pubs.acs.

org/JPCL Perspective

In Situ Irradiated X‑ray Photoelectron Spectroscopy Investigation on

Electron Transfer Mechanism in S‑Scheme Photocatalyst
Jianjun Zhang, Liuyang Zhang, Wang Wang,* and Jiaguo Yu*

Cite This: J. Phys. Chem. Lett. 2022, 13, 8462−8469 Read Online

ACCESS Metrics & More Article Recommendations

See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: S-scheme photocatalysts have demonstrated great potential in solar fuel

production. To study the electron transfer pathways in S-scheme heterojunctions, in situ
irradiated X-ray photoelectron spectroscopy (ISIXPS) is an effective and widely used
technology. However, the mechanism of ISIXPS in identifying the electron transfer pathways
Downloaded via TU DELFT on January 2, 2023 at 15:56:46 (UTC).

in S-scheme heterojunction has not yet been elucidated. In this Perspective, the development
process and the formation mechanism of S-scheme photocatalysts are first introduced.
Afterward, the principles of XPS and ISIXPS measurements are thoroughly explained, and
the applications of XPS and ISIXPS in confirming the interfacial electron transfer in S-
scheme heterojunctions are discussed. Finally, suggestions for future research on the
utilization of ISIXPS in S-scheme heterojunctions are proposed. This Perspective will provide
deep insight into the electron transfer mechanism in S-scheme photocatalysts through
ISIXPS.

T he energy demand is growing because of rapid economic

and social development. The overexploitation and
consumption of fossil fuels have caused an energy crisis and
environmental pollution.1−4 To achieve carbon neutrality, the
shift from fossil fuels to renewable energy is essential. Solar
energy is a clean and abundant renewable energy source.5−7
Emerging semiconductor photocatalysis is one of the most
promising technologies for solar energy utilization. Photo-
catalytic water splitting and photocatalytic CO2 reduction can
convert solar energy into storable and transportable chemical
fuels (also known as solar fuels, such as hydrogenand methanol)
at ambient temperature and pressure.8−10
Currently, the key scientific problem in photocatalysis is the
rapid recombination of photogenerated electrons and
holes.11−13 For single semiconductor photocatalysts, the
photogenerated carriers are easily recombined inside photo-
catalysts because of the strong Columbic interaction between
electrons and holes. To suppress the recombination of
photogenerated carriers in single photocatalysts, coupling two
semiconductors has been confirmed to be an effective
strategy.14,15 For a long time, numerous researchers have used
type-II heterojunctions to explain the electron transfer
mechanism in these composite photocatalysts. As exhibited in
Figure 1a, under photoexcitation, photogenerated electrons
transfer from the conduction band (CB) of semiconductor II
(SII) to the CB of semiconductor I (SI), while photogenerated
holes transfer from the valence band (VB) of SI to the VB of SII.
Although type-II heterojunctions seem to spatially separate
photogenerated carriers, they are faced with some problems.
Thermodynamically, the electron and hole transfer pathways
lead to decreased redox capacity of the photocatalytic systems.
From the viewpoint of dynamics, the repulsion between the
electrons (or holes) in SI and electrons (or holes) in SII and the
electron−hole attraction hinder the charge transfer between SI
and SII. To improve the redox capacity of the photocatalytic
systems, inspired by the natural photosynthesis of plants, Bard
proposed traditional (liquid) Z-scheme systems with suitable
redox ion pairs (RIPs) in 1979.16 The RIPs generally consist of
an electron acceptor and an electron donor (taking Fe3+/Fe2+ as
an example). After careful consideration, the supposed electron
transfer pathway in traditional Z-scheme systems is found to be
incorrect (Figure 1b). From the perspective of thermodynamics
and electrochemistry, Fe3+ is more likely to accept electrons
from the CB of SII, whereas Fe2+ is more easily oxidized by the
holes in SI. Besides, the existence of RIPs confines the
application of traditional Z-scheme systems to the liquid
phase. To remove this restriction, an all-solid-state Z-scheme
heterojunction was proposed by Tada et al. in 2006.17 Solid
metal conductors are used to replace the RIPs, extending the
application of Z-scheme photocatalysts to gas/solid-phase
reactions. However, the electron transfer pathway in all-solid-
state Z-scheme heterojunction still has the same problem as that
in the traditional Z-scheme systems.
Received: July 7, 2022
Accepted: August 31, 2022
Published: September 2, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.jpclett.2c02125

