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揭示无铅锑溴化铅钙钛矿在光催化C(sp³)-H键活化中的A位效应

Revealing the A-Site Effect of Lead-Free A Sb Br Perovskite in Photocatalytic C(sp )-H Bond Activation.

作者信息

Zhang Zhenzhen, Yang Yuying, Wang Yingying, Yang Lanlan, Li Qi, Chen Langxing, Xu Dongsheng

机构信息

Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.

Research Center for Analytical Sciences, College of Chemistry, Tianjin Key Laboratory of Biosensing and Molecular Recognition, State Key Laboratory of Medicinal Chemical Biology, Nankai University, Tianjin, 300071, China.

出版信息

Angew Chem Int Ed Engl. 2020 Oct 5;59(41):18136-18139. doi: 10.1002/anie.202005495. Epub 2020 Aug 13.

Abstract

The lead-free halide perovskite A Sb Br is utilized as a photocatalyst for the first time for C(sp )-H bond activation. A Sb Br nanoparticles (A Sb Br NPs) with different ratios of Cs and CH NH (MA) show different photocatalytic activities for toluene oxidation and the photocatalytic performance is enhanced when increasing the amount of Cs. The octahedron distortion caused by A-site cations can change the electronic properties of X-site ions and further affect the electron transfer from toluene molecules to Br sites. After the regulation of A-site cations, the photocatalytic activity is higher with A Sb Br NPs than that with classic photocatalysts (TiO , WO , and CdS). The main active species involved in photocatalytic oxidation of toluene are photogenerated holes (h ) and superoxide anions ( O ). The octahedron distortion by A-site cations affecting photocatalytic activity remains unique and is also a step forward for understanding more about halide-perovskite-based photocatalysis. The relationship between octahedron distortion and photocatalysis can also guide the design of new photocatalytic systems involving other halide perovskites.

摘要

无铅卤化物钙钛矿ASbBr首次被用作光催化剂用于C(sp³)-H键活化。具有不同Cs和CH₃NH₃(MA)比例的ASbBr纳米颗粒(ASbBr NPs)对甲苯氧化表现出不同的光催化活性,并且当增加Cs的量时光催化性能增强。由A位阳离子引起的八面体畸变可以改变X位离子的电子性质,并进一步影响从甲苯分子到Br位的电子转移。在调节A位阳离子后,ASbBr NPs的光催化活性高于经典光催化剂(TiO₂、WO₃和CdS)。参与甲苯光催化氧化的主要活性物种是光生空穴(h⁺)和超氧阴离子(O₂⁻)。由A位阳离子引起的八面体畸变影响光催化活性仍然是独特的,并且也是在更深入了解基于卤化物钙钛矿的光催化方面向前迈出的一步。八面体畸变与光催化之间的关系也可以指导涉及其他卤化物钙钛矿的新型光催化系统的设计。

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