Applied Surface Science 526 (2020) 145749

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0D/2D CeO2/ZnIn2S4 Z-scheme heterojunction for visible-light-driven T

photocatalytic H2 evolution
⁎
Min Zhanga, Jiacheng Yaoa, Muhammad Arifa, Bo Qiua, Hongfei Yina, Xiaoheng Liua, ,
⁎
Shen-ming Chenb,
a
Key Laboratory of Education Ministry for Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Nanjing 210094, China
b
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei 106, Taiwan, ROC

A R T I C LE I N FO A B S T R A C T

Keywords: The electronic transmission mode can effectively influence the photogenerated electron-hole separation effi-
CeO2 ciency, which further influence the photocatalytic hydrogen production performance. Herein, we synthesized a
ZnIn2S4 CeO2/ZnIn2S4 composite photocatalyst having a 0D/2D heterojunction by facile solvothermal and room tem-
Z-scheme perature precipitation methods. The successful construction of the heterojunction was demonstrated by XRD and
Photocatalytic hydrogen evolution
XPS. Meanwhile, the interesting findings shows that the 0D “chess” CeO2 compounded on the 2D “checkerboard”
ZnIn2S4 in SEM and TEM. The ESR test of %O2− and %OH demonstrates the photocatalytic mechanism of Z-
scheme electron transport in the catalyst. The highest hydrogen production rate of the catalyst reaches
847.42 μmol·g−1·h−1. This work provides a simple and effective strategy to achieve a rationally design photo-
catalyst for efficient, stable and cost-effective solar hydrogen production applications.

1. Introduction but also improve the photostability of chalcogenides [18–21].

The application of ZnO [22], TiO2 [23], CeO2 [24], Fe2O3 [25],
In recent decades, semiconductor materials have been under-going WO3 [26,27], g-C3N4 [28,29] and other traditional semiconductors in
fast development because of their intrinsically fascinating properties the field of photocatalysis has received extensive attention. Among
and potentially promising applications in a wide range of fields, such as them, CeO2 is a promising photocatalytic materials with abundant re-
in catalysis, sensing, supercapacitor and bioimaging [1–5]. The semi- serves, environmental friendliness and physical and chemical stability
conductor photocatalytic hydrogen production as an efficient energy [30–32]. CeO2 is also one of the most important rare-earth materials
conversion technology can be regarded as an effective way to solve and it has been extensively studied for energy conversion applications
future energy crisis. including fuel cells and solar cells because of its high oxygen storage
Semiconductor material ZnIn2S4 is a ternary chalcogen compound capacity. At present, hydrothermal and calcination methods are mainly
belongs to the AB2X4 (A = Zn, Cd, Cu; B = Al, Ga, In; X = S, Se, Te) employed for CeO2 photocatalyst preparation [33].
family [6–8]. The band gap is moderate, and it strong visible light In this work, we have prepared CeO2/ZnIn2S4 Z-scheme hetero-
absorption capacity and tremendous catalytic performance. It has a junction by using a facile solvothermal method and room temperature
homomorphic polymorphism, mainly composed of two typical struc- deposition of CeO2 in NH3·H2O. The XRD patterns showed successful
tures, cubic spinel and hexagonal phase [9,10]. For cubic phase of synthesis of CeO2/ZnIn2S4 heterojunction composite photocatalyst.
ZnIn2S4 crystal, the Zn atom in the crystal structure is bonded to the S Compared with the agglomerated CeO2 synthesized at room tempera-
atom in a tetrahedral coordination manner, and the In atom is bonded ture, the CeO2 nanoparticles were dispersed on the surface of ZnIn2S4
to the S atom in an octahedral coordination manner [11–15]. Although nanosheets, which confirmed by transmission electron microscopy
ZnIn2S4 has various photocatalytic advantages, it still has the defect (TEM) and scanning electron microscopy (SEM). The photocatalytic
that metal sulfide has been photoetched and its application is limited performance of CeO2/ZnIn2S4 has a significant improvement in pho-
[16,17]. How to overcome the corrosion of S2− becomes the focus of tocatalytic hydrogen production contrasted with pure CeO2 and
research. Research shown that the formation of ZnIn2S4-based Z- ZnIn2S4. Therefore, constructing the 0D/2D CeO2/ZnIn2S4 Z-scheme
scheme photocatalyst can not only improve the photocatalytic activity, heterojunction is beneficial to reduce the recombination rate of