8462 J. Phys. Chem. Lett. 2022, 13, 8462−8469
The Journal of Physical Chemistry Letters
Figure 1. (a) Charge transfer pathways in type-II heterojunction and its
problems: Thermodynamically, the redox ability is weakened;
dynamically, the interelectron (or interhole) repulsion hinders the
supposed electron (or hole) transfer. (b) Supposed (solid lines) and
actual (dotted lines) charge transfer pathways in traditional Z-scheme
heterojunction. Thermodynamically, the supposed electron transfer
pathway is wrong. The actual electron transfer pathway is from CB of
SII to RIPs to VB of SI.
To resolve the problems and shortcomings of type-II
heterojunction and Z-scheme heterojunctions, our group
proposed a new concept of S-scheme (step-scheme) hetero-
junction in 2019.18,19 An S-scheme heterojunction photocatalyst
is generally composed of a reduction semiconductor (RS)
photocatalyst and an oxidation semiconductor (OS) photo-
catalyst with a staggered band structure.20 Prerequisites for the
formation of the S-scheme heterojunction are that both the CB
and Ef positions of RS are higher than those of OS. Herein, we
analyze the formation process of S-scheme heterojunction for
two n-type semiconductors. Since RS possesses higher Ef than
OS (Figure 2a), when RS and OS are in close contact, electrons
Figure 2. Formation process of S-scheme heterojunction photocatalyst: (a) positions of the energy bands and Ef before contact; (b) generation of BEF
and band bending near the interface after contact; (c) transfer pathway of photogenerated carriers under photoexcitation. The photogenerated
electrons will transfer from the CB of OS to the VB of RS driven by the BEF.
8463
pubs.acs.org/JPCL Perspective
will transfer from RS to OS until an equilibrium state is reached
(Figure 2b). Accordingly, the energy bands near the RS interface
are bent upward and the RS interface is positively charged
because of the depletion of electrons. In contrast, the energy
bands near the OS interface are bent downward and the OS
interface is negatively charged owing to the acceptance of
electrons. Therefore, a built-in electric field (BEF) is generated
at the interface with the direction pointing from RS to OS.
Additionally, the Ef near the RS interface gradually decreases and
the Ef near the OS interface gradually increases until the same
point is reached. Under photoexcitation, electrons are excited
into the CB and holes are generated in VB. The photogenerated
electrons in the CB of OS will transfer to the VB of RS driven by
the BEF (Figure 2c). Furthermore, the photogenerated electron
in the CB of RS will transfer to the surface of RS because of the
action of BEF. In contrast, the photogenerated holes in the VB of
RS will transfer to the interface of OS to recombine with the
photogenerated electrons of OS driven by the BEF (Figure 2c).
Also, the photogenerated holes in the VB of OS will further
transfer to the surface of OS. Consequently, the electrons with
strong reduction ability in the CB of RS and holes with superb
oxidation ability in the VB of OS are retained and separated in S-
scheme heterojunctions.
To verify the electron transfer pathways in S-scheme
photocatalysts, in situ irradiated X-ray photoelectron spectros-
copy (ISIXPS) is a powerful tool.21,22 However, the principle of
ISIXPS has not yet been revealed. This Perspective will provide
detailed explanations of the mechanism of XPS and ISIXPS in
evaluating the electron transfer in S-scheme heterojunctions.
Before discussing the applications of ISIXPS, it is important to
understand the fundamentals of XPS. XPS is an advanced and
sensitive surface analysis technology, which can provide
information on the elemental composition and content,
chemical state, and chemical bonding of various compounds.23
As is known to all, substances are composed of atoms, molecules,
and ions. Molecules and ions are formed through the covalent or
ionic bonding of atoms. Furthermore, an atom is made up of a
nucleus and electrons that are constantly moving in atomic
orbitals around the nucleus. During XPS measurements, a solid
sample electrically connected to the equipment is placed in a
chamber with an ultrahigh vacuum (<10−9 Pa). When the
sample surface is irradiated by a beam of high-energy X-rays
(1486.6 eV for Al Kα X-rays), the excited electrons are able to
escape from the sample surface into the vacuum (also known as
the photoelectric effect), causing ionization of the atoms (Figure
https://doi.org/10.1021/acs.jpclett.2c02125
J. Phys. Chem. Lett. 2022, 13, 8462−8469
The Journal of Physical Chemistry Letters pubs.acs.org/JPCL Perspective

Figure 3. (a) Principle of XPS measurements. When X-rays irradiate the sample surface, the excited electrons will escape from the sample surface and
enter the analyzer. (b) Generation process of photoelectron during XPS measurements. The excited electrons have sufficient energy to break through
the restrictions of Eb and Ws and escape from the sample surface with Eb. (c−e) Structures of carbon atoms after losing or accepting an electron. The Eb
of C 1s is increased when losing one electron, and the Eb of C 1s is decreased when accepting one electron.

