Regulation of Metal‒Sulfur bond polarizability in Zn0.5Cd0.5S for visible-light-driven photocatalytic overall water splitting

doi:10.1016/S1872-2067(26)65099-1

Abstract

Abstract:

The development of efficient and stable visible-light-driven Z-scheme systems for overall water splitting was crucial for solar hydrogen production. However, performance was often limited by photocorrosion of sulfide-based hydrogen evolution photocatalysts and competing, deactivating side reactions involving the redox shuttle. Herein, we construct a robust Z-scheme system by employing a CoP-modified Ni-doped Zn_0.5Cd_0.5S heterojunction with strong interfacial interaction as the HEP, coupled with BiVO₄ as the oxygen evolution photocatalyst. The optimized system exhibited an apparent quantum yield of 4.06% at 420 nm and enabled sustained co-evolution of hydrogen and oxygen at a near-stoichiometric ratio. It also demonstrated outstanding cycling stability. Crucially, it had been demonstrated that the regulation of the internal polarizability of HEP effectively suppressed the competitive reduction of the redox medium and the formation of passivated Prussian blue derivatives on the catalyst surface. This work provides fundamental insights into mitigating the side effects caused by fusion through polarizability regulation.

Key words: Polarizability, Ni doping, Prussian blue derivative

Chen Wang, Yue Zhang, Haolin Luo, Huoshuai Huang, Qianxiang Su, Zhen Ye, Zhi Jiang, Yong Zhu, Mingxia Chen, Zhidong Wei, Wenfeng Shangguan. Regulation of Metal‒Sulfur bond polarizability in Zn_0.5Cd_0.5S for visible-light-driven photocatalytic overall water splitting[J]. Chinese Journal of Catalysis, 2026, 87: 217-229.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65099-1

https://www.cjcatal.com/EN/Y2026/V87/I8/217

Figures/Tables 5

Fig. 1. XRD pattern (a,b), Raman spectra (c), high-resolution Zn 2p (d), Cd 3d (e), S 2p (f), Ni 2p (g), Co 2p (h), and P 2p (i) XPS spectra of as-prepared photocatalysts.

Fig. 2. SEM images of ZCS (a), 5NZCS (b), 6CoP-5NZCS (c), 6CNZCS-400 (d). (e-g) TEM images of 6CNZCS-400. (h) Elemental mapping images for Zn, Cd, S, Ni, Co and P with the overlay image of the mapping images.

Fig. 3. (a) Photocurrent transient spectra. (b) TRPL spectra. (c) EIS Nyquist plots. (d) Transient photocurrent responses. CV curves of aqueous solutions without (e) and containing K3[Fe(CN)6] (f). (g) Anodic currents for [Fe(CN)6]3− reduction. (h) Anodic currents for [Fe(CN)6]4− oxidation.

Fig. 4. (a, b) H2 generation rate of different photocatalysts in the lactic acid aqueous solution. (c) O2 generation rate of different photocatalysts in the K3 [Fe(CN)6] aqueous solution. (d) H2 and O2 yields of Z-type photocatalytic water splitting with different HEPs. (e) Time process of H2 and O2 yields of 6CoP-5NZCS-400 in the Z-scheme system. (f) The content of K and Fe elements on the surface of the catalyst after 10 h reaction. (g) Apparent quantum yields of Z-scheme system using 6CoP-5NZCS-400-Pt-CrOx and BiVO4-IrOx. OWS performance with different Pt (h) and CrOx (i) contents under the Z scheme system.

Fig. 5. (a) The mechanism of Z-type water decomposition reaction. Stability of H2 and O2 production over HEP (6CNZCS) and OER (BiVO4-0.8 wt%IrOx) (b) and HEP (6CNZCS-400) and OER (BiVO4-0.8 wt%IrOx) (c). XRD patterns (d), Raman spectra (e), and IR spectra (f) of different HEPs and OER used in the Z-scheme reaction. The structure of [Fe(CN)6]3− adsorption by the optimized ZCS (g) and 5NZCS-400 (h). Charge difference density of ZCS (i) and 5NZCS-400 (j) after adsorbing ferric cyanide.

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