Efficient Photocatalytic Two-Electron Halide Oxidation over p-Block Metal Bi- and Sb-Based Catalysts

IF 13.1 1区 化学 Q1 CHEMISTRY, PHYSICAL
Ruofan Li, Ling Zhang*, Xin Qin, Shenyan Xu, Chunyu Che, Wenjing Wang, Chuanqi Zhang and Wenzhong Wang*, 
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Abstract

Halide (X, X = Cl, Br) oxidation provides a promising alternative to water oxidation reaction (WOR) due to the feasibility of the reaction, richness of the reactants, and extensive application of the products (X2, HOX, and OX) for photocatalysis. Bismuth oxyhalide (BiOX) is still the most efficient photocatalyst applied for halide oxidation ever reported, but relative reaction mechanisms remain understudied, and the reactivity needs to be optimized. Herein, Sb(III) is introduced into BiOX (Sb-BiOX), and by involving itself in the cycle of reactive oxygen species, the reaction was significantly boosted, affording HClO up to 482.5 μM within 30 min. Endowed by the favorable 2e redox couple due to their unique s2 electron configuration of Bi(III) and Sb(III), the oxidation of X was performed in a 2e manner over Sb-BiOX. Because of the introduction of Sb(III), high-valent metal (M(V), M = Sb, Bi) and metal peroxide (M-OOH) could be generated more expeditiously and more easily in situ under light irradiation, which are revealed to be the key oxidizing species for halide oxidation. This work provides an in-depth understanding of promoting the photocatalytic oxidation of halide and could offer more inspiring photocatalytic paradigms for energy-related small-molecule conversion reactions that rely on the WOR half-reaction.

Abstract Image

p嵌段金属铋基和sb基催化剂上的高效光催化双电子卤化物氧化
卤化物(X -, X = Cl, Br)氧化由于其反应的可行性、反应物的丰富性以及产物(X2, HOX, OX -)在光催化方面的广泛应用,为水氧化反应(WOR)提供了一种很有前途的替代方法。氧化卤化物铋(BiOX)是目前报道的卤化物氧化最有效的光催化剂,但其反应机理仍有待进一步研究,反应活性有待进一步优化。在此,Sb(III)被引入到BiOX (Sb-BiOX)中,通过参与活性氧的循环,该反应被显著促进,在30分钟内提供高达482.5 μM的HClO。由于Bi(III)和Sb(III)独特的s2电子构型赋予了有利的2e -氧化还原对,X -在Sb-BiOX上以2e -方式氧化。由于引入了Sb(III),在光照射下可以更快速、更容易地原位生成高价金属(M(V), M = Sb, Bi)和金属过氧化物(M- ooh),这是卤化物氧化的关键氧化物质。该研究为促进卤化物的光催化氧化提供了深入的理解,并为依赖WOR半反应的能量相关小分子转化反应提供了更有启发性的光催化范式。
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来源期刊
ACS Catalysis
ACS Catalysis CHEMISTRY, PHYSICAL-
CiteScore
20.80
自引率
6.20%
发文量
1253
审稿时长
1.5 months
期刊介绍: ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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