (32.78
mVdec−1) and WO3-0 (48.54 mVdec−1), indicating that Cs doping gives a faster kinetic re-
sponse in the OER and makes the Cs-WO3 catalysts have higher photocatalytic activities
for the OER.
The electrochemical impedance was utilized to give an insight into the kinetics of the
charge transfer process and to evaluate its effect on photocatalytic O2 evolution activity.
As seen in the results of the Nyquist plots in Figure 9C, Cs-WO3-0.1 exhibited smaller
Molecules 2024, 29, 3126 9 of 13

semicircles than WO3-0 and Cs-WO3-0.3. As is well known, the diameter of the semicircle
in the Nyquist plot corresponds to the impedance of the electrode, and the larger the ra-
dius, the larger the impedance [46]. This result indicates that the Cs-WO3-0.1 has a lower
charge transfer resistance and higher separation efficiency for photogenerated electron–
hole pairs than other electrodes and inhibits the recombination of photogenerated
charges. This is mainly due to the n-type doping of WO3 by cesium doping, which injects
electrons into the Fermi level, enhances the CB potential and also increases lattice defects
and oxygen vacancies in WO3, thereby improving the conductivity of the WO3. The Tafel
and electrochemical impedance results provide favorable evidence for the improvement
of photocatalytic activity for the OER.

Figure 9. (A) Mott–Schottky plots of the (black) WO3-0, (red) Cs-WO3-0.1 and (blue) Cs-WO3-0.3
electrodes in a 0.1 M phosphate-buffered solution of pH, 6.0; frequency, 0.1 Hz; amplitude potential,
10 mV. (B) Tafel plots and (C) Nyquist plots of the (black) WO3-0, (red) Cs-WO3-0.1 and (blue) Cs-
WO3-0.3 electrodes for photoelectrocatalytic water oxidation in a 0.1 M phosphate-buffered solution
(pH = 6).

The energy positions were investigated to elucidate Cs-doping effects on the band
energy of WO3. Figure 10 shows energy positions for WO3-0, Cs-WO3-0.1 and Cs-WO3-0.3.
It has been well documented that the VB of Cs-WO3 consists of the hybridization between
O2p and Cs 4s, and the CB is from W 5d electronic components. The enhanced optical
absorption is illustrated for the contribution from the Cs 4s hybridization in VB.

Figure 10. The proposed band natures of WO3-0, Cs-WO3-0.1 and Cs-WO3-0.3.
Molecules 2024, 29, 3126 10 of 13

3. Experimental Section
3.1. Materials
Tungstic acid (H2WO4), Hydrogen peroxide (H2O2), Marpolose (60MP-50), Ethylene
glycol (EG, molecular weight = 300), Cs2CO3 and Fe2(SO4)3·9H2O were purchased from
Aladdin’s Reagent. A Fluorine-doped tin oxide (FTO)-coated glass substrate was obtained
from Dalian HeptaChroma Co., Ltd. (Dalian, China) Millipore water (DIRECT-Q 3UV,
Merck Ltd., Shanghai, China) was used for all the experiments. All other chemicals were
of analytical grade and used as received unless mentioned otherwise.

3.2. Synthesis of WO3 Powders

Typically, 1.0 g H2WO4 (4.0 mmol) was dissolved into the H2O2 (20 mL) under vigor-
ous stirring at room temperature, forming the pale-yellow solution A. Cs2CO3 (0.33 g) was
dissolved in water to form the B solution. The B solution was added into the A solution
dropwise to form the C solution. Then, the C solution was transferred to Teflon-lined
stainless-steel autoclaves (reactor volume: 50 mL) at 120–150 °C in 12–36 h for hydrother-
mal reaction. The 0.1 mol% Cs-doped WO3 (Cs-WO3-0.1) powder was obtained after cen-
trifugation, washed repeatedly with ethanol, and air-dried. The Cs-WO3-0.3 and Cs-WO3-
0.5 were prepared in the same manner by changing the Cs2CO3 amounts of 1.0 g and 1.63
g, respectively. A pure WO3 sample denoted as WO3-0 was prepared in the same manner
without the addition of Cs2CO3.