⁎
Corresponding authors.
E-mail addresses: xhliu@[Link] (X. Liu), smchen78@[Link] (S.-m. Chen).

[Link]
Received 19 November 2019; Received in revised form 5 February 2020; Accepted 11 February 2020
Available online 12 February 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
M. Zhang, et al. Applied Surface Science 526 (2020) 145749

Scheme 1. Synthetic route of 0D/2D CeO2/ZnIn2S4 heterojunction.

semiconductor photogenerated electron-hole pairs and improve pho- diffuse reflectance spectroscopy (DRS, Shimadzu UV-2450) was used to
tocatalytic performance. characterize the light absorption properties of samples. The time-re-
solved fluorescence attenuation spectra were measured with a FL3-
2. Experimental TCSPC spectrometer and the excitation light source was a 360 nm laser.
The electron spin resonance (ESR) signals of spin-trapped oxidative
2.1. Materials radicals were obtained on a Bruker model ESR JES-FA300 spectrometer
equipped with a quanta-Ray Nd: YAG laser system as the light source
Zinc chloride (ZnCl2, AR), thioacetamide (CH3CSNH2, TAA, AR) and with a UV-cutoff filter (λ > 420 nm).
ammonia solution (30 wt%) were provided by Sinopharm Chemical
Reagent Co., Ltd (Shanghai, China). Indium(III) chloride tetrahydrate 2.5. Electrochemical test
(InCl3·4H2O, 98%), cerium nitrate hexahydrate (Ce(NO3)3·6H2O, AR)
were purchased from Aladdin. All reagents were used without further Transient photocurrents were executed on a CHI 760E electro-
purification. chemical workstation in standard three-electrode system, consisting of
a sample (0.2 mg of sample loaded on an area of 1.5 cm2 of conductive
2.2. Preparation of ZnIn2S4 nanosheets glass), platinum wire, and saturated Ag/AgCl electrodes as the working,
counter, and reference electrodes, respectively. The transient photo-
The ZnIn2S4 nanosheets was fabricated by mixed solvothermal current test conditions for the samples were 0.5 M Na2SO4 aqueous
method according to previous work [34]. Typically, 0.4 mmol ZnCl2, solution and 300 W xenon lamp with λ > 420 nm filter added.
0.8 mmol InCl3·4H2O and 3.2 mmol TAA added in a 30 mL of ethanol
and water (volume ratio is 1:1) under magnetic stirring 10 min. Sub- 2.6. Photocatalytic H2 evolution
sequently, the mixture was transferred to a 50 mL Teflon-lined stainless
steel autoclave and reacted at 180 °C for 24 h. After the reactor was In photocatalytic hydrogen evolution, 50 mg of CeO2/ZnIn2S4 cat-
naturally cooled to room temperature, it was washed three times by alyst was added to a 200 mL aqueous solution containing 0.35 M Na2S
centrifugation with ethanol and deionized water, and then dried at and 0.25 M Na2SO3. A 300 W Xenon lamp (λ > 420 nm) was used as a
60 °C for 8 h to obtain ZnIn2S4. visible light source. The amount of evolved hydrogen was measured by
a gas chromatograph (GC-1690, boundary, TCD).
2.3. Preparation of CeO2/ZnIn2S4 composites
3. Results and discussion
