journal article·2024-04-12

Modulating Adsorption–Redox Sites and Charge Separation of Cs3Bi2Br9–x@AgBr Core–Shell Heterostructure for Selective Toluene Photooxidation

Biao Zhou, Kezhou Fan, Yanan Chong, Shuang Xu, Jianwu Wei, Jiake Wei, Aleksandr A. Sergeev, Kam Sing Wong, Tan Li, Guangxu Chen, Daiqi Ye, Keyou Yan

ACS Energy Letters· Volume 9· Issue 4
Publisher page

Abstract

Constructing vacancy-decorated heterojunction photocatalysts is a feasible strategy for highly efficient photooxidation of toluene to benzaldehyde. However, poor interface interaction and vacancy-triggered mismatched redox kinetics seriously impede photocatalytic activity improvement. Herein, a chemically bonded Cs 3 Bi 2 Br 9– x @AgBr core–shell heterojunction with unified adsorption-redox sites is fabricated via an in-situ light-assisted Ag + insertion method. Experiments and theoretical calculations demonstrate that the type-II band alignment with interfacial Bi–Br–Ag bonds boosts the charge separation. Moreover, because of the greater oxygen adsorption energy and the steric-hindrance effect of the AgBr shell, the preferred adsorption site of O 2 is modulated from Br vacancy (V Br, trapping holes) to its corresponding reduction site (AgBr, gathering electrons), thereby ensuring V Br -enhancing toluene adsorption/oxidation on Cs 3 Bi 2 Br 9 . Therefore, Cs 3 Bi 2 Br 9– x @AgBr exhibits an improved benzaldehyde production rate of 5.61 mmol g –1 h –1 (selectivity: 91%), outperforming pure Cs 3 Bi 2 Br 9 by a factor of 6. This work underlines the importance of the rational design of vacancy-decorated heterointerface and redox sites at the atomic level in photocatalysis.
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Research context

OpenAlex topics: Perovskite Materials and Applications · Advanced Photocatalysis Techniques · Polyoxometalates: Synthesis and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

School of Environment and Energy, State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, South China University of Technology, Guangzhou 510000, Guangdong China

Department of Physics and William Mong Institute of Nano Science and Technology, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon 999077, Hong Kong China

School of Chemistry and Chemical Engineering, Guangxi Key Laboratory of Electrochemical Energy Materials, Guangxi University, Nanning 530004, Guangxi China

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023 Dalian, China

Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, People’s Republic of China

Funding

Science and Technology Planning Project of Guangdong Province · National Key Research and Development Program of China · National Natural Science Foundation of China · International Training Program for Young Talents of Guangdong Province

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