3.3. Fabrication of Electrodes

In the typical procedure, 0.4 g of powder (Cs-WO3-0.1and Cs-WO3-0.3) was mixed in
the PEG (0.4 mL) with slow stirring until there were no bubbles; a smooth paste was
formed. The resulting paste was squeezed over a clean FTO glass substrate by a doctor-
blade coater and dried under a 100W infrared lamp. After repeating the procedure twice,
the Cs-WO3-0.1 and Cs-WO3-0.3 electrodes were prepared. The pure WO3 electrode was
fabricated by the same method using a precursor prepared without the addition of
Cs2CO3.

3.4. Characterization of the Photocatalysts

The crystal structure of the samples was analyzed using an X-ray diffractometer
(XRD-6000, Japan) and a scanning speed (4 °C/min). A UV-2700 UV–Vis spectrophotom-
eter (Shimadzu, International Trade (Shanghai) Co., Ltd., Shanghai, China) was used to
examine the absorption spectra of solid powder samples. Using a thermal field emission
scanning electron microscope, the surface morphology of the samples was examined
(SIGMA:500, Jena, Germany). The Energy Dispersive X-ray Spectroscopic (EDS) data were
taken using electron probe microanalysis (JEOL JED-2300, Tokyo, Japan) operated at an
accelerating voltage of 10 kV. Elemental and valence analyses of the samples were per-
formed using an ES-CALAB Xi X-ray photoelectron spectrometer (manufactured by
Thermo Fisher Scientific (China) Co., Ltd., Shanghai, China) and calibrated by the C 1 s
peak appearing at 284.2 eV.

3.5. Photocatalytic Activity Measurement

Photocatalytic experiments were conducted in a quartz glass reactor ca. 40 cm3, and
10 mg of catalyst was suspended in Fe2(SO4)3·9H2O (2.1 mM, 30 mL) solution. Then, the
system was degassed by bubbling Ar gas to remove oxygen. Under a 300 W xenon lamp,
the photocatalytic process was carried out under continuous stirring to ensure the catalyst
dispersed in the solution well. The evolution amount of oxygen was detected by gas chro-
matography with a TCD detector (Shimadzu GC-8A with a TCD, 5 A column, Ar as car-
rier).
Molecules 2024, 29, 3126 11 of 13

3.6. Photoelectrocatalytic Property Measurement

The photoelectric properties of the samples were tested on a Chenhua CHI760E elec-
trochemical workstation (Shanghai Chenhua Instrument Co., Ltd., Shanghai, China) using
a three-electrode system: the FTO photoelectrode as the working electrode (with an ap-
proximate working area of 1 cm2), platinum wire as the counter electrode, and saturated
AgCl electrode (Ag/AgCl) as the reference electrode.
For photovoltaic performance testing, a 300 W xenon lamp was used (Optical Module
X; Ushio Inc., Tokyo, Japan) to simulate sunlight and its light intensity was adjusted to
100 mW cm−2. The linear sweep voltammograms (LSVs) were measured at a scan rate of 5
mV s−1. Light was irradiated from the back side of the working electrode using a 300 W
xenon lamp with a UV-cut filter (λ ≥ 420 nm). Electrochemical impedance spectra were
measured at an applied potential of 0.68 V vs. Ag/AgCl (1.23 V vs. RHE) in a frequency
range of 10 mHz to 20 kHz (amplitude of 50 mV). Light irradiation (λ ≥ 420 nm) was con-
ducted with the electrode with a 300 W xenon lamp (Ushio Inc., Tokyo, Japan, Optical
ModuleX).