Figure 4. (a) Principle of ISIXPS measurements. X-rays and UV−vis light simultaneously irradiate the sample surface, and photoelectrons are collected
by an analyzer. (b) Excitation processes of electrons during ISIXPS measurements. X-rays can excite the inner-shell electrons to become free
photoelectrons with Ek, while UV−vis light can only excite the valence electrons in the energy levels of VB into the energy levels of CB. (c) Changes in
electron density and elemental Eb of S-scheme photocatalyst under photoexcitation. Decreased electron density of OS leads to the increased elemental
Eb, while increased electron density of OS causes the reduced elemental Eb.

3a). The emitted electrons (photoelectrons) with different
kinetic energy (Ek) will pass the analysis slit of the XPS device,
and the electron current (related to the number of photo-
electrons per unit time), which depends on Ek, can be
recorded.24 A vivid description of the above-mentioned process
is illustrated in Figure 3b. From a microscopic perspective, the
energy of atomic orbitals is quantized, and thus, each electron
has a discrete energy. According to the distance from the nucleus
8464
(from close to far), the independent atomic orbitals around the
nucleus can be divided into different orbitals such as 1s, 2s, 2p,
and 3s. The energy required to eject an electron from the sample
is known as the electron’s ionization energy or binding energy
(Eb). Specifially, electrons in inner orbitals (such as 1s orbital)
have a higher Eb than those in outer orbitals (such as 2p orbital).
X-rays can excite the inner-shell electrons because of their
extremely high energy (for instance, Al Kα X-rays have an hν of
https://doi.org/10.1021/acs.jpclett.2c02125
J. Phys. Chem. Lett. 2022, 13, 8462−8469
The Journal of Physical Chemistry Letters
Figure 5. High-resolution XPS spectra of (a) C 1s in PT, CP, and CP under UV irradiation. High-resolution XPS spectra of (b) Cd 3d and (c) S 2p in
CdS, CP, and CP under UV irradiation. (d) Formation process of CdS/PT S-scheme heterojunction. Reproduced with permission from ref 27.
Copyright 2021, Wiley-VCH.
1486.6 eV). The excited electrons thus possess sufficient energy
to break through the restrictions of the Eb and the work function
of sample (Ws), and finally escape from the sample surface with
Ek. Therefore, the Eb can be calculated by the following format:25
E b = hv Ek Ws
In practical XPS measurements, the Eb of inner-shell electrons
can be obtained through measuring the Ek of photoelectrons.
Subsequently, the elements contained in the sample can be
identified based on the value of Eb, because the Eb is almost
unique for each element.
Furthermore, the Eb of inner-shell electrons is related to the
chemical state of the atom. When electron loss and acceptance
occur in the outer orbitals of an atom, the Eb of inner-shell
electrons is changed (also called chemical shift). Taking the
carbon atom as an example, it possesses two electrons in each of
the 1s orbital, 2s orbital, and 2p orbital (Figure 3d). Besides, the
carbon nucleus consists of six protons and six neutrons, and thus,
it has six positive charges. The attractive forces between atomic
nuclei and electrons are Coulombic force and nuclear force. The
Coulombic force stems from protons, while the nuclear force is
generated by both protons and neutrons. Since the number of
protons and neutrons in a carbon nucleus is fixed, the attractive
force that the nucleus can provide is constant. When a carbon
atom loses one valence electron in the 2p orbital, the total
number of electrons bound around the nucleus is reduced to five
(Figure 3c). Considering the atom as a whole, the attractive
force assigned to each electron by the nucleus is enhanced, and
thus, the Eb of C 1s increases. In contrast, when a carbon atom
accepts one electron in its 2p orbital, the total number of
electrons increases to seven. Hence, the attractive force assigned
to each electron is weakened and the Eb of C 1s decreases
(Figure 3e). In some cases, the acceptance or loss of electrons is
difficult to happen. For example, hybridization of atomic orbitals
8465
pubs.acs.org/JPCL Perspective
occurs in covalent compounds and new molecular orbitals are
formed, leading to a redistribution of electrons and a change in
electron density. Therefore, the Eb of C 1s will also change when
the carbon atom is in different chemical environments. The Eb of
C 1s increases when the electron density decreases in a carbon
atom, while the Eb of C 1s decreases when the electron density
increases in a carbon atom. Although this kind of change in Eb is
relatively smaller than that of electron acceptance or loss, the
consequent chemical shift is detectable in XPS.
With the fundamentals of general XPS having been
introduced, the mechanism of ISIXPS measurements is analyzed
next. During ISIXPS measurements, the high-energy X-rays and
ultraviolet−visible (UV−vis) light simultaneously irradiate the
sample surface (Figure 4a). Subsequently, the excited photo-
electrons with Ek will escape from the sample surface to the
vacuum and be collected by the analyzer. To analyze in detail the
functions of UV−vis light on the sample during ISIXPS
measurements, the excitation process of electrons is illustrated
in Figure 4b. X-rays with extremely high energy (Al Kα = 1486.6
eV) can excite the inner-shell electrons to overcome the
restrictions of Eb and Ws and finally become free photoelectrons
with the energy of Ek. However, the energy of UV−vis light (2−4
eV) is quite low in comparison with the X-ray and can only excite
the valence electrons from VB to CB, while the excited valence
electrons remain bound to the nucleus (Figure 4b). Hence, in
ISIXPS measurements, the analyzer detects the Eb of inner-shell
electrons after the excitation of the outer-shell valence electrons.
The excitation process of valence electrons also corresponds to
the electron transition from VB to CB in semiconductors. The
excited electrons in the CB are also known as photogenerated
electrons, which remain inside the semiconductors and can
transfer between two semiconductors. Similar to the analysis in
normal XPS, the loss of photogenerated electrons will result in
decreased electron density and increased elemental Eb, whereas
https://doi.org/10.1021/acs.jpclett.2c02125
J. Phys. Chem. Lett. 2022, 13, 8462−8469
The Journal of Physical Chemistry Letters pubs.acs.org/JPCL Perspective

