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org/JPCC Article

Type-II Band Alignment Enhances Unassisted Photoelectrochemical

Water-Splitting Performance of the BaTiO3/CdS Ferroelectric
Heterostructure Photoanode under Solar Light Irradiation
Tianci Fang, Hong Hu, Jie Liu, Meng Jiang, Sibo Zhou, Junli Fu,* Wenzhong Wang, and Yuping Yang

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ABSTRACT: Here, we first use CdS nanoparticles to sensitize ferroelectric BaTiO3 nanostructures to construct the BaTiO3/CdS
heterostructure photoanodes by a facile hydrothermal method and subsequent successive ionic layer adsorption and reaction.
Combining the measurements of the valence band and core-level X-ray photoelectron spectroscopy spectra with energy band
calculation, the type-II energy structure established at the BaTiO3 and CdS interface is confirmed. Benefiting from the type-II band
alignment of the heterostructures, the spontaneous polarization electric field induced by BaTiO3, and the remarkable visible light
absorption ability of CdS, the as-prepared BaTiO3/CdS heterostructure photoanode exhibits significantly improved and stable
photoelectrochemical water-splitting activity. The highest photocurrent density of the constructed BaTiO3/CdS heterostructure
photoanode with optimized CdS nanoparticle loading reaches up to 0.5 mA cm−2 at 0 V versus Ag/AgCl, which is about 12-fold that
of the pure BaTiO3 photoanode. Additionally, the solar-to-hydrogen conversion efficiency of the BaTiO3/CdS heterostructure
photoanode is 0.48% at 0.13 V versus reversible hydrogen electrode, 24-fold that of the bare BaTiO3 photoanode. In contrast with
the photoelectrochemical performance of the other reported BaTiO3-based heterostructure photoanodes, the photocurrent density
(0 V versus Ag/AgCl) and the solar-to-hydrogen conversion efficiency (0.13 V versus reversible hydrogen electrode) achieved by the
present BaTiO3/CdS photoanode are the highest.

1. INTRODUCTION the effective transport and separation of photogenerated charge

The efficient exploitation of renewable solar energy has been
regarded as a hopeful strategy to address the growing energy
crisis.1,2 Recently, considerable studies have shown that the
solar light-driven photoelectrochemical (PEC) water splitting
of a nanoscale semiconductor photoanode is a promising
technology to use solar energy to generate hydrogen directly.3,4
Therefore, various semiconductor photoanodes have been
widely applied to split water through a PEC cell.5−8 However,
the poor absorption ability of visible light and rapid
recombination of photogenerated charge carriers need to be
solved for the semiconductor photoanodes to improve PEC
performance.9−11
In recent years, ferroelectric materials with a spontaneous
polarization electric field (SPEF) have been introduced into
the PEC water-splitting field because the SPEF can promote
carriers, thus improving the PEC properties of ferroelectric
material-based photoanodes.12,13 As one of the typical
ferroelectric materials, BaTiO3 (BTO) possesses a perovskite
structure with a band gap of 3.2 eV. Most importantly, it has
suitable band positions to split water into hydrogen and
oxygen.14−17 Thus, BTO has attracted extensive attention in
the field of PEC water splitting due to its unique structure
features and outstanding ferroelectric properties. For example,
Received: June 26, 2021
Revised: August 7, 2021
Published: August 19, 2021

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Cui et al. studied the photocatalytic and PEC performance of
BTO/α-Fe2O3 heterogeneous photocatalysts in which the
SPEF of BTO was used to improve the photocatalytic
efficiency and PEC activity.18 Li et al. reported that the PEC
activity of the ferroelectricity-driven BTO/Ag2O heterostruc-
ture microsphere photoanode was greatly enhanced due to the
ferroelectricity of BTO.19 Our previous study showed that the
effective separation of photogenerated charge carriers achieved
by SPEF of BTO led to the enhanced PEC performance of the
BTO@α-Fe2O3 photoanode.20 However, the wide band gap of
BTO makes it only absorb ultraviolet light (about 4%
sunlight); furthermore, it has a high recombination rate and
short lifetime of charge carriers, limiting the practical
applications as photoanode material for PEC water split-
ting.21,22
Considering the disadvantages of BTO, many methods have
been employed to boost its PEC performance.15,23,24 Previous
research results have shown that the heterojunction structure
of BTO modified with narrow band gap semiconductors can
not only greatly improve the absorption ability of visible light
but also significantly promote the effective separation of
photoproduced charge carriers due to synergistic effect of the
SPEF and the suitable energy band matching structure
between coupling semiconductors. Therefore, several narrow
band gap semiconductors such as CuO, CdS, and Cu2O have
been employed to modify the BTO photoanode for
significantly boosting PEC performance.25−27 As displayed in
previous studies, CdS is one of the important visible light
response semiconductors due to its narrow band gap.