4. Conclusions
The Cs-doped WO3 with spatial charge separation was synthesized using a hydro-
thermal approach, which exhibited a significant enhancement of the photocatalytic per-
formance for water spitting to boost the production of oxygen. The addition of Cs depend-
ence on the physiochemical properties and the performance of the photocatalytic OER of
the WO3-0 and Cs-WO3 catalysts were investigated to characterize Cs doped into the WO3
lattice and reveal the mechanism of superior performance for the photocatalytic OER of
Cs-WO3. The Cs doping is responsible for the significant red shift in the absorption edge,
with a new shoulder appearing at 440–520 nm compared to that in WO3-0. The Cs-WO3
catalyst is able to utilize visible light at longer wavelengths below 520 nm for photocata-
lytic OER, in contrast to utilization below 440 nm for the WO3-0 catalyst. These results
demonstrate that Cs doping is an effective strategy for improving the photocatalytic per-
formance of WO3 photocatalysts for the OER, and thus it is expected to be applied for
photocatalytic OERs as artificial photosynthesis to improve the solar energy conversion
efficiency.

Author Contributions: Conceptualization, D.L., S.T. and F.H.; methodology, Q.Q., S.T., H.S. and
F.H.; investigation and data curation, Q.Q.; formal analysis, C.G.; supervision, D.L.; writing—orig-
inal draft preparation, D.L.; writing—review and editing, D.L. All authors have read and agreed to
the published version of the manuscript.
Funding: This project was supported by the National and Local Joint Engineering Research Center
of Advanced Carbon-Based Ceramics Preparation Technology, grant number 2024TJZX03. This pro-
ject was supported by the Natural Science Foundation of Ningxia Province, grant numbers
2023AAC03292; 2023AAC03306.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The original contributions presented in the study are included in the
article, further inquiries can be directed to the corresponding authors.
Acknowledgments: The authors thank the the National and Local Joint Engineering Research Cen-
ter of Advanced Carbon-Based Ceramics Preparation Technology (2024TJZX03) and the Natural Sci-
ence Foundation of Ningxia Province (Grant No. 2023AAC03292; 2023AAC03306).
Conflicts of Interest: The authors declare no conflicts of interest.
Molecules 2024, 29, 3126 12 of 13