Figure 6. High-resolution XPS spectra of (a) Ti 2p and (b) O 1s in TiO2, TiO2@ZnIn2S4, and TiO2@ZnIn2S4 under light illumination. High-
resolution XPS spectra of (c) Zn 2p, (d) In 3d, and (e) S 2p in ZnIn2S4, TiO2@ZnIn2S4, and TiO2@ZnIn2S4 under light illumination. (f) Electron
transfer in TiO2@ZnIn2S4 S-scheme heterojunction under light irradiation. Reproduced with permission from ref 21. Copyright 2021, Wiley-VCH.

the acceptance of photogenerated electrons will lead to
increased electron density and decreased elemental Eb.
According to the above discussion, the evidence of electron
transfer in S-scheme heterojunctions under darkness and
irradiation can be obtained through the combined analysis of
normal XPS and ISIXPS results. The change in Eb of a specific
element can be used to estimate the change of electron density.
Therefore, the electron transfer direction in S-scheme
heterojunctions can be determined.26 Normal XPS can detect
the electron transfer between RS and OS when they come into
contact. Since RS has a higher Ef than OS, electrons will transfer
from RS to OS after contact. Compared with RS before contact,
the electron density of RS decreases after contact, and the Eb of
constituent elements in RS increase correspondingly. Con-
versely, compared with OS before contact, the electron density
of OS within the S-scheme photocatalyst increases, and the
elemental Eb of OS should be decreased. Furthermore, ISIXPS
can also confirm the transfer direction of photogenerated
electrons in the S-scheme heterojunction. Under photo-
excitation, the photogenerated electrons in the CB of OS will
transfer to the VB of RS driven by the BEF, leading to increased
8466
electron density in RS and reduced electron density in OS
(Figure 4c). Hence, the elemental Eb of RS decreases, and that of
OS increases within the S-scheme photocatalyst under
illumination.
Based on the mechanism analysis of XPS and ISIXPS, two
examples are given, employing ISIXPS to disclose the charge
transfer mechanism in S-scheme heterojunctions. Cheng et al.
reported an inorganic/organic S-scheme heterojunction photo-
catalyst with high hydrogen production efficiency.27 CdS
nanocrystals are grown on the surface of pyrene-alt-triphenyl-
amine conjugated polymer (PT) via a solvothermal process.
Both CdS and PT are n-type semiconductors with a staggered
band structure, and the CB and Ef positions of PT are higher
than those of CdS, satisfying the conditions for the formation of
an S-scheme heterojunction. Normal XPS and ISIXPS measure-
ments are performed to confirm the electron transfer in CdS/PT
(CP) S-scheme photocatalyst. As shown in the high-resolution
XPS spectra of C 1s, the peak located at 284.8 eV is the aromatic
sp2 carbon which is used for calibration, and the peak of the C−
N bond in PT is situated at 286.3 eV (Figure 5a). In comparison
to PT, the peak of C−N in CP shifts toward higher Eb,
https://doi.org/10.1021/acs.jpclett.2c02125
J. Phys. Chem. Lett. 2022, 13, 8462−8469
The Journal of Physical Chemistry Letters
suggesting that PT loses electrons and its electron density
decreases. In contrast, compared with CdS, both Cd 3d and S 2p
peaks of CP shift toward lower Eb (Figure 5b,c), indicating that
CdS obtains electrons from PT and its electron density
increases. The changes in the electron density of CP and CdS
verify the electron transfer from PT to CdS after contact in
darkness (Figure 5d). In ISIXPS measurements, UV light, whose
