title: Defect Engineering and Phase Junction Architecture of Wide-Bandgap ZnS for Conflicting Visible Light Activity in Photocatalytic H₂ Evolution.
abstract: ZnS is among the superior photocatalysts for H2 evolution, whereas the wide bandgap restricts its performance to only UV region. Herein, defect engineering and phase junction architecture from a controllable phase transformation enable ZnS to achieve the conflicting visible-light-driven activities for H2 evolution. On the basis of first-principle density functional theory calculations, electron spin resonance and photoluminescence results, etc., it is initially proposed that the regulated sulfur vacancies in wurtzite phase of ZnS play the key role of photosensitization units for charge generation in visible light and active sites for effective electron utilization. The symbiotic sphalerite-wurtzite phase junctions that dominate the charge-transfer kinetics for photoexciton separation are the indispensable configuration in the present systems. Neither ZnS samples without phase junction nor those without enough sulfur vacancies conduct visible-light photocatalytic H2 evolution, while the one with optimized phase junctions and maximum sulfur vacancies shows considerable photocatalytic activity. This work will not only contribute to the realization of visible light photocatalysis for wide-bandgap semiconductors but also broaden the vision on the design of highly efficient transition metal sulfide photocatalysts.
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Zhibin
authors.initials: Z
authors.lastname: Fang
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Sunxian
authors.initials: S
authors.lastname: Weng
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Xinxin
authors.initials: X
authors.lastname: Ye
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Wenhui
authors.initials: W
authors.lastname: Feng
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Zuyang
authors.initials: Z
authors.lastname: Zheng
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Meiliang
authors.initials: M
authors.lastname: Lu
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Sen
authors.initials: S
authors.lastname: Lin
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Xianzhi
authors.initials: X
authors.lastname: Fu
authors.affiliation: Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P. R. China.
authors.forename: Ping
authors.initials: P
authors.lastname: Liu
keywords: ZnS; first principle DFT; phase junction; sulfur vacancy; visible light photocatalysis