Step-scheme ZnO@ZnS hollow microspheres for improved photocatalytic H2 production performance

doi:10.1016/S1872-2067(21)63889-5

Abstract

Abstract:

Constructing a step-scheme heterojunction at the interface between two semiconductors is an efficient way to optimize the redox ability and accelerate the charge carrier separation of a photocatalytic system for achieving high photocatalytic performance. In this study, we prepared a hierarchical ZnO@ZnS step-scheme photocatalyst by incorporating ZnS into the outer shell of hollow ZnO microspheres via a simple in situ sulfidation strategy. The ZnO@ZnS step-scheme photocatalysts had a large surface area, high light utilization capacity, and superior separation efficiency for photogenerated charge carriers. In addition, the material simulation revealed that the formation of the step-scheme heterojunction between ZnO and ZnS was due to the presence of the built-in electric field. Our study paves the way for design of high-performance photocatalysts for H₂ production.

Key words: ZnO@ZnS, Hollow microspheres, Step-scheme heterojunction, Photocatalytic H₂ production

Jie Jiang, Guohong Wang, Yanchi Shao, Juan Wang, Shuang Zhou, Yaorong Su. Step-scheme ZnO@ZnS hollow microspheres for improved photocatalytic H₂ production performance[J]. Chinese Journal of Catalysis, 2022, 43(2): 329-338.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63889-5

https://www.cjcatal.com/EN/Y2022/V43/I2/329

Figures/Tables 11

Fig. 1. Schematic of the synthesis of ZnO@ZnS composite hollow microspheres.

Fig. 2. XRD patterns of ZnO (a), ZOS-0.05 (b), ZOS-0.1 (c), ZOS-0.15 (d), and ZOS-0.2 (e) samples.

Fig. 3. SEM images of ZnO (a) and ZOS-0.15 (b); TEM (c) and HRTEM (d) images of ZOS-0.15; (e) EDS elemental mappings of Zn, O, and S in ZOS-0.15.

Table 1 Physical properties of the as-prepared samples.

Sample	A_BET (m² g^-1)	Pore size (nm)	Pore volume (cm³ g^-1)
ZnO	9.6	13.0	0.03
ZOS-0.05	42.8	10.9	0.12
ZOS-0.1	58.4	8.6	0.13
ZOS-0.15	63.0	7.7	0.12
ZOS-0.2	60.6	7.8	0.12

Fig. 4. N2 adsorption-desorption isotherms (a) and the corresponding pore size distribution curves (b) of ZnO, ZOS-0.05, ZOS-0.1, ZOS-0.15, and ZOS-0.2.

Fig. 5. (a) XPS survey spectra of the ZnO, ZnS, and ZOS-0.15 samples; High-resolution XPS spectra of Zn 2p (b), O 1s (c), and S 2p (d) in the ZOS-0.15 samples.

Fig. 6. UV-visible diffuse reflectance spectra (a), band gap structures (b), Mott-Schottky curves (500 Hz) (c), and schematic illustrations (d) of the energy-band structures of ZnO and ZnS.

Fig. 7. (a) Comparison of photocatalytic hydrogen production activity of all samples; (b) Cycling H2 production stability for the ZOS-0.15 sample; (c) Photocatalytic hydrogen production activity of ZOS-0.15 using different sacrificial reagents.

Fig. 8. (a) PL spectra of pure ZnO and ZnO@ZnS composites under 265 nm excitation; (b) Transient photocurrent responses; (c) Nyquist plots of pure ZnO and ZnO@ZnS composites in 1 M Na2SO4 (pH = 7) under the illumination of UV-LED; (d) Change in PL spectra changes at different times for the ZOS-0.15 sample under illumination in a mixed solution with TA (0.5 mM) and NaOH (2 mM).

Fig. 9. Calculated electrostatic potentials for (002) face of ZnO (a) and (111) face of ZnS (b).

Fig. 10. Proposed step-scheme photocatalytic mechanism for the ZnO@ZnS hollow microspheres.

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Step-scheme ZnO@ZnS hollow microspheres for improved photocatalytic H₂ production performance

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