Issue 22, 2023

Synergetic microstructure engineering by induced ZB/WZ twin boundaries and S vacancies in a Zn0.5Cd0.5S-based S-scheme photocatalyst for highly efficient photocatalytic hydrogen production

Abstract

Surface-abundant active sites, rapid charge transport and associated prolonged electron lifetime are vital factors that determine efficient photocatalysis. A series of different Zn0.5Cd0.5S solid solutions, including single crystalline Zn0.5Cd0.5S (ZCS), single crystalline Zn0.5Cd0.5S with S vacancies (ZCS-V), twin structured-Zn0.5Cd0.5S (T-ZCS) and twin-structure Zn0.5Cd0.5S with S vacancies (T-ZCSv) were successfully prepared in the present work by manipulating the conditions of the hydrothermal reaction. Experimental results confirm that the optimized T-ZCSv photocatalyst that possesses a hexagonal wurtzite/zinc blende (WZ/ZB) twin structure and rich-surface S vacancies exhibits an excellent photocatalytic hydrogen production efficiency of approximately 551.74 μmol h−1. The outstanding performance of the optimized T-ZCSv is attributed to the prolonged electron lifetime and effectively facilitated separation and migration of charge carriers. These are provided by the periodically aligned WZ/ZB interfacial homojunctions that form the S-scheme staggered energy band structure across the junction and abundant S vacancies that serve as electron trapping sites in the T-ZCSv. Furthermore, T-ZCSv are uniformly dispersed on 2-methylimidazole zinc salt [zeolitic imidazolate framework-8 (ZIF-8 polyhedron)], which not only could inhibit the aggregation of T-ZCSv but also expose more active sites for photocatalytic-redox reactions. Finally, a possible charge separation and transfer mechanism explaining the optimum activity of the outperforming sample is proposed on the basis of the results obtained from a range of investigation methods [scanning electron microscopy and energy-dispersive spectroscopy (SEM-EDS), transmission electron microscopy and high-resolution transmission electron microscopy (TEM/HRTEM), X-ray diffraction (XRD) technique, ultraviolet-visible (UV-vis) diffuse reflection spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy]. This study demonstrates the development of a structurally unique Zn0.5Cd0.5S (with twin structure and S vacancies) and a Zn0.5Cd0.5S-based metal–organic framework (MOF) for photocatalytic applications.

Graphical abstract: Synergetic microstructure engineering by induced ZB/WZ twin boundaries and S vacancies in a Zn0.5Cd0.5S-based S-scheme photocatalyst for highly efficient photocatalytic hydrogen production

Supplementary files

Article information

Article type
Research Article
Submitted
26 juin 2023
Accepted
19 sept. 2023
First published
21 sept. 2023

Inorg. Chem. Front., 2023,10, 6683-6700

Synergetic microstructure engineering by induced ZB/WZ twin boundaries and S vacancies in a Zn0.5Cd0.5S-based S-scheme photocatalyst for highly efficient photocatalytic hydrogen production

Y. Zhang, D. Lu, Z. Wang, M. Zhou, K. K. Kondamareddy, J. Li, H. Fan, D. Cao and W. Ho, Inorg. Chem. Front., 2023, 10, 6683 DOI: 10.1039/D3QI01187A

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