The CeO2/ZnIn2S4 nanocomposites was synthesized by room tem-
perature hydrolysis. Firstly, the 100 mg as-prepared ZnIn2S4 nanosheets 3.1. Synthetic route of 0D/2D CeO2/ZnIn2S4 heterojunction
were added in 60 mL of ethanol and water (volume ratio is 1:1). Then,
the nanosheets were evenly dispersed in mixture by ultrasonication for Scheme 1 shows the synthetic route of 0D/2D CeO2/ZnIn2S4 het-
30 min. Subsequently, a certain amount of cerium nitrate hexahydrate erojunction. First, the ZnIn2S4 nanosheets prepared by mixture sol-
was added with continuous ultrasonication. After 30 min of ultra- vothermal method. Then added cerium nitrate hexahydrate to the al-
sonication, 50 μL, 100 μL, 300 μL and 500 μL of 30 wt% concentrated cohol-water mixed solution. Since the surface of ZnIn2S4 is negatively
ammonia solution was added dropwise under magnetic stirring. Finally, charged [35], Ce 3+ is adsorbed on the surface of ZnIn2S4 nanosheets
the solution was stirred at room temperature for another 3 h, followed after stirring. When ammonia solution was added, the cerium precursor
by multiple centrifugation with ethanol and deionized water dried for is hydrolyzed to obtain a 0D/2D heterojunction nanocomposites.
8 h under 60 °C to obtain a CeO2/ZnIn2S4 nanocomposites. The amount
of cerium precursor added was 12.6 mg, 25.2 mg, 75.6 mg and 126 mg, 3.2. Characterization of samples
respectively. Thus, the apparent mass ratios of CeO2 and ZnIn2S4 are
5%, 10%, 30% and 50%, respectively (named CZIS-5, CZIS-10, CZIS-30 The samples crystalline structure was characterized by XRD. The
and CZIS-50). The preparation of pure CeO2 was the same as above, CeO2, ZnIn2S4 and different mass ratio CeO2/ZnIn2S4 nanocomposites
without adding ZnIn2S4. XRD patterns were displayed in Fig. 1. As shown in Fig. 1, CeO2, CZIS-5,
CZIS-10, CZIS-30 and CZIS-50 shows 2-theta peaks at values of 28.5°,
2.4. Characterization 33°, 47.5° and 56.3°, which can be assigned to (1 1 1), (2 0 0), (2 2 0)
and (3 1 1) crystallographic planes of cubic CeO2 (JCPDS No:04-0593)
The as-prepared samples were characterized using a D8 Advance X- [36]. In addition to this, the pure ZnIn2S4 and CeO2/ZnIn2S4 nano-
ray diffractometer (Cu K, λ = 1.5406 Å, tube voltage 40 kV, tube cur- composites which performed characteristic peaks of hexagonal phase
rent 40 mA) and scan angle range 2 was 10°−80°. The morphology of ZnIn2S4 (JCPDS No: 89-3963) [37]. It can be seen from the XRD pat-
the samples was characterized by transmission electron microscopy terns that as the compounding amount of CeO2 increases, the (0 0 6)
(TEM), scanning electron microscopy (SEM) and JEM-2100 high re- peak intensity of ZnIn2S4 also decreases, which proves that the com-
solution transmission electron microscopy (HR-TEM). UV–visible pounding of CeO2 and ZnIn2S4 is successful.

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M. Zhang, et al. Applied Surface Science 526 (2020) 145749