wavelength is 365 nm, irradiates the sample surface. The peak of
C−N in CP shifts toward lower Eb, while the peaks of Cd 3d and
S 2p in CP move toward higher Eb. This phenomenon indicates
the electron density increment and decrement in PT and CdS,
respectively, further confirming the electron transfer from CdS
to PT under UV light irradiation. Therefore, normal XPS and
ISIXPS results successfully reveal the electron transfer pathways
in the CdS/PT S-scheme heterojunction.
In addition, Wang et al. constructed an S-scheme TiO2@
ZnIn2S4 core−shell photocatalyst with superb photocatalytic
CO2 reduction performance.21 ZnIn2 S4 nanosheets are
deposited on the surface of TiO2 hollow spheres by an in situ
chemical bath, and the TiO2@ZnIn2S4 composite also meets the
requirements of constructing S-scheme heterojunctions. Com-
pared with single TiO2, both the identified Ti 2p and O 1s peaks
in TiO2@ZnIn2S4 shift toward lower Eb after contact in darkness
(Figure 6a,b). Conversely, all the peaks of Zn 2p, In 3d, and S 2p
move toward higher Eb compared with single ZnIn2S4 (Figure
6c−e). These results suggest that the electron density of TiO2
increases and that of ZnIn2S4 decreases in TiO2@ZnIn2S4,
further validating the electron transfer from ZnIn2S4 to TiO2
after contact in darkness. Under 365 nm UV light irradiation, the
peaks of Ti 2p and O 1s in TiO2@ZnIn2S4 move toward higher
Eb (Figure 6a,b), while the peaks of Zn 2p, In 3d, and S 2p in
TiO2@ZnIn2S4 shift toward lower Eb (Figure 6c−e). This
outcome illustrates that electron density decreases in TiO2 and
increases in ZnIn2S4, confirming the transport of photo-
generated electrons from TiO2 to ZnIn2S4 driven by the BEF
(Figure 6f). Consequently, the XPS and ISIXPS measurements
effectively clarify the electron transfer direction in TiO2@
ZnIn2S4 S-scheme heterojunction under dark conditions and
photoexcitation.
In conclusion, XPS and ISIXPS, with great sensitivity, are
powerful means to detect subtle changes of elemental Eb due to
changes in electron density in darkness and under illumination.
Hence, the interactions and electron transfer between two
substances can be reflected by the changes in elemental Eb. XPS
and ISIXPS measurements are also universal methods for
monitoring electron transfer in heterojunction photocatalysts.
Apart from ascertaining the electron transfer pathways in S-
scheme heterojunctions, the applications of XPS and ISIXPS can
be extended to other photocatalytic systems, such as dye-
sensitized semiconductors and noble metal-semiconduc-
tors.28,29 Furthermore, current research works using ISIXPS in
S-scheme heterojunctions mainly focus on the electron transfer
direction between RS and OS. The influence of UV−vis light
intensity and the BEF strength on the electron transfer process
between RS and OS have rarely been studied. Hence, further
research works on S-scheme photocatalysts based on ISIXPS can
be conducted in the following aspects:
(1) Reveal the effects of UV−vis light intensity on the electron
transfer in S-scheme heterojunctions. The number of electrons
and holes generated in RS and OS is positively correlated with
the intensity of UV−vis light. With increasing intensity of UV−
vis light, more photogenerated electrons are produced and
transfer from the CB of OS to the VB of RS driven by the BEF.
8467
pubs.acs.org/JPCL Perspective
Within S-scheme heterojunctions, the electron density of OS
should be further reduced and that of RS should be further
increased, resulting in a greater shift of the XPS peaks.