References
1. Hisatomi, T.; Kubota, J.; Domen, K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water split-
ting. Chem. Soc. Rev. 2014, 43, 7520–7535.
2. Zeng, F.; Mebrahtu, C.; Liao, L.; Beine, A.K.; Palkovits, R. Stability and deactivation of OER electrocatalysts: A review. J. Energy
Chem. 2022, 69, 301–329.
3. Bignozzi, C.A.; Caramori, S.; Cristino, V.; Argazzi, R.; Meda, L.; Tacca, A. Nanostructured photoelectrodes based on WO3: Ap-
plications to photooxidation of aqueous electrolytes. Chem. Soc. Rev. 2013, 42, 2228–2246.
4. Wang, L.; Lian, W.; Liu, B.; Lv, H.; Zhang, Y.; Wu, X.; Wang, T.; Gong, J.; Chen, T.; Xu, H. A transparent, high-performance, and
stable Sb2S3 photoanode enabled by heterojunction engineering with conjugated polycarbazole frameworks for unbiased pho-
toelectrochemical overall water splitting devices. Adv. Mater. 2022, 34, 2200723.
5. Ahmed, J.; Mao, Y. Ultrafine iridium oxide nanorods synthesized by molten salt method toward electrocatalytic oxygen and
hydrogen evolution reactions. Electrochim. Acta 2016, 212, 686–693.
6. Li, H.; Zhu, B.; Sun, J.; Gong, H.; Yu, J.; Zhang, L. Photocatalytic hydrogen production from seawater by TiO2/RuO2 hybrid
nanofiber with enhanced light absorption. J. Colloid Interface Sci. 2024, 654, 1010–1019.
7. Yang, M.; Li, J.; Ke, G.; Liu, B.; Dong, F.; Yang, L.; He, H.; Zhou, Y. WO3 homojunction photoanode: Integrating the advantages
of WO3 different facets for efficient water oxidation. J. Energy Chem. 2021, 56, 37–45.
8. Jiang, S.; Zhang, X.; Nawaz, M.; Fan, X.; Tao, R. Boosting the photoelectrochemical water splitting of Fe2O3 by surface-state
regulation. Inorg. Chem. Front. 2024, 11, 526–533.
9. del Olmo, L.; Dommett, M.; Oevreeide, I.H.; Walsh, A.; Di Tommaso, D.; Crespo-Otero, R. Water oxidation catalysed by quan-
tum-sized BiVO 4. J. Mater. Chem. A 2018, 6, 24965–24970.
10. He, Y.; Thorne, J.E.; Wu, C.H.; Ma, P.; Du, C.; Dong, Q.; Guo, J.; Wang, D. What limits the performance of Ta3N5 for solar water
splitting? Chem 2016, 1, 640–655.
11. Maeda, K.; Lu, D.; Domen, K. Solar-Driven Z-scheme water splitting using modified BaZrO3–BaTaO2N solid solutions as pho-
tocatalysts. Acs Catal. 2013, 3, 1026–1033.
12. Wang, Y.; Tian, W.; Chen, L.; Cao, F.; Guo, J.; Li, L. Three-dimensional WO3 nanoplate/Bi2S3 nanorod heterojunction as a highly
efficient photoanode for improved photoelectrochemical water splitting. ACS Appl. Mater. Interfaces 2017, 9, 40235–40243.
13. Liu, Y.; Wygant, B.R.; Mabayoje, O.; Lin, J.; Kawashima, K.; Kim, J.-H.; Li, W.; Li, J.; Mullins, C.B. Interface engineering and its
effect on WO3-based photoanode and tandem cell. ACS Appl. Mater. Interfaces 2018, 10, 12639–12650.
14. Chen, G.; Wang, Q.; Zhao, Z.; Gao, L.; Li, X. Synthesis and photocatalytic activity study of S-doped WO3 under visible light
irradiation. Environ. Sci. Pollut. Res. 2020, 27, 15103–15112.