Moreover, its energy band positions are suitable to split
water into hydrogen and oxygen. The superior visible light
absorption ability and suitable band structure make CdS
exhibit excellent PEC water-splitting activity.28,29 Therefore,
CdS nanostructures are commonly applied to sensitize other
semiconductor photoelectrodes to achieve remarkably en-
hanced PEC activity.30−32
In view of the ferroelectricity of BTO and the remarkable
visible light harvesting capability of CdS, the BTO/CdS
heterostructure photoanode is expected to obtain improved
PEC performance. Most importantly, the energy level
alignment between BTO and CdS plays a vital role in
constructing the efficient BTO/CdS photoanodes with
improved PEC activity. Liu et al. studied a BTO-CdS
composite structure system with improved hydrogen produc-
tion performance in which a type-I energy band structure was
built between BTO nanospheres and CdS nanoparticles
(NPs).33 While Thampi et al. reported that a type-II energy
structure was established between CdS quantum dots and
BTO films.34 Herein, we first calculate the energy band
alignment between the BTO nanostructure and CdS NPs by
combining the results of X-ray photoelectron spectroscopy
(XPS) with ultraviolet−visible (UV−vis) optical absorption
spectra and prove that the type-II energy alignment is formed
in BTO/CdS heterostructure photoanodes.
In this study, CdS NP-modified BTO nanostructure
photoanodes have been successfully prepared via ingenious
combination of a facile hydrothermal method with successive
ionic layer adsorption and reaction (SILAR). The PEC
performance of BTO/CdS heterostructure photoanodes with
different loading amounts of CdS NPs is investigated by a
three-electrode electrochemical system. Compared with the
pure BTO photoanode, the PEC performance and solar-to-
hydrogen (STH) conversion efficiency of BTO/CdS photo-
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anodes are significantly improved, which is attributed to the
type-II energy structure of BTO/CdS photoanodes, the
ferroelectric property of BTO nanostructures, and the
outstanding ability for absorbing visible light of CdS NPs.
2. EXPERIMENTAL SECTION
2.1. Synthesis of TiO2 Nanorod Arrays (NRAs). TiO2
NRAs were synthesized by an easy hydrothermal reaction.
Initially, the FTO glass with a size of 15 × 50 mm was
ultrasonically cleaned with deionized water, acetone, absolute
ethanol, and deionized water, respectively. Subsequently, 15
mL of concentrated hydrochloric acid was slowly dropped into
an autoclave (50 mL) with 15 mL of deionized water under
stirring. The concentrated hydrochloric acid was used to guide
the oriented growth of TiO2 nanorods.35 Then, 500 μL of
tetrabutyl titanate solution was added and stirred for 30 min
followed by placing the cleaned FTO glass into the tank of the
autoclave vertically. After this, the sealed autoclave was placed
in a 150 °C furnace for 3.5 h. After cooling down to room
temperature, the samples were washed with ultrapure water.
2.2. Preparation of BTO Nanostructures. A facile
hydrothermal reaction was used to convert the prepared
TiO2 NRAs into BTO nanostructures. Briefly, a mixed solution
with a pH value of 12 was prepared by mixing 0.06 M
Ba(OH)2·8H2O solution and ammonia solution followed by
transferring to an autoclave with TiO2 NRAs grown in FTO
glass. The mixed solution with a pH of 12 was prepared to
prevent etching of the FTO substrate.16 Then, the autoclave
was heated in an oven at 210 °C for 8 h and cooled down to
room temperature naturally. Finally, the FTO glass grown with
BTO nanostructures was cleaned with diluted HCl, anhydrous
ethanol, and pure water for several times.
