A hollow core-shell TiO2 /NiCo2 S4 Z-Scheme heterojunction photocatalyst for efficient hydrogen evolution

doi:10.1016/j.jmst.2024.06.016

Abstract

Abstract: Constructing heterojunctions have received significant attention in photocatalysis because of their effi-cient separation of photogenerated carriers and improving light utilization efficiency. Bimetallic sulfides (e.g. NiCo₂ S₄) are applied in electrocatalysis and supercapacitors that can be coupled with TiO₂ to form a heterojunction. Owing to the staggered energy band arrangement between TiO₂ and NiCo₂ S₄, the es-tablishing of a Z-scheme heterojunction between them is expected to enhance the carrier separation effi-ciency and reduce the sulfide photo-corrosion. However, the application of NiCo₂ S₄ in photocatalysis and studies on the mechanism of the TiO₂ /NiCo₂ S₄ Z-scheme heterojunction have seldom been reported. In this work, we obtained a hollow core-shell TiO₂ /NiCo₂ S₄ Z-scheme photocatalyst through a solvothermal method for photocatalytic hydrogen evolution (PHE). The PHE rate of the optimized TiO₂ /NiCo₂ S₄-0.3 is 8.55 mmol g^-1 h^-1, approximately 34 times higher than pure TiO₂, 94 times higher than pure NiCo₂ S₄. The remarkable photocatalytic activity can be ascribed to the hollow structure and the in-situ constructed Z-scheme heterojunction. The photogenerated charge transfer mechanism is revealed by hydroxyl radical trapping experiments and electron paramagnetic resonance (EPR) characterization. The in-situ construc-tion of the Z-scheme heterojunction not only enhances the efficiency of separating the photogenerated carriers but also reduces the photo-corrosion of NiCo₂ S₄. This study proposes an effective strategy for the design of TiO₂-based Z-scheme heterojunctions and the application of NiCo₂ S₄ in photocatalysis.

Key words: TiO₂, NiCo₂ S₄, Hollow core-shell, Z-Scheme Heterojunction, Photocatalytic H₂ evolution

Mao-Jin Ran, Meng Wang, Zhi-Yi Hu, Yi-Fu Huang, Lin-Dong Wang, Lu Wu, Man-Man Yuan, Jian Zhang, Bei Li, Gustaaf Van Tendeloo, Yu Li, Bao-Lian Su. A hollow core-shell TiO₂ /NiCo₂ S₄ Z-Scheme heterojunction photocatalyst for efficient hydrogen evolution[J]. J. Mater. Sci. Technol., 2025, 212: 182-191.

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A hollow core-shell TiO₂ /NiCo₂ S₄ Z-Scheme heterojunction photocatalyst for efficient hydrogen evolution

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