Therefore, studying the effects of UV−vis light intensity in
ISIXPS measurements can provide additional evidence for
electron transfer in S-scheme heterojunctions.
(2) Elucidate the influence of BEF strength on the electron
transfer in S-scheme heterojunctions. According to the
formation mechanism of the S-scheme heterojunction, the
BEF strength is related to the difference of Ef between RS and
OS. When the difference of Ef between RS and OS increases, the
BEF strength should be enhanced, leading to a stronger driving
force for the interfacial electron transfer. Photogenerated
electrons are easier to transfer from the CB of OS to the VB
of RS, bringing about greater changes in the electron density and
elemental Eb of OS and RS. Hence, further evidence on S-
scheme heterojunctions can be obtained by studying electron
transfer in S-scheme photocatalysts with different BEF strengths
through ISIXPS measurements.
■ AUTHOR INFORMATION
Corresponding Authors
Wang Wang − Department of Chemistry, Wuhan University,
Wuhan 430072, P.R. China; Email: doublewang@
whu.edu.cn
Jiaguo Yu − Laboratory of Solar Fuel, Faculty of Materials
Science and Chemistry, China University of Geosciences,
Wuhan 430074, P.R. China; orcid.org/0000-0002-0612-
8633; Email: yujiaguo93@cug.edu.cn
Authors
Jianjun Zhang − Laboratory of Solar Fuel, Faculty of Materials
Science and Chemistry, China University of Geosciences,
Wuhan 430074, P.R. China
Liuyang Zhang − Laboratory of Solar Fuel, Faculty of Materials
Science and Chemistry, China University of Geosciences,
Wuhan 430074, P.R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpclett.2c02125
Notes
The authors declare no competing financial interest.
Biographies
Jianjun Zhang received his B.S. and Ph.D. degrees in Materials Science
from Wuhan University of Technology in 2017 and 2021, respectively.
He is now a postdoctoral researcher working in the Laboratory of Solar
Fuel at China University of Geosciences. His current research focuses
https://doi.org/10.1021/acs.jpclett.2c02125
J. Phys. Chem. Lett. 2022, 13, 8462−8469
The Journal of Physical Chemistry Letters
on the electron transfer mechanisms in heterojunction photocatalysts
and perovskite solar cells.
Liuyang Zhang received her Bachelor of Science degree (2012) from
Shanghai Jiao Tong University. Subsequently, she received her Ph.D.
degree in Materials Science and Engineering from National University
of Singapore (NUS) in 2016. She worked as a Research Fellow in NUS
before joining the State Key Laboratory of Advanced Technology for
Materials Synthesis and Processing at Wuhan University of Technology
as an associate professor. She became a professor at China University of
Geosciences in November 2021. Her main research background lies in
the area of photocatalysis and electrochemical energy storage.
Wang Wang received his B.S. in Chemistry from Sun Yat-sen
University and Ph.D. in Physical Chemistry from Wuhan University.
Currently, he is working with Prof. Shengli Chen at Wuhan University.
His research interests include fuel cells, electrochemical water splitting,
electrochemical synthesis, and so on.
Jiaguo Yu received his B.S. and M.S. in Chemistry from Central China
Normal University and Xi’an Jiaotong University, respectively; his
8468
pubs.acs.org/JPCL Perspective
Ph.D. in Materials Science is from Wuhan University of Technology
(WUT). His research interests include semiconductor photocatalysis,
photocatalytic hydrogen production, CO2 reduction, perovskite solar