2.3. Fabrication of BTO/CdS Heterostructures. The
CdS NP-sensitized BTO nanostructures were prepared by an
improved SILAR process. Typically, the BTO nanostructures
grown onto FTO glass were immersed in 0.05 M ethanol
solution of Cd(NO3)2·4H2O for 1 min followed by washing
with anhydrous ethanol. After this, the sample was soaked in
0.05 M Na2S methanol solution for 1 min and then washed
with methanol solution. The above mentioned reaction process
was referenced as one SILAR cycle. In order to evaluate the
effect of CdS loading on the PEC water-splitting performance,
the samples loaded with different amounts of CdS NPs were
fabricated through 5, 10, and 15 SILAR cycles. The prepared
samples were denoted as BTO/CdS-5, BTO/CdS-10, and
BTO/CdS-15 heterostructures, respectively. The synthesis
process of BTO/CdS heterojunction structure photoanodes
is presented in Figure 1.
2.4. Characterization. X-ray diffraction (XRD, employing
Cu Ka radiation) and XPS were applied to characterize the
crystalline phase and surface chemical compositions of the as-
synthesized BTO/CdS heterostructures. Scanning electron
microscopy (SEM) was employed to study the morphological
features of the samples. The elemental mappings were
collected using a scanning electron microscope by an energy
dispersive X-ray (EDX) detector. The light absorption
property was studied with UV−vis spectroscopy (Lambda
950). A fluorescence spectrophotometer (Edinburgh FLS 980)
was employed to record photoluminescence (PL) spectra
under excitation of 320 nm light.
2.5. PEC Measurements. The PEC water-splitting
performance of the BTO and BTO/CdS heterostructure
photoanodes was tested by a three-electrode electrochemical
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Figure 1. Synthesis process of BTO/CdS heterojunction structures.
workstation (CHI 760C). An FTO glass grown with the
sample was employed as the working electrode, and a Pt wire
and a Ag/AgCl were used as the counter electrode and
reference electrode, respectively. The BTO/CdS heterostruc-
ture photoanodes were irradiated by a 300 W Xe lamp
(simulated light), and the power density illustrated on the
working photoanode is 100 mW cm−2. The photocurrent
density−time (I−t) curves, linear sweep voltammogram (LSV)
plots, and electrochemical impedance spectroscopy (EIS)
curves were obtained in 0.35 M Na2S and 0.25 M Na2SO3
electrolyte.
3. RESULTS AND DISCUSSION
The XRD measurement was employed to characterize the
composition and crystal structure of the as-prepared samples.
As shown in Figure 2a, five characteristic diffraction peaks of
BTO match well with the tetragonal BTO crystal (JCPDS 05-
0626). After loading with CdS NPs on BTO nanostructures,
the XRD patterns of BTO/CdS heterostructures present two
weak characteristic peaks of CdS at 36.6 and 66.7°, which can
be assigned to (102) and (203) planes of hexagonal CdS
(JCPDS 41-1049), respectively. In the XRD pattern, CdS only
exhibits two weak diffraction peaks, indicating that the content
of the CdS NPs on the surface of BTO is low. Additionally, as
demonstrated in Figure 2a, no impurity peaks are observed,
confirming that the as-synthesized samples are composed of
high-pure BTO and CdS.
