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Research Article

Vacancy-engineering-mediated activation of excitonic transition for boosting visible-light-driven photocatalytic oxidative coupling of amines

Wenxiu Liu1, Lei Li1, Peng Zhang1, Manqin Guan1, Ming Zuo1, Yinhua Zhao1, Hui Wang1,2(), Xiaodong Zhang1,2(), Yi Xie1,2()
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Institute of Energy, Hefei Comprehensive National Science Center, Hefei 230031, China
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Using bismuth oxybromide (BiOBr) as a model system, the light absorption cut-off edge could be effectively extended up to 500 nm by introducing Bi vacancies. And the broadening of light absorption could be attributed to Bi-vacancy-induced activation of forbidden excitonic transition.

Abstract

The light absorption properties of semiconductor-based photocatalysts to a large extent determine the relevant catalytic performance. Traditional strategies in broadening the light absorption range are usually accompanied with unfavorable changes in redox ability and dynamics of photoinduced species that would confuse the comprehensive optimization. In this work, we propose a nontrivial excitonic transition regulation strategy for gaining sub-bandgap light absorption in low-dimensional semiconductor-based photocatalysts. Using bismuth oxybromide (BiOBr) as a model system, we highlight that the light absorption cut-off edge could be effectively extended up to 500 nm by introducing Bi vacancies. On the basis of theoretical simulations and spectroscopic analyses, we attributed the broadening of light absorption to the promotion of excitonic transition that is generally forbidden in pristine BiOBr system, associated with Bi-vacancy-induced excited-state symmetry breaking. In addition, Bi vacancy was demonstrated to implement negligible effects on other photoexcitation properties like excited-state energy-level profiles and kinetics. Benefiting from these features, the defective sample exhibits a notable advantage in gaining visible-light-driven photocatalytic reactions.

Keywords

semiconductor-based photocatalystslight absorptionvacancy engineeringexcitonic transitionselective oxidation

Electronic Supplementary Material

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Nano Research
Volume 16 Issue 11,
November 2023
Pages 12655-12661
DOI: 10.1007/s12274-023-5941-2
Cite this article:
Liu W, Li L, Zhang P, et al. Vacancy-engineering-mediated activation of excitonic transition for boosting visible-light-driven photocatalytic oxidative coupling of amines. Nano Research, 2023, 16(11): 12655-12661. https://doi.org/10.1007/s12274-023-5941-2
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