15. Mi, Q.; Ping, Y.; Li, Y.; Cao, B.; Brunschwig, B.S.; Khalifah, P.G.; Galli, G.A.; Gray, H.B.; Lewis, N.S. Thermally stable N2-inter-
calated WO3 photoanodes for water oxidation. J. Am. Chem. Soc. 2012, 134, 18318–18324.
16. Kalanur, S.S.; Yoo, I.-H.; Eom, K.; Seo, H. Enhancement of photoelectrochemical water splitting response of WO3 by Means of
Bi doping. J. Catal. 2018, 357, 127–137.
17. Radecka, M.; Sobas, P.; Wierzbicka, M.; Rekas, M. Photoelectrochemical properties of undoped and Ti-doped WO3. Phys. B
Condens. Matter 2005, 364, 85–92.
18. Song, H.; Li, Y.; Lou, Z.; Xiao, M.; Hu, L.; Ye, Z.; Zhu, L. Synthesis of Fe-doped WO3 nanostructures with high visible-light-
driven photocatalytic activities. Appl. Catal. B Environ. 2015, 166, 112–120.
19. Song, Z.; Ma, J.; Sun, H.; Wang, W.; Sun, Y.; Sun, L.; Liu, Z.; Gao, C. Synthesis of NiWO4 nano-particles in low-temperature
molten salt medium. Ceram. Int. 2009, 35, 2675–2678.
20. Quyen, V.T.; Kim, J.; Park, P.-M.; Huong, P.T.; Viet, N.M.; Thang, P.Q. Enhanced the visible light photocatalytic decomposition
of antibiotic pollutant in wastewater by using Cu doped WO3. J. Environ. Chem. Eng. 2021, 9, 104737.
21. Cheng, X.; Leng, W.; Liu, D.; Zhang, J.; Cao, C. Enhanced photoelectrocatalytic performance of Zn-doped WO3 photocatalysts
for nitrite ions degradation under visible light. Chemosphere 2007, 68, 1976–1984.
22. Liew, S.; Zhang, Z.; Goh, T.G.; Subramanian, G.; Seng, H.D.; Hor, T.A.; Luo, H.-K.; Chi, D. Yb-doped WO3 photocatalysts for
water oxidation with visible light. Int. J. Hydrog. Energy 2014, 39, 4291–4298.
23. Mehtab, A.; Ahmed, J.; Alshehri, S.M.; Mao, Y.; Ahmad, T. Rare earth doped metal oxide nanoparticles for photocatalysis: A
perspective. Nanotechnology 2022, 33, 142001.
24. Sudrajat, H.; Babel, S. Rapid photocatalytic degradation of the recalcitrant dye amaranth by highly active N-WO 3. Environ.
Chem. Lett. 2016, 14, 243–249.
25. Sun, Y.; Murphy, C.J.; Reyes-Gil, K.R.; Reyes-Garcia, E.A.; Thornton, J.M.; Morris, N.A.; Raftery, D. Photoelectrochemical and
structural characterization of carbon-doped WO3 films prepared via spray pyrolysis. Int. J. Hydrog. Energy 2009, 34, 8476–8484.
26. Li, W.; Li, J.; Wang, X.; Chen, Q. Preparation and water-splitting photocatalytic behavior of S-doped WO3. Appl. Surf. Sci. 2012,
263, 157–162. https://doi.org/10.1016/j.apsusc.2012.09.021.
27. Sun, J.; Li, B.; Wang, Q.; Zhang, P.; Zhang, Y.; Gao, L.; Li, X. Preparation of phosphorus-doped tungsten trioxide nanomaterials
and their photocatalytic performances. Environ. Technol. 2021, 42, 4104–4114.
28. Liu, G.; Xu, J.; Li, R. Facile synthesis of Cs0. 3WO3 nanofibers by hydrothermal method and their optical properties. Opt. Mater.
2020, 107, 110147.
29. Kako, T.; Zou, Z.; Ye, J. Photocatalytic oxidation of 2-propanol in the gas phase over cesium bismuth niobates under visible
light irradiation. Res. Chem. Intermed. 2005, 31, 359–364.
Molecules 2024, 29, 3126 13 of 13