0.325 nm and 0.31 nm which corresponds to the (1 0 2) and (1 1 1)

planes of ZnIn2S4 and CeO2, respectively [38–40]. Especially, the good
contact CeO2 with ZnIn2S4 in CeO2/ZnIn2S4 heterojunction, it’s con-
ducive to the transport of charge carriers and the improvement in
photocatalytic performance.
The surface elemental composition and valence state of the Z-
scheme heterojunction can be obtained by XPS analysis. Fig. 4a shows
the XPS spectra for a survey scan of CeO2, ZnIn2S4 and CZIS-10. The
XPS spectra of Ce 3d and O 1 s for CZIS-10 and CeO2 were displayed in
Fig. 4b and c. As shown in Fig. 4b, the Ce 3d spectra can be fitted into
two pairs of peaks {(v0, u0), (v', u')} referred to Ce3+ and three pairs of
peaks {(v, u), (v'', u''), (v ''' , u ''')} belongs to Ce4+. Generally, the Ce3+
peaks of v0, v', u0, u' (880.0, 898.4, 884.3, 902.3 eV) coexist with the
Ce4+ peaks of v, v'', v''', u, u'', u''' (882.4, 896.3, 905.34, 886.92, 900.6,
914.6 eV)[41,42]. For O 1s spectra (Fig. 4c), the peak labeled as O' (ca.
527.6 eV) was attributed to the lattice oxygen in CeO2, and a broad
peak centered at ca. 530.2 eV labeled as O'' was the adsorbed oxygen
(e.g. oxygen in hydroxyl groups) [43,44].
Furthermore, the In 3d, Zn 2p and S 2p spectra for pure ZnIn2S4 and
Fig. 1. XRD patterns of 0D/2D CeO2/ZnIn2S4 heterojunction nanocomposites. CZIS-10 were illustrated in Fig. 4d-f, respectively. Notably, by in-
troducing CeO2 nanoparticles on ZnIn2S4 nanosheets to form CeO2/
The morphology of as-prepared samples was examined by SEM and ZnIn2S4 composite, both the O1s and S2p (2p3/2: 159.8 eV; 2p1/2:
TEM. Fig. 2a and 2b, indicates that the CeO2 crystallized in nano- 160.9 eV) XPS characteristic signals in CeO2 and ZnIn2S4 shifted slightly
particles and ZnIn2S4 in the form of nanosheets, respectively. As the towards lower binding energies (Fig. 4c, f). On the contrary, the binding
CeO2 mass ratio increases, the smooth surface of the ZnIn2S4 nanosheets energies of Zn 2p (2p3/2: 1020.5 eV; 2p1/2: 1043.6 eV) and In 3d (3d5/2:
gradually becomes rougher (Fig. 2c–f), which can be attributed to the 443.3 eV; 3d3/2: 450.8 eV) for the CZIS-10 are higher than the corre-
hydrolysis nucleation of CeO2 after electrostatic adsorption on the sponding values of the pure ZnIn2S4 material {Zn 2p (2p3/2: 1020.4 eV;
surface of nanosheets. In particular, a portion of CeO2 agglomerated 2p1/2: 1043.1 eV) and In3d (3d5/2: 443.2 eV; 3d3/2: 450.7 eV)} (Fig. 4d
particles appeared in CZIS-50. All elements (Zn, In, S, Ce and O) were and 4e) [45–47]. The binding energy shift of heterojunction samples
present in Fig. S1, which indicates that nanocomposites synthesis suc- indicate a strong interaction between ZnIn2S4 nanosheets and CeO2
cessfully. nanoparticles, which facilitates the transfer and separation of photo-
To further illustrate the morphology of the CeO2/ZnIn2S4 hetero- generated carriers to improve carrier utilization [48,49].
junction nanocomposites, the samples was examined by TEM and Fig. 5 shows the optical properties of the fabricated photocatalyst. It
HRTEM. Fig. 3a shows the morphology of CeO2 nanoparticles with can be seen in Fig. 5a, the absorption of visible light of pure CeO2 is
particles size of about 10 nm. Its can be seen in Fig. 3b, the ZnIn2S4 slightly higher than that of ZnIn2S4, which is attributed to the conver-
clear present the nanosheets morphology. When the amount of cerium sion of Ce3+ and Ce4+ species in CeO2 to facilitate electron transfer
nitrate precursor is increased at room temperature, the growth of CeO2 [50]. Furthermore, the CZIS-10 has a higher absorption in the visible
on the surface of ZnIn2S4 nanosheets is also gradually increased (Fig. 3c region than a single photocatalytic material. It's implied that the com-
and Fig. S2). This is consistent with the increase in the roughness of posite heterojunction can enhance the visible light absorption of the
nanosheets in the SEM observation. Interestingly, this 0D CeO2 nano- catalyst, so that the number of photogenerated carriers generated by
particle grows on the 2D ZnIn2S4 nanosheets as a “chess” on the light absorption is increased, which is beneficial to the improvement of
“checkerboard” (simulated Go in Fig. 3c). To further demonstrate the the photocatalytic activity of photocatalyst. The bandgap energy of
existence of the CeO2/ZnIn2S4 heterojunction, HRTEM was used to in- CeO2/ZnIn2S4 heterojunction materials can be calculated by the fol-
vestigate the nanoscale structure. Fig. 3d shows lattice spacing of lowing formula (αhυ)n = k(hυ − Eg). The α, hυ, Eg and k expressed as