XPS spectra were applied to further determine surface
compositions and elemental valence states. Figure 2b−f
presents XPS spectra of BTO/CdS-10 heterostructures. The
high-resolution spectrum of Ba 3d in Figure 2b shows two
peaks at 779.4 and 794.7 eV, which correspond to the Ba 3d5/2
and Ba 3d3/2 of Ba2+,20,27 respectively. The binding energies of
458.9 and 464.6 eV presented in Figure 2c can be assigned to
the Ti 2p3/2 and Ti 2p1/2 of Ti4+,20,27 respectively. In XPS
spectra of BTO/CdS heterostructures, the loading of the CdS
NPs on the surface of BTO possibly is responsible for the weak
peaks of Ba 3d and Ti 2p. As shown in Figure 2d, the binding
mode located at 531.1 eV arises from coordinative unsaturated
oxygen species.31 By fitting the spectrum of the S element in
Figure 2e, it can be seen that two peaks at 162.5 and 161.4 eV
originate from the binding energies of S 2p1/2 and S 2p3/2,28,31
respectively. Two characteristic peaks for Cd 3d3/2 and Cd
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Figure 2. (a) XRD patterns of pure BTO nanostructures and BTO/
CdS heterostructures. XPS spectra of BTO/CdS-10 heterostructures:
(b) Ba 3d, (c) Ti 2p, (d) O 1s, (e) S 2p, and (f) Cd 3d.
3d5/2 are found at 411.8 and 405.1 eV, as shown in Figure
2f.28,31 Therefore, the experimental measurements of XPS
confirm that the BTO/CdS heterostructures can be success-
fully fabricated by growing CdS NPs on the BTO
nanostructure surface through SILAR.
The morphology and size of the as-fabricated products were
investigated by SEM. Figure 3 shows the SEM photographs of
the obtained samples at low and high magnifications. As
displayed in Figure 3a,b, the BTO nanostructures exhibit
almost nanoarray morphology composed of NPs. As
apparently shown in Figure 3b, the BTO nanostructures
possess a smooth surface. Figure 3c−h exhibits the SEM
morphologies of the BTO/CdS heterostructures fabricated by
loading with CdS NPs on the surfaces of BTO nanostructures
through 5, 10, and 15 SILAR cycles. As shown in Figure 3c,d,
the SEM images of BTO/CdS-5 prepared via 5 SILAR cycles
clearly demonstrate that the BTO nanostructure surfaces are
evenly covered with small dense CdS NPs. After cycling 10
SILAR cycles, the surfaces of BTO become rather rough as
exhibited in Figure 3e,f, showing that the amounts of CdS NPs
on the surfaces of BTO increase. More importantly, the CdS
NPs become denser with the increasing of SILAR cycles. As
shown in Figure 3g,h, when the cycling numbers increase to 15
times, a large amount of CdS NPs cover onto the surfaces of
BTO nanostructures. The SEM images show that the BTO/
CdS heterostructures have been successfully prepared via a
facile SILAR process.
In order to further study the composition of BTO/CdS
heterostructures, the EDX elemental mapping images of
heterostructures are displayed in Figure 4. Figure 4a presents
the SEM photograph of a single BTO/CdS heterostructure,
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Figure 3. SEM photographs of (a, b) BTO nanostructures, (c, d)
BTO/CdS-5, (e, f) BTO/CdS-10, and (g, h) BTO/CdS-15
heterostructures at low and high magnifications.
Figure 4. (a) SEM photograph of an individual BTO/CdS
heterostructure. Elemental mappings of (b) Ba, (c) Ti, (d) O, (e)
Cd, and (f) S elements.
which is employed to collect elemental mappings. Figure 4b−f
shows the elemental mapping images of the heterostructure,
demonstrating that Ba, Ti, O, Cd, and S elements coexist in the
BTO/CdS heterostructure. Thus, the elemental mappings
exhibit that the CdS NPs have successfully covered onto the
surfaces of BTO nanostructures.
The light absorption capacity of bare BTO nanostructures
and BTO/CdS heterostructures were studied by the UV−vis
spectra. From Figure 5a, it can be seen that pure BTO
nanostructures exhibit obvious ultraviolet light absorption at
around 400 nm, which is consistent with the intrinsic
absorption edge of the BTO nanostructures.20,27 However,
after loading with CdS NPs onto the surfaces of BTO, the
absorption band edge of BTO/CdS heterostructures gradually
extends from 400 to 560 nm. Moreover, the absorption
intensity in the visible light region increases with the increase
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Figure 5. (a) Light absorption and (b) Tauc curves of samples.
