Efficient photocatalytic hydrogen production by space separation of photo-generated charges from S-scheme ZnIn2S4/ZnO heterojunction

Ziyu Xie; Linjun Xie; Fangfang Qi; Haizhen Liu; Lingyi Meng; Jiangli Wang; Yiming Xie; Jing Chen; Can-Zhong Lu

doi:10.1016/j.jcis.2023.07.032

Efficient photocatalytic hydrogen production by space separation of photo-generated charges from S-scheme ZnIn₂S₄/ZnO heterojunction

J Colloid Interface Sci. 2023 Nov 15;650(Pt A):784-797. doi: 10.1016/j.jcis.2023.07.032. Epub 2023 Jul 7.

Authors

Ziyu Xie¹, Linjun Xie², Fangfang Qi², Haizhen Liu², Lingyi Meng², Jiangli Wang², Yiming Xie³, Jing Chen⁴, Can-Zhong Lu⁵

Affiliations

¹ Engineering Research Center of Environment-Friendly Functional Materials, Ministry of Education, Institute of Materials Physical Chemistry, Huaqiao University, Xiamen 361021, China; CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China; Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare-earth Materials, Haixi Institutes, Chinese Academy of Sciences, Xiamen 361021, China.
² CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China; Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare-earth Materials, Haixi Institutes, Chinese Academy of Sciences, Xiamen 361021, China.
³ Engineering Research Center of Environment-Friendly Functional Materials, Ministry of Education, Institute of Materials Physical Chemistry, Huaqiao University, Xiamen 361021, China. Electronic address: ymxie@hqu.edu.cn.
⁴ CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China; Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare-earth Materials, Haixi Institutes, Chinese Academy of Sciences, Xiamen 361021, China. Electronic address: jing.chen@fjirsm.ac.cn.
⁵ CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China; Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare-earth Materials, Haixi Institutes, Chinese Academy of Sciences, Xiamen 361021, China; University of Chinese Academy of Sciences, Beijing, 100049, China. Electronic address: czlu@fjirsm.ac.cn.

PMID: 37441971
DOI: 10.1016/j.jcis.2023.07.032

Abstract

ZnIn₂S₄/ZnO heterostructures have been achieved by a simple in-situ growth solvothermal method. Under full spectrum irradiation, the optimal photocatalyst 2ZnIn₂S₄/ZnO exhibits H₂ evolution rate of 13,638 (water/ethanol = 1:1) and 3036 (water) μmol·g^-1h^-1, which is respectively 4 and 5 times higher than that of pure ZnIn₂S₄. In situ illumination X-ray photoelectron spectroscopy (ISI-XPS) analysis and density functional theory (DFT) calculations show that the electrons of ZnIn₂S₄ are removed to ZnO through hybridization and form an internal electric field between ZnIn₂S₄ and ZnO. The optical properties of the catalyst and the effect of internal electric field (IEF) can increase photo-generated electrons (e^-)-holes (h⁺) transport rate and enhance light collection, resulting in profitable photocatalytic properties. The photoelectrochemical and EPR results show that a stepped (S-scheme) heterojunction is formed in the ZnIn₂S₄/ZnO redox center, which greatly promotes separation of e^--h⁺ pairs and efficient H₂ evolution. This research offers an effective method for constructing an efficient S-Scheme photocatalytic system for H₂ evolution.

Keywords: Full spectrum irradiation; Photocatalytic hydrogen evolution (PHE); S-scheme photocatalytic; ZnIn(2)S(4)/ZnO heterojunction.