30. Friesen, D.A.; Morello, L.; Headley, J.V.; Langford, C.H. Factors influencing relative efficiency in photo-oxidations of organic
molecules by Cs3PW12O40 and TiO2 colloidal photocatalysts. J. Photochem. Photobiol. A Chem. 2000, 133, 213–220.
31. Qiao, X.; Seo, H.J. A visible-light-driven photocatalyst of cesium vanadate Cs2V4O11 nanowires by hydrothermal method. Mater.
Lett. 2014, 136, 322–324.
32. Huang, Y.; Qin, J.; Hu, C.; Liu, X.; Wei, D.; Seo, H.J. Cs-doped α-Bi2O3 microplates: Hydrothermal synthesis and improved
photochemical activities. Appl. Surf. Sci. 2019, 473, 401–408.
33. Rajput, H.; Changotra, R.; Sangal, V.K.; Mahla, S.K.; Dhir, A. A facile synthesis of Cs loaded TiO2 nanotube photoelectrode for
the removal of 4-chloroguaiacol. Chemosphere 2019, 218, 687–695.
34. Guan, D.Q.; Shi, C.L.; Xu, H.Y.; Gu, Y.X.; Zhong, J.; Sha, Y.C.; Hu, Z.W.; Ni, M.; Shao, Z.P. Simultaneously mastering operando
strain and reconstruction effects via phase-segregation strategy for enhanced oxygen-evolving electrocatalysis. J. Energy Chem.
2023, 82, 572–580. https://doi.org/10.1016/j.jechem.2023.03.033.
35. Wang, X.; Zhao, Y.; Jiang, X.; Liu, L.; Li, X.; Li, H.; Liang, W. In-situ self-assembly of plant polyphenol-coated Fe3O4 particles for
oleaginous microalgae harvesting. J. Environ. Manag. 2018, 214, 335–345.
36. Sivakarthik, P.; Thangaraj, V.; Parthibavarman, M. A facile and one-pot synthesis of pure and transition metals (M=Co & Ni)
doped WO3 nanoparticles for enhanced photocatalytic performance. J. Mater. Sci. Mater. Electron. 2017, 28, 1–7.
37. Wang, Y.; Zhang, F.; Zhao, G.; Zhao, Y.; Ren, Y.; Zhang, H.; Zhang, L.; Du, J.; Han, Y.; Kang, D.J. Porous WO3 monolith-based
photoanodes for high-efficient photoelectrochemical water splitting. Ceram. Int. 2019, 45, 7302–7308.
38. Zou, D.; Yi, Y.N.; Song, Y.F.; Guan, D.Q.; Xu, M.G.; Ran, R.; Wang, W.; Zhou, W.; Shao, Z.P. The BaCe0.16Y0.04Fe0.8O3-δnanocom-
posite: A new high-performance cobalt-free triple-conducting cathode for protonic ceramic fuel cells operating at reduced tem-
peratures. J. Mater. Chem. A 2022, 10, 5381–5390. https://doi.org/10.1039/d1ta10652j.
39. Zhang, Y.; Guo, D.; Li, R.X. Synthesis ofCs0.3WO3 with visible transparency and near-infrared absorption from commercial WO3.
J. Solid State Chem. 2022, 306, 122768. https://doi.org/10.1016/j.jssc.2021.122768.
40. Windisch, C.F., Jr.; Exarhos, G.J.; Yao, C.; Wang, L.Q. Raman study of the influence of hydrogen on defects in ZnO. J. Appl. Phys.
2007, 101, 1012.
41. Wei, Z.; Wang, W.; Li, W.; Bai, X.; Zhao, J.; Tse, E.C.M.; Phillips, D.L.; Zhu, Y. Steering Electron-Hole Migration Pathways Using
Oxygen Vacancies in Tungsten Oxides to Enhance Their Photocatalytic Oxygen Evolution Performance. Angew. Chem. 2021, 60,
8236–8242.
42. Li, D.; Chandra, D.; Takeuchi, R.; Togashi, T.; Kurihara, M.; Saito, K.; Yui, T.; Yagi, M. Dual-Functional Surfactant-Templated
Strategy for Synthesis of an In Situ N2-Intercalated Mesoporous WO3 Photoanode for Efficient Visible-Light-Driven Water Ox-
idation. Chem. A Eur. J. 2017, 23, 6596–6604. https://doi.org/10.1002/chem.201700088.
43. Huang, H.; Li, D.; Lin, Q.; Zhang, W.; Shao, Y.; Chen, Y.; Sun, M.; Fu, X. Efficient degradation of benzene over LaVO4/TiO2
nanocrystalline heterojunction photocatalyst under visible light irradiation. Environ. Sci. Technol. 2009, 43, 4164–4168.
44. Wu, H.; Li, C.; Che, H.; Hu, H.; Hu, W.; Liu, C.; Ai, J.; Dong, H. Decoration of mesoporous Co3O4 nanospheres assembled by
monocrystal nanodots on g-C3N4 to construct Z-scheme system for improving photocatalytic performance. Appl. Surf. Sci. 2018,
440, 308–319.
45. Ye, M.; Gong, J.; Lai, Y.; Lin, C.; Lin, Z. High-efficiency photoelectrocatalytic hydrogen generation enabled by palladium quan-
tum dots-sensitized TiO2 nanotube arrays. J. Am. Chem. Soc. 2012, 134, 15720–15723.
46. Bertoluzzi, L.; Bisquert, J. Equivalent circuit of electrons and holes in thin semiconductor films for photoelectrochemical water
splitting applications. J. Phys. Chem. Lett. 2012, 3, 2517–2522.

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