cells, electrocatalysis, and so on. He is Foreign Member of Academia
Europaea (2020), Foreign Fellow of the European Academy of Sciences
(2020), and Fellow of the Royal Society of Chemistry (2015).
■ ACKNOWLEDGMENTS
This work was supported by National Key Research and
Development Program of China (2018YFB1502001), National
Natural Science Foundation of China (51932007,
51961135303, 21871217, U1905215, and 52073223), China
Postdoctoral Science Foundation (2021TQ0311 and
2021M702990), and International Postdoctoral Exchange
Fellowship Program (PC2022051).
■ REFERENCES
(1) Sayed, M.; Yu, J.; Liu, G.; Jaroniec, M. Non-Noble Plasmonic
Metal-Based Photocatalysts. Chem. Rev. 2022, 122, 10484−10537.
(2) Xiong, H.; Dong, Y.; Liu, D.; Long, R.; Kong, T.; Xiong, Y. Recent
Advances in Porous Materials for Photocatalytic CO2 Reduction. J.
Phys. Chem. Lett. 2022, 13, 1272−1282.
(3) Bie, C.; Wang, L.; Yu, J. Challenges for Photocatalytic Overall
Water Splitting. Chem. 2022, 8, 1567−1574.
(4) Zhang, D.; He, W.; Ye, J.; Gao, X.; Wang, D.; Song, J. Polymeric
Carbon Nitride-Derived Photocatalysts for Water Splitting and
Nitrogen Fixation. Small 2021, 17, 2005149.
(5) Xu, Q.; Wageh, S.; Al-Ghamdi, A.; Li, X. Design Principle of S-
Scheme Heterojunction Photocatalyst. J. Mater. Sci. Technol. 2022, 124,
171−173.
(6) Zhang, J.; Wang, L.; Jiang, C.; Cheng, B.; Chen, T.; Yu, J. CsPbBr3
Nanocrystal Induced Bilateral Interface Modification for Efficient
Planar Perovskite Solar Cells. Adv. Sci. 2021, 8, 2102648.
(7) Liu, Y.; Zheng, X.; Yang, Y.; Song, Y.; Yang, Y.; Li, J.; Shim, C.;
Shen, Y.; Tian, X. Recent Advances in the Hydrogen Evolution
Reaction of ZnxCd1‑xS-Based Photocatalysts. Sol. RRL 2022, 6,
2101061.
(8) Shen, R.; Ding, Y.; Li, S.; Zhang, P.; Xiang, Q.; Ng, Y.; Li, X.
Constructing Low-Cost Ni3C/Twin-Crystal Zn0.5Cd0.5S Heterojunc-
tion/Homojunction Nanohybrids for Efficient Photocatalytic H2
Evolution. Chin. J. Catal. 2021, 42, 25−36.
(9) Zhu, B.; Cheng, B.; Fan, J.; Ho, W.; Yu, J. g-C3N4-Based 2D/2D
Composite Heterojunction Photocatalyst. Small Structures 2021, 2,
2100086.
(10) Liu, S.; Wang, K.; Yang, M.; Jin, Z. Rationally Designed
Mn0.2Cd0.8S@CoAl LDH S-Scheme Heterojunction for Efficient
Photocatalytic Hydrogen Production. Acta Phys. Chim. Sin. 2022, 38,
2109023.
(11) Sayed, M.; Xu, F.; Kuang, P.; Low, J.; Wang, S.; Zhang, L.; Yu, J.
Sustained CO2-Photoreduction Activity and High Selectivity over Mn,
C-codoped ZnO Core-Triple Shell Hollow Spheres. Nat. Commun.
2021, 12, 4936.
(12) Ri, C.; Han, H.; Kim, Y.; Jong, U.; Kye, Y.; Yu, C. Enhancing the
Photocatalytic Hydrogen Evolution Performance of the CsPbI3/MoS2
Heterostructure with Interfacial Defect Engineering. J. Phys. Chem. Lett.
2022, 13, 4007−4014.
(13) Ran, L.; Qiu, S.; Zhai, P.; Li, Z.; Gao, J.; Zhang, X.; Zhang, B.;
Wang, C.; Sun, L. C.; Hou, J. G. Conformal Macroporous Inverse Opal
Oxynitride-Based Photoanode for Robust Photoelectrochemical Water
Splitting. J. Am. Chem. Soc. 2021, 143, 7402−7413.
(14) Li, Y.; Xia, Z.; Yang, Q.; Wang, L.; Xing, Y. Review on g-C3N4-
Based S-Scheme Heterojunction Photocatalysts. J. Mater. Sci. Technol.
2022, 125, 128−144.
(15) Wang, Z.; Lin, Z.; Shen, S.; Zhong, W.; Cao, S. Advances in
Designing Heterojunction Photocatalytic Materials. Chin. J. Catal.
2021, 42, 710−730.
https://doi.org/10.1021/acs.jpclett.2c02125
J. Phys. Chem. Lett. 2022, 13, 8462−8469
The Journal of Physical Chemistry Letters pubs.acs.org/JPCL Perspective