of CdS NP loading. The enhancement for visible light
absorption of the BTO/CdS heterostructures contributes to
the superior visible light harvesting capacity of CdS NPs. The
result of UV−vis spectroscopy measurements demonstrates
that the CdS NPs grown on the BTO nanostructure surface
can effectively enhance visible light absorption of the BTO/
CdS heterostructures. In order to study the absorption band
gap values of the BTO/CdS heterostructures, the Tauc plots of
the samples are presented in Figure 5b. It can be seen that the
band gap of BTO is 3.11 eV. After the surfaces of BTO are
modified with CdS NPs, the band gap of BTO/CdS
heterostructures decreases from 2.9 eV (BTO/CdS-5) to
2.34 eV (BTO/CdS-15) because of a relatively small band gap
(2.32 eV) of CdS NPs.
The PEC activities of the as-constructed photoanodes were
studied under simulated sunlight illumination in 0.35 M Na2S
and 0.25 M Na2SO3 electrolyte. I−t curves of the prepared
photoanodes are shown in Figure 6a. It can be observed that
Figure 6. (a) Photocurrent density vs. time curves without bias, (b)
plots of photocurrent density vs. applied potential, (c) STH
conversion efficiency curves, and (d) photocurrent densities of the
pure BTO and BTO/CdS photoanodes.
there is no obvious dark current in the samples without light
illumination. When the light illuminates on the photoanodes,
both pure BTO and BTO/CdS photoanodes produce obvious
photocurrent immediately, and the sharp peak in the
photocurrent density plots is induced by the accumulation of
the photogenerated holes at the interface of the photoelectrode
and electrolyte.36 Furthermore, the photocurrent density of
BTO/CdS heterostructure photoanodes increases significantly
compared with that of the pure BTO photoanode. As clearly
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Table 1. PEC Activity of the BTO-Based Photoanodes

STH conversion
photoanodes photocurrent density (bias) efficiency (bias) light and intensity electrolyte ref
BTO/CdS heterostructures 0.5 mA cm−2 (0 V vs. Ag/AgCl) 0.48% (0.13 V vs. simulated light 300 W Xe 0.35 M Na2S + 0.25 M Na2SO3 this
RHE) lamp work
BTO/α-Fe2O3 heterostructures 0.6 μA cm−2 (0.8 V vs. Ag/AgCl) simulated light 300 W Xe 0.5 M Na2SO4 18
lamp
BTO/α-Fe2O3 heterostructures 0.37 mA cm−2 (0 V vs. Ag/AgCl) simulated light 300 W Xe 0.1 M NaOH 20
lamp
BTO/Ag2O heterostructures 3.8 μA cm−2 (0.5 V vs. SCE) simulated light 300 W Xe 0.1 M Na2SO4 21
lamp
BTO/CuO heterostructures 300 nA cm−2 (0 V vs. Ag/AgCl) 370 nm light 0.5 mW cm−2 0.5 M Na2SO4 25
BTO/Cu2O heterostructures 0.26 mA cm−2 (0 V vs. Ag/AgCl) 0.11% (0.72 V vs. 370 nm light 0.5 mW cm−2 0.1 M NaOH 27
RHE)
BTO-CdS nanospheres 0.3 μA cm−2 (0 V vs. Ag/AgCl) visible light 300 W Xe lamp 0.2 M Na2SO4 33

Figure 7. (a) EIS plots and the equivalent circuit model (inset), (b) PL spectra, (c) OCVD measurements, and (d) average charge carrier lifetimes
of the BTO nanostructures and BTO/CdS-10 heterostructures.

exhibited in Figure 6a, the highest photocurrent density
generated by the BTO/CdS-10 heterostructure photoanode is
0.5 mA cm−2, which is 12 times higher than that of the pure
BTO photoanode. Whereas, the photocurrent density of BTO/
CdS photoanodes first increase and then decrease with the
increase of CdS contents. The results indicate that an excess
amount of CdS NPs is unfavorable for the light absorption of
BTO, thus suppressing the photoexcitation of BTO nano-
structures.
