g-C3N4 as ballistic electron transport "Tunnel" in CsPbBr3-based ternary photocatalyst for gas phase CO2 reduction

Dong Li; Renyi Li; Yizhou Zhao; Kaixuan Wang; Ke Fan; Wei Guo; Qi Chen; Yujing Li

doi:10.1016/j.jcis.2024.03.193

g-C₃N₄ as ballistic electron transport "Tunnel" in CsPbBr₃-based ternary photocatalyst for gas phase CO₂ reduction

J Colloid Interface Sci. 2024 Jul 15:666:66-75. doi: 10.1016/j.jcis.2024.03.193. Epub 2024 Apr 3.

Authors

Dong Li¹, Renyi Li², Yizhou Zhao¹, Kaixuan Wang¹, Ke Fan³, Wei Guo⁴, Qi Chen¹, Yujing Li⁵

Affiliations

¹ Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, Experimental Center of Advanced Materials, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, PR China.
² Key Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement (MOE), Frontiers Science Center for High Energy Material (MOE), State Key Laboratory of Explosion Science and Technology, School of Physics, Beijing Institute of Technology, Beijing 100081, PR China.
³ State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, Institute for Energy Science and Technology, Dalian University of Technology, Dalian 116024, PR China.
⁴ Key Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement (MOE), Frontiers Science Center for High Energy Material (MOE), State Key Laboratory of Explosion Science and Technology, School of Physics, Beijing Institute of Technology, Beijing 100081, PR China. Electronic address: weiguo7@bit.edu.cn.
⁵ Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, Experimental Center of Advanced Materials, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, PR China. Electronic address: yjli@bit.edu.cn.

PMID: 38583211
DOI: 10.1016/j.jcis.2024.03.193

Abstract

Perovskite CsPbBr₃ quantum dot shows great potential in artificial photosynthesis, attributed to its outstanding optoelectronic properties. Nevertheless, its photocatalytic activity is hindered by insufficient catalytic active sites and severe charge recombination. In this work, a CsPbBr₃@Ag-C₃N₄ ternary heterojunction photocatalyst is designed and synthesized for high-efficiency CO₂ reduction. The CsPbBr₃ quantum dots and Ag nanoparticles are chemically anchored on the surface of g-C₃N₄ sheets, forming an electron transfer tunnel from CsPbBr₃ quantum dots to Ag nanoparticles via g-C₃N₄ sheets. The resulting CsPbBr₃@Ag-C₃N₄ ternary photocatalyst, with spatial separation of photogenerated carriers, achieves a remarkable conversion rate of 19.49 μmol·g^-1·h^-1 with almost 100 % CO selectivity, a 3.13-fold enhancement in photocatalytic activity as compared to CsPbBr₃ quantum dots. Density functional theory calculations reveal the rapid CO₂ adsorption/activation and the decreased free energy (0.66 eV) of *COOH formation at the interface of Ag nanoparticles and g-C₃N₄ in contrast to the g-C₃N₄, leading to the excellent photocatalytic activity, while the thermodynamically favored CO desorption contributes to the high CO selectivity. This work presents an innovative strategy of constructing perovskite-based photocatalyst by modulating catalyst structure and offers profound insights for efficient CO₂ conversion.

Keywords: Carbon dioxide fixation; Graphitic carbon nitride; Halide perovskite; Photocatalysis; Quantum dots.