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协同聚酰亚胺-二氧化钛光催化和三乙胺催化选择性氧化硫化物。

Selective aerobic oxidation of sulfides by cooperative polyimide-titanium dioxide photocatalysis and triethylamine catalysis.

机构信息

Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.

Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.

出版信息

J Colloid Interface Sci. 2020 Apr 1;565:614-622. doi: 10.1016/j.jcis.2020.01.046. Epub 2020 Jan 16.

Abstract

The selective aerobic oxidation of sulfides is highly attractive for modern organic and pharmaceutical synthesis. Thus, there is an urgent need for exploring new photocatalytic system on this reaction. In this work, we investigated the polyimide-titanium dioxide (Aeroxide P25 TiO, denoted as P25) photocatalyst in visible light-driven selective aerobic oxidation of sulfides. Polyimide-P25 shows enhanced absorption of visible light. Subsequently, this makes polyimide-P25 exhibits observable photocatalytic activity on visible light-driven selective aerobic oxidation of sulfides while pure polyimide and P25 individually have none. Aided by triethylamine (TEA), the yield of sulfoxide by polyimide-P25 photocatalysis reaches more than 3 folds compared to that without TEA, highlighting the remarkable cooperative effect between polyimide-P25 photocatalysis and TEA catalysis. Moreover, a plausible mechanism is figured out based on the quenching control experiments, kinetic studies and in-situ electron paramagnetic resonance (EPR) tests. This work could provide useful guidance for the rational design of hybrid photocatalysts to undertake challenging selective chemical transformations.

摘要

硫化物的选择性有氧氧化在现代有机和药物合成中极具吸引力。因此,迫切需要在这一反应中探索新的光催化体系。在这项工作中,我们研究了聚酰亚胺-二氧化钛(Aeroxide P25 TiO,记为 P25)光催化剂在可见光驱动的硫化物选择性有氧氧化中的作用。聚酰亚胺-P25 表现出增强的可见光吸收。随后,这使得聚酰亚胺-P25 在可见光驱动的硫化物选择性有氧氧化中表现出可观察到的光催化活性,而纯聚酰亚胺和 P25 则没有。在三乙胺(TEA)的辅助下,聚酰亚胺-P25 光催化作用下亚砜的产率比没有 TEA 时提高了 3 倍以上,这突出了聚酰亚胺-P25 光催化作用与 TEA 催化作用之间的显著协同效应。此外,通过猝灭控制实验、动力学研究和原位电子顺磁共振(EPR)测试,提出了一种可能的反应机理。这项工作为设计用于承担挑战性的选择性化学转化的混合光催化剂提供了有用的指导。

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