The potential versus (vs.) Ag/AgCl electrode is converted to
the reversible hydrogen electrode (RHE) through the Nernst
formula:
simulated sunlight irradiation. Figure 6b shows the LSV curves
of the as-prepared photoanodes, showing that the photocurrent
densities of all photoanodes increase with the bias. Especially,
the BTO/CdS-10 heterostructure photoanode generates the
highest photocurrent density at the same bias. The LSV results
are consistent with the above I−t measurements. The result
further shows that PEC properties of BTO nanostructures can
be effectively enhanced by optimizing the loading content of
CdS NPs.
As an important property for the photoanode, the STH
conversion efficiency (η) of the fabricated photoanode can be
determined through the following equation:37

VRHE = VAg/AgCl + VAg/AgCl 0 + 0.059PH JP × (1.23 − VRHE)

(1) η= × 100%
P light
(2)
where the value of VAg/AgCl 0 is 0.197 V at 25 °C, and the pH
value of the electrolyte is 13. The PEC performance of bias- where JP (mA cm−2) and VRHE (V) represent the photocurrent
dependent photocurrent density of the samples was also density and corresponding applied voltage vs. RHE,
measured under the bias from 0.2 to 1.8 V vs. RHE and respectively. Plight is the light intensity density (100 mW
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cm−2). As displayed in Figure 6c, after optimizing the loading
of CdS NPs, the BTO/CdS-10 heterostructure photoanode
achieves a maximum STH conversion efficiency of 0.48% at
0.13 V vs. RHE, which is about 24 times that (0.02%) of the
BTO photoanode.
To evaluate the photostability of the photoanodes, the
photocurrent densities were tested under bias-free light
irradiation during the PEC process. Figure 6d exhibits the
photocurrent density patterns of the photoanodes for four
consecutive cycles with 30 min per cycle. After four
consecutive cycles, the BTO/CdS heterostructure photo-
anodes retain the stable photocurrent, verifying that the
photoanodes exhibit good stability and reusability during the
PEC water-splitting process.
For comparing PEC performance, a detailed comparison for
PEC performance of the BTO/CdS photoanode with other
related BTO-based photoanodes is given in Table 1. The result
shows that the photocurrent density (0.5 mA cm−2) under the
bias-free condition and STH conversion efficiency (0.48%)
acquired by the BTO/CdS-10 photoanode is the highest in all
reported BTO-based photoanodes, confirming that a promis-
ing photoanode is constructed in the present work.
Study of the charge transport and separation behavior is very
important to evaluate the PEC activity of the photoanode. As
an effective technology to elucidate the charge separation
behavior, the EIS measurement was conducted. The EIS plots
of BTO and BTO/CdS-10 photoanodes are shown in Figure
7a. The arc radius of the BTO/CdS-10 heterostructure
photoanode is smaller than that of the pure BTO photoanode,
indicating that the BTO/CdS-10 photoanode has smaller
transfer resistance and higher separation efficiency of charge
carriers. The equivalent circuit model (inset of Figure 7a) of
the EIS plots was employed to further investigate the charge
transport property. The fitting parameters of the equivalent
circuit are displayed in Table 2. The definitions of Rs, Rct1, and
Table 2. Fitting Parameters of BTO and BTO/CdS-10
Photoanodes
photoanodes Rs (Ω) Rct1 (Ω) Rct2 (Ω)
BTO 9.323 4857 39.60
BTO/CdS-10 4.054 471.3 20.37
Rct2 are the same as those in the reported literature.27 The Rct1
value (471.3 Ω) of the BTO/CdS-10 photoanode is much
lower than that (4857 Ω) of the bare BTO photoanode,
demonstrating that the effective separation of the photo-
generated charge carriers in the BTO/CdS-10 heterostructure
photoanode is achieved. Thus, the EIS results show that the
boosted PEC property of the BTO/CdS-10 heterostructure
photoanode is attributed to the effective separation of the
photoproduced charge carriers.
