Ru3+-doped lead-free perovskite Cs3Bi2Br9 for photocatalytic selective oxidation of sulfides to sulfoxides using trace water as an oxygen source

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis Pub Date : 2025-01-07 DOI:10.1016/j.jcat.2025.115945

Qiangwen Fan, Dawei Liu, Zhaohong Liao, Debo Wu, Zongbo Xie, Haibo Zhu, Zhanggao Le

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引用次数: 0

Abstract

It remains great challenges to keep long-term photocatalytic performance of metal halide perovskites (MHPs) under oxygen-rich and moisture environments owing to their intrinsic lability to these conditions. Herein, we employed high oxyphilic trivalent ruthenium ions (Ru³⁺) as oxygen atom anchors to dope into the lattice of lead-free perovskite Cs₃Bi₂Br₉ (CBB), aiming to enhance the structural stability by inhibiting the penetration of reactive oxygen species (ROS) and water (H₂O) into CBB. Besides, the photocatalytic performance of Ru³⁺-doped CBB (Ru-CBB) for the selective oxidation of sulfides was evaluated in the presence of O₂ and H₂O. Series of sulfides (38 examples) were converted into corresponding sulfoxides with excellent yields and the Ru-CBB were recycled at least 5 times without the change of crystalline structure. The enhanced photocatalytic activity of Ru-CBB, compared to the pristine CBB, can be attributed to its more positive valence band position and more efficient formation of ROS. Mechanism studies revealed that two reaction pathways, predominated by H₂O and ROS respectively, were involved in the titled transformation. In the former, H₂O served as an essential oxygen source for the formation of sulfoxides as established by isotope labelling experiment.

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.