Fig. 2. SEM images of (a) pure CeO2 nanoparticles; (b) pure ZnIn2S4 nanosheets; (c-f) CZIS-5, CZIS-10, CZIS-30 and CZIS-50.

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M. Zhang, et al. Applied Surface Science 526 (2020) 145749

Fig. 3. TEM images of (a) pure CeO2 nanoparticles; (b) pure ZnIn2S4 nanosheets; (C) CZIS-10 and (d) HRTEM of CZIS-10.

absorption coefficient, absorption energy, bandgap energy and effective 10 has a more enhanced photocurrent compared to other samples
masses, respectively. Apart from this, the n is a constant related to the (Fig. 7a), suggesting the formation and transfer of photogenerated
electronic transition mode (n = 1/2 or 2 for direct semiconductor or electron-hole pairs in heterostructures. In addition, electrochemical
indirect semiconductor, respectively) [51–53]. impedance spectrum (EIS) of CZIS-10 shows a smaller semicircle in the
The corresponding band gap energies (Eg) of CeO2 and ZnIn2S4 Nyquist plot (Fig. 7b), indicating that the charge transfer resistance in
were estimated to be 2.87 and 2.02 eV (Fig. 5b). Fig. S3 exhibits the heterostructure is lower, allowing light-induced charges to be rapidly
Mott-Schottky plots of CeO2 and ZnIn2S4. The CeO2 and ZnIn2S4 transmitted and separated. These results show that the construction of
showed positive slopes, indicating the n-type semiconductor properties 0D CeO2 and 2D ZnIn2S4 heterostructure can effectively improves the
of CeO2 and ZnIn2S4. The flat band position of n-type semiconductors is photoelectron-hole separation efficiency and enhances the photo-
closer to their CB position. Thus, the extrapolated CB positions of CeO2 catalytic hydrogen production performance.
and ZnIn2S4. are −0.65 and −0.1.48 V (vs Ag/AgCl, pH = 7). These
two potentials are converted to −0.45 and −1.28 V (vs NHE, pH = 7). 3.3. Photocatalytic performance and mechanism study
Combined with the band gap of CeO2 (2.87 eV) and ZnIn2S4 (2.02 eV),
their valence band positions are 2.42 and 0.74 V, respectively. The photocatalytic performance of 0D/2D CeO2/ZnIn2S4 (CZIS)
The separation efficiency of photogenerated carriers can largely heterojunction was investigated for H2 evolution under visible light
affect the photocatalytic performance of the catalytic materials. First, (λ > 420 nm). A mixture solution of 0.25 M Na2SO3 and 0.35 M Na2S
the specific charge carrier dynamics of CeO2/ZnIn2S4, ZnIn2S4 and was used as a sacrificial agent in the reaction system. In Fig. 8a, as can
CeO2 particles are probed by time-resolved photoluminescence (PL) be seen, the CZIS-x (x = 5, 10 and 30) heterojunction composites
spectroscopy (Fig. 6a). The average emission lifetime of ZnIn2S4 and showed improved photocatalytic performance as compared to pristine
CeO2 is shorter than that of CZIS-10. Meanwhile, steady-state PL spectra CeO2 and ZnIn2S4, suggesting that the interfacial effects play a key role
show the significant PL quenching of the heterostructures (Fig. 6b). The in photocatalytic activity [44]. Especially, the CZIS-5 represented the
obvious PL quenching and lifetime decrease indicate the formation of highest hydrogen evolution efficiency (847.42 μmol·g−1·h−1). The hy-
an electron-transfer pathway from ZnIn2S4 to CeO2 in a nonradiative drogen production rate of CZIS-50 is slightly lower than that of pure
quenching manner. ZnIn2S4, which may be due to high CeO2 contents, indicating that the
Further more, the transient photocurrent spectrum shows that CZIS- partial agglomeration of CeO2 reduce photocatalytic activity [54]. The