In order to further study the recombination and separation
behavior of charge carriers, the PL emission curves of BTO
nanostructures and BTO/CdS-10 heterostructures are dis-
played in Figure 7b. Apparently, the pure BTO nanostructures
demonstrate two strong peaks at about 410 and 460 nm in the
PL spectra, indicating the high recombination rate of the
photogenerated charges in BTO nanostructures.38 Never-
theless, compared to that of BTO nanostructures, the emission
intensity of the BTO/CdS-10 heterostructures is apparently
suppressed, indicating that the photogenerated charge carriers
of BTO/CdS-10 heterostructures are separated effectively. The
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results of PL spectra further confirm that the improved PEC
activity of BTO/CdS heterostructure photoanodes results from
the effective separation of photoproduced charge carriers.
The charge carrier lifetime of BTO/CdS heterostructure
photoanodes was evaluated by the measurement of transient
open-circuit voltage decay (OCVD), which was employed to
further investigate the recombination and separation behavior
of charge carriers. The OCVD plots of the pure BTO and
BTO/CdS-10 photoanodes are shown in Figure 7c. According
to the result of OCVD measurement, the average lifetime (τn)
of the charge carrier in the photoanode can be obtained
through the following formula:39,40
kBT ji dVOC zy
jj zz
q jk dT z{
−1
τn = −
(3)
where the definitions of all variables are the same as those in
the reported literature. As apparently presented in Figure 7d,
the average lifetime of the charge carrier in the BTO/CdS-10
heterostructure photoanode is longer than that in the pure
BTO photoanode, demonstrating that the BTO nanostructure
modified with CdS NPs prolongs the charge carrier lifetime of
the BTO/CdS heterostructure photoanode. The measurement
results of OCVD and UV−vis apparently display that the BTO
nanostructures modified with CdS NPs not only acquire
enhanced visible light absorption capacity but also achieve
prolonged charge carrier lifetime, leading to the remarkable
improved PEC performance of BTO/CdS heterostructures.
Study on the energy band alignment of BTO/CdS
heterostructures is a crucial issue for elucidating the transfer
and separation process of photogenerated charge carriers and
the mechanism of improved PEC activity. To investigate the
relative conduction band (CB) and valence band (VB)
positions of the BTO and CdS in the BTO/CdS hetero-
structure, XPS spectra of the pure BTO and CdS and the core-
level XPS spectra of the heterostructures were measured. The
VB XPS spectra of bare BTO and CdS nanostructures are
displayed in Figure 8a,b. The valence band maximum (VBM)
value of BTO is 1.68 eV, as shown in Figure 8a. Meanwhile,
the VBM value of CdS is 1.16 eV, as seen in Figure 8b. As seen
from Figure 8c, the binding energies of Cd 3d5/2 for the bare
CdS NPs and the BTO/CdS heterostructures are 404.57 and
404.46 eV, respectively. Meanwhile, Figure 8d shows that the
binding energies of Ti 2p3/2 for the pure BTO nanostructures
and BTO/CdS heterostructures are 458.24 and 458.89 eV,
respectively. In addition, the UV−vis measurements (Figure
5b) show that the band gaps of the pure BTO and CdS
nanostructures are 3.11 and 2.32 eV, respectively.
Based on these experimental data, the VB (ΔEV) and CB
(ΔEc) offsets between BTO and CdS in the BTO/CdS
heterostructures can be calculated via the following equa-
tions:41
ΔE V (BTO/CdS) = (ECd 3d5/2 − E VBM)CdS
− (E Ti 2p3/2 − E VBM)BTO − ΔECL (4)
ΔECL = (ECd 3d5/2 − E Ti 2p3/2)BTO/CdS (5)
ΔEC (BTO/CdS) = (Egap)CdS − (Egap)BTO + ΔE V (BTO/CdS)
(6)
The values for ΔEV and ΔEC acquired from XPS
measurement data are 1.28 and 0.49 eV, respectively.
https://doi.org/10.1021/acs.jpcc.1c05639
J. Phys. Chem. C 2021, 125, 18734−18742
The Journal of Physical Chemistry C
Figure 8. VB XPS spectra of (a) BTO nanostructures and (b) CdS NPs. (c) Cd 3d5/2 core-level peaks for pure CdS NPs and BTO/CdS
heterostructures, and (d) Ti 2p3/2 core-level binding energies of BTO nanostructures and BTO/CdS heterostructures.
