Synthesis of Double Trivalent Perovskite Quantum Dots Cs3BiSbX9 (X = Cl, Br, I) for Efficient CO2 Photoreduction Performance

Jie Tian; Zhijian Wang; Yaqin Hou; Yatao Yang; Haijun Chen; Zhanggen Huang

doi:10.1002/smll.202401301

Synthesis of Double Trivalent Perovskite Quantum Dots Cs₃BiSbX₉ (X = Cl, Br, I) for Efficient CO₂ Photoreduction Performance

Small. 2024 Apr 26:e2401301. doi: 10.1002/smll.202401301. Online ahead of print.

Authors

Jie Tian^{1

2}, Zhijian Wang^{2

3}, Yaqin Hou^{1

2}, Yatao Yang^{1

2}, Haijun Chen⁴, Zhanggen Huang^{1

2

5}

Affiliations

¹ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi, 030001, China.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi, 030001, China.
⁴ Tianjin Key Laboratory of Optoelectronic Thin Film Devices and Technology, College of Electronic Information and Optical Engineering, Nankai University, Tianjin, 300350, China.
⁵ Dalian National Laboratory for Clean Energy, Dalian, Liaoning, 116023, China.

PMID: 38671565
DOI: 10.1002/smll.202401301

Abstract

Non-toxic Bi halides have great potential in the field of CO₂ photoreduction, but strong charge localization limits their charge separation and transfer. In this study, a series of Cs₃BiSbX₉ (X = Cl, Br, I) perovskite quantum dots (PQDs) are synthesized by antisolvent recrystallization at room temperature, in which Cs₃BiSbBr₉ PQDs has high selectivity (94.51%) and yield (15.32 µmol g^-1 h^-1) of CO₂ to CO. In situ DRIFTS and theoretical calculations suggest that the surface charge can be tailored by halogen modulation, allowing for the customization of intermediate species. The Bi─Br─Sb symmetric charge distribution induced by the halogen Br promotes the formation of b─HCOO and reduces the reaction energy barrier of the rate-limiting step, while the weak electronegativity of Cl and the high electronegativity of I leads to m─HCOO and ─COOH production, which are detrimental to CO generation. This work provides new insights into the design of halide alloy perovskites for CO₂ photoreduction.

Keywords: carbon dioxide; halogen; perovskite; photoreduction.

Abstract

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