(16) Bard, A. J. Photoelectrochemistry and Heterogenous Photo-

Catalysis at Semiconductors. J. Photochem. 1979, 10, 59−75.
(17) Tada, H.; Mitsui, T.; Kiyonaga, T.; Akita, T.; Tanaka, K. All-
Solid-State Z-Scheme in CdS-Au-TiO2 Three-Component Nano-
junction System. Nat. Mater. 2006, 5, 782−786.
(18) Fu, J.; Xu, Q.; Low, J.; Jiang, C.; Yu, J. Ultrathin 2D/2D WO3/g-
C3N4 Step-Scheme H2-Production Photocatalyst. Appl. Catal., B 2019,
243, 556−565.
(19) Xu, Q.; Zhang, L.; Cheng, B.; Fan, J.; Yu, J. S-Scheme
Heterojunction Photocatalyst. Chem. 2020, 6, 1543−1559.
(20) Zhang, L.; Zhang, J.; Yu, H.; Yu, J. Emerging S-Scheme
Photocatalyst. Adv. Mater. 2022, 34, 2107668.
(21) Wang, L.; Cheng, B.; Zhang, L.; Yu, J. In situ Irradiated XPS
Investigation on S-Scheme TiO2@ZnIn2S4 Photocatalyst for Efficient
Photocatalytic CO2 Reduction. Small 2021, 17, 2103447.
(22) Xu, F.; Meng, K.; Cao, S.; Jiang, C.; Chen, T.; Xu, J.; Yu, J. Step-
by-Step Mechanism Insights into the TiO2/Ce2S3 S-Scheme Photo-
catalyst for Enhanced Aniline Production with Water as a Proton
Source. ACS Cata. 2022, 12, 164−172.
(23) Corcoran, C.; Tavassol, H.; Rigsby, M.; Bagus, P.; Wieckowski,
A. Application of XPS to Study Electrocatalysts for Fuel Cells. J. Power
Sources 2010, 195, 7856−7879.
(24) Bagus, P.; Ilton, E.; Nelin, C. The Interpretation of XPS Spectra:
Insights into Materials Properties. Surf. Sci. Rep. 2013, 68, 273−304.
(25) Greczynski, G.; Hultman, L. X-ray Photoelectron Spectroscopy:
Towards Reliable Binding Energy Referencing. Prog. Mater. Sci. 2020,
107, 100591.
(26) Wang, L.; Zhang, J.; Yu, H.; Patir, I. H.; Li, Y.; Wageh, S.; Al-
Ghamdi, A. A.; Yu, J. Dynamics of Photogenerated Charge Carriers in
Inorganic/Organic S-Scheme Heterojunctions. J. Phys. Chem. Lett.
2022, 13, 4695−4700.
(27) Cheng, C.; He, B.; Fan, J.; Cheng, B.; Cao, S.; Yu, J. An
Inorganic/Organic S-Scheme Heterojunction H2-Production Photo-
catalyst and its Charge Transfer Mechanism. Adv. Mater. 2021, 33,
2100317.
(28) Bai, S.; Mei, H.; Zhu, G.; Zhang, M.; Huang, W.; Cheng, L. In
Situ Irradiated X-ray Photoelectron Spectroscopy on the Ag- Recommended by ACS
Zn0.5Cd0.5S Core-Shell Structure and the Hydrogen Production
Activity. ACS Sustainable Chem. Eng. 2020, 8, 6488−6495.
(29) Bai, S.; Mei, H.; Huang, W.; Zhang, M.; Cheng, L. In Situ Light-Induced Structural Dynamic Evolution of Pt Single
Irradiated X-ray Photoelectron Spectroscopy on Ag-WS2 Hetero- Atoms for Highly Efficient Photocatalytic CO2 Reduction
structure for Hydrogen Production Enhancement. J. Materiomics 2021, Jiaxuan Fan, Junting Feng, et al.
7, 320−327. JUNE 06, 2022
ACS APPLIED MATERIALS & INTERFACES READ

Step-by-Step Mechanism Insights into the TiO2/Ce2S3 S-

Scheme Photocatalyst for Enhanced Aniline Production with
Water as a Proton Source
Feiyan Xu, Jiaguo Yu, et al.
DECEMBER 14, 2021
ACS CATALYSIS READ

Tailoring Surface Oxygen Vacancies in Tungsten Oxides for

Surface Plasmon Resonance-Enhanced Near-Infrared
Photoreduction of Cr(VI)
Jia-Min Zheng, Zhao-Qing Liu, et al.
JULY 13, 2022
ACS ES&T WATER READ

SnO2–x Nanoparticles Decorated on Graphitic Carbon Nitride

as S-Scheme Photocatalysts for Activation of
Peroxymonosulfate
Dai-Phat Bui, Viet Van Pham, et al.
AUGUST 30, 2021
ACS APPLIED NANO MATERIALS READ
Get More Suggestions >

8469 https://doi.org/10.1021/acs.jpclett.2c02125
J. Phys. Chem. Lett. 2022, 13, 8462−8469