Therefore, the measurements and analyses of XPS data
evidently confirm that a type-II energy band structure is
formed between BTO and CdS in the BTO/CdS hetero-
structures as shown in Figure 9. The type-II band alignment
Figure 9. Schematic of band energies and the charge transfer process
of BTO/CdS heterostructures.
between BTO and CdS can drive the photoinduced electrons
on the CdS CB to migrate to the BTO CB, gathering with the
photogenerated electrons of BTO and then arriving at the
counter electrode to conduct the reduction reaction of water.
Furthermore, the photoinduced holes move from the VB of
BTO to that of CdS. The separated holes react with the
sacrificial agents of Na2S and Na2SO3 (S2−/SO32−) in the
electrolyte solution to take part in the water oxidation reaction.
Additionally, the SPEF of ferroelectric BTO could also enable
the photoexcited charge carriers to transfer and separate
effectively.20 Therefore, the enhanced PEC activity of the
BTO/CdS heterostructure photoanode mainly contributes to
the effective separation of photoexcited charges induced by the
type-II energy band structure of BTO/CdS heterostructures
and the SPEF of ferroelectric BTO nanostructures.
18740
pubs.acs.org/JPCC Article
4. CONCLUSIONS
A novel heterostructure photoanode of BTO/CdS was
designed and prepared by combining the hydrothermal
method with the SILAR process. Under solar light irradiation,
the photocurrent density of the BTO/CdS heterostructure
photoanode is up to 0.5 mA cm−2, 12-fold that of the BTO
photoanode without applying any bias. Furthermore, the
BTO/CdS photoanodes exhibit good stability and reusability.
Additionally, after optimizing the loading of CdS NPs, the
BTO/CdS-10 heterostructure photoanode achieves a max-
imum STH conversion efficiency of 0.48% at 0.13 V vs RHE,
which is about 24 times that (0.02%) of the BTO photoanode.
The photocurrent density (0 V vs. Ag/AgCl) and STH
conversion efficiency (0.13 V vs. RHE) achieved by our present
work is the highest compared with other reported relative
BTO-based photoanodes. The type-II band alignment is
formed between BTO and CdS in the BTO/CdS hetero-
structures, which is confirmed by the measurements of the XPS
spectra and the band energy calculation. The remarkable
improved PEC performance is ascribed to the type-II band
alignment of the heterostructures, the SPEF of ferroelectric
BTO nanostructures, and the outstanding visible light
harvesting ability of CdS NPs. This study offers a promising
pathway for the design of BTO-based nanostructures to
enhance the PEC activity by integrating type-II band
alignment, the SPEF effect, and narrower band gap semi-
conductors into a photoanode.
■
AUTHOR INFORMATION
Corresponding Author
Junli Fu − School of Science, Minzu University of China,
Beijing 100081, P. R. China; orcid.org/0000-0001-9142-
5431; Phone: 86-10-68930239; Email: fujl08@
muc.edu.cn; Fax: 86-10-68930239
https://doi.org/10.1021/acs.jpcc.1c05639
J. Phys. Chem. C 2021, 125, 18734−18742
The Journal of Physical Chemistry C
Authors
Tianci Fang − School of Science, Minzu University of China,
Beijing 100081, P. R. China
Hong Hu − School of Science, Minzu University of China,
Beijing 100081, P. R. China
Jie Liu − School of Science, Minzu University of China, Beijing
100081, P. R. China
Meng Jiang − School of Science, Minzu University of China,
Beijing 100081, P. R. China
Sibo Zhou − School of Science, Minzu University of China,
Beijing 100081, P. R. China
Wenzhong Wang − School of Science, Minzu University of
China, Beijing 100081, P. R. China; orcid.org/0000-
0003-1366-3498
Yuping Yang − School of Science, Minzu University of China,
Beijing 100081, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.1c05639
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Key R&D Program
of China (Grant Nos. 2017YFB0405400 and
2020YFB2009300), the National Natural Science Foundation
of China (Grant Nos.11074312, 61575225, 11474174,
11374377 11404414, and 62075248), and the Undergraduate
Research Training Program of Minzu University of China
(Grant Nos. URTP2021110034, URTP2021110042, and
URTP2021110031).
■
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