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M. Zhang, et al. Applied Surface Science 526 (2020) 145749

Fig. 4. (a) XPS spectra for a survey scan and high-resolution XPS spectra of (b) Ce 3d, (c) O 1s in CeO2 and CZIS-10. High-resolution XPS spectra of (d) In 3d, (e) Zn 2p
and (f) S 2p in CZIS-10 and ZnIn2S4.

excellent photocatalytic hydrogen production activity of the CeO2/ indicates that the constructed Z-scheme photocatalyst has excellent
ZnIn2S4 (CZIS) heterojunction composites can be attributed to several photostability.
factors. On the one hand, the Close coupling of CeO2 and ZnIn2S4 fa- Under visible light excitation, the photoinduced electron-hole pairs
cilitates electron transport [55]. On the other hand, the combination of can produce active species (%O2− and %OH), followed by separation and
0D materials and 2D materials is beneficial for materials distribution of transferring on the photocatalyst surface [58,59]. Fig. 8a and b presents
0D, while the plane “bulge” of 0D CeO2 nanoparticles acts to enhance the EPR spectra to detect the photocatalytic active species generated
the photocatalytic activity due to the “tip effect” [56,57]. under visible light illumination. As shown in Fig. 9a, the ESR signal for
Moreover, Fig. 8b displayed stability investigation of photocatalytic DMPO-%O2− can be observed for CeO2, ZnIn2S4 and CZIS-10, which
hydrogen evolution over CZIS-10. No significant decrease in H2 evo- means that %O2− was generated in the reaction system during visible
lution was observed after three cycles of photocatalytic reaction. light irradiation [60]. Moreover, the characteristic peak of DMPO-%OH
Comparing the crystal structure and morphology of the catalytic ma- for pure ZnIn2S4 does not appeared under visible light irradiation
terials before and after the reaction, the XRD (Fig. S4) and TEM (Fig. (Fig. 9b) but four weak peaks were detected for pure CeO2. As for CZIS-
S5) showed no significant change in crystallinity and morphology. This 10 heterojunction composites, the DMPO-%OH signals intensities of %OH

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M. Zhang, et al. Applied Surface Science 526 (2020) 145749

Fig. 5. (a) UV–vis DRS of CeO2, ZnIn2S4 and CZIS-10 and (b) the estimated band gap energies of ZnIn2S4 and CeO2.

Fig. 6. (a) The time-resolved PL spectra and (b) PL spectra of CeO2, ZnIn2S4 and CZIS-10 samples.

