Perovskite CsCuClxBr3-x Microcrystals: Band Structure, Photochemical Stability, and Photocatalytic Properties

Shuang Chao Tang; Yan Jie Li; Jing Yang; Ting Zhao; Jie Tian; Yan Jie Wang; Zhuo Yu Ji; Yu Li; Yi Tao Dai; Tao He; Yong-Wei Zhang; Alexei V Emeline; Qi Pang; Detlef W Bahnemann; Jia Hong Pan

doi:10.1002/cssc.202402094

Perovskite CsCuCl_xBr_3-x Microcrystals: Band Structure, Photochemical Stability, and Photocatalytic Properties

ChemSusChem. 2025 May 5;18(9):e202402094. doi: 10.1002/cssc.202402094. Epub 2025 Jan 31.

Authors

Shuang Chao Tang^{1

2}, Yan Jie Li^{1

2}, Jing Yang³, Ting Zhao⁴, Jie Tian², Yan Jie Wang⁵, Zhuo Yu Ji¹, Yu Li¹, Yi Tao Dai^{6

7}, Tao He⁵, Yong-Wei Zhang³, Alexei V Emeline⁸, Qi Pang⁹, Detlef W Bahnemann^{10

11}, Jia Hong Pan^{1

2}

Affiliations

¹ College of Environmental Science and Engineering, North China Electric Power University, Beijing, 102206, China.
² State Key Laboratory of Featured Metal Materials and Life-Cycle Safety for Composite Structures, School of Resources, Environment and Materials, Guangxi University, Nanning, 530004, Guangxi, China.
³ ASTAR, Inst High Performance Comp IHPC, 1 Fusionopolis Way 16-16 Connexis, Singapore, 138632, Singapore.
⁴ National Engineering Laboratory for VOCs Pollution Control Material & Technology, University of Chinese Academy of Sciences, Beijing, 101408, China.
⁵ CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing, 100190, China.
⁶ Key Laboratory of Precision and Intelligent Chemistry, School of Nano Science and Technology, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, 230026, Anhui, China.
⁷ Sustainable Energy and Environmental Materials Innovation Center, Suzhou Institute for Advanced Research, University of Science and Technology of China, Suzhou, 215123, Jiangsu, China.
⁸ Laboratory "Photonics of Crystals", Saint Petersburg State University, Peterhof, Saint, Petersburg, 198504, Russia.
⁹ College of Chemistry and Chemical Engineering of Guangxi University, Nanning, 530004, China.
¹⁰ Institut für Technische Chemie, Leibniz Universität Hannover, D-30167, Hannover, Germany.
¹¹ Laboratory "Photoactive Nanocomposite Materials", Saint Petersburg State University, Peterhof, Saint, Petersburg, 198504, Russia.

PMID: 39714848
DOI: 10.1002/cssc.202402094

Abstract

Although Pb-based metal halide perovskites (MHPs) have excellent photoelectric characteristics, its toxicity remains a limiting factor for its widespread application. In the paper, a series of CsCuCl_xBr_3-x (x=1, 2, 3) MHPs microcrystals were developed and their hydrogen evolution performance in ethanol and HX (X=Cl, Br) were also studied. Among them, CsCuCl₃ microcrystals exhibit high hydrogen evolution performance in both HX and ethanol, attributed to its longest average lifetime and suitable band structure. Additionally, the effect of different sacrificial agents on photocatalytic hydrogen production indicates that the photogenerated hole (h⁺) plays a critical role. MHPs can maintain a dynamic equilibrium of dissolution and precipitation in HX saturated aqueous solutions, thereby overcoming the stability issues associated with perovskite. The phase transition of CsCuCl_xBr_3-x during photocatalysis is monitored by XRD technique. CsCuCl₃ shows high stability in saturated HCl aqueous solution, and excellent photocatalytic performance with a hydrogen production rate of CsCuCl₃ microcrystals reached 103.98 μmol g^-1 at 210 min. Our study expands the development prospects of CsCuCl₃ in the field of photocatalytic solar fuel generation.

Keywords: CsCuCl3; MHPs; hydrogen evolution; lead-free perovskites; photocatalysis.

Abstract

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