Fig. 7. (a) Transient photocurrent spectra and (b) electrochemical impedance spectra (EIS) of CeO2, CZIS-x (x = 5, 10, 30, 50) and ZnIn2S4.

are obviously much higher than those in pure CeO2, which can be at- reaction process, which agrees well with the results of ESR.
tributed to the construction of 0D and 2D heterojunction to improve % According to previously reported literatures [61,62], the potentials
OH production. Besides, the presence of %OH in the CZIS-x photo- of E0(O2/%O2−) and E0(H2O/%OH) are −0.33 V and +2.4 V (vs NHE),
catalyst under visible-light can be measured by PL spectroscopy using respectively. The calculated CB and VB potentials of CeO2 and ZnIn2S4
2-hydroxyterephthalic acid (TA-OH) as a molecular probe [52]. It can is −1.28 to 0.74 V and −0.45 to 2.42 V. The conduction band position
be seen from Fig. S6 that the PL intensity of TAOH is gradually in- of CeO2 is more negative than E0(O2/%O2−) and the valence band is
creasing at 482 nm as the illumination time increases, which indicating more positive than E0(H2O/%OH), which indicates that the %O2− and %
an increase in %OH. NBT can be applied to detect %O2− due to the ex- OH can be produced under visible light irradiation. Meanwhile, the
clusive reaction between %O2− and NBT. As shown in Fig. S7, a distinct ZnIn2S4 conduction band is far negative than E0(O2/%O2−) and the
change of NBT over the CZIS-10 was observed, firmly manifesting that % valence band is much smaller than E0(H2O/%OH), it means that only %
O2− was produced during the CZIS-10 composite photocatalytic O2− can be produced under the same conditions. Particularly, both

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M. Zhang, et al. Applied Surface Science 526 (2020) 145749

Fig. 8. (a) H2 evolution of CZIS-x (x = 5,10,30,50), CeO2 and ZnIn2S4 under visible light irradiation and (b) stability investigation of photocatalytic hydrogen
evolution over CZIS-10.

Fig. 9. ESR spectra of radical adducts trapped by DMPO (a) DMPO-%O2− (b) DMPO-%OH in the CeO2, ZnIn2S4 and CZIS-10 dispersion solution.

DMPO-%O2− and DMPO-%OH high-intensity signals were generated by

CZIS-10 are shown in Fig. 8a and 8b, which demonstrates the successful
construction of the 0D/2D CeO2/ZnIn2S4 (CZIS) Z-scheme heterojunc-
tion and the electrons of CeO2 conduction band can be transferred to
the valence band of ZnIn2S4. On the other hand, it is assumed that CeO2
and ZnIn2S4 are constructed as a type II heterojunction (Fig. S8). Under
visible light excitation, electrons on the conduction band of ZnIn2S4 are
transferred to the conduction band of CeO2 while holes of CeO2 are
transferred to the valence band of ZnIn2S4. CZIS-x composites photo-
catalyst will not be able to produce %OH, and the ability to produce %
O2− will be greatly weakened, which is contrary to results of ESR, NBT
and TA-OH active species capture experiment.
Based on the above discussion and characterizations, a possible
reaction mechanism for photocatalytic H2 evolution over 0D/2D CeO2/
ZnIn2S4 (CZIS) Z-scheme heterojunction under light irradiation is de-
scribed (Fig. 10). Firstly, under visible light excitation, the CeO2 and
ZnIn2S4 electrons can be excited and transfer to their CB, leaving be-
hind holes or electron deficient holes in their VB. Similarly, when
heterojunction formed after close contact between the CeO2 and
ZnIn2S4, the CeO2 conduction band electrons are transferred to valence
band of ZnIn2S4 and then bound with the holes. Finally, the electrons
remaining on the conduction band of ZnIn2S4 participate in the re-
duction reaction to produce H2.

4. Conclusions
Fig. 10. The proposed photocatalytic H2 evolution mechanism for the CeO2/
ZnIn2S4 under visible-light irradiation.
In summary, a CeO2/ZnIn2S4 heterojunction of the Chess-like shape
was used for efficient photocatalytic hydrogen evolution by growing

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M. Zhang, et al. Applied Surface Science 526 (2020) 145749

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