Photocatalytic Multielectron Reduction of Nitroarenes to Anilines by Utilizing an Electron-Storable Polyoxometalate-Based Metal–Organic Framework

作者：Jiachen Jiao, Hui Sun, Si Chen, Jiangbo Xu, Ting Zhang, Qiuxia Han · 发表于：ACS Applied Materials & Interfaces · 年份：2022 · DOI：10.1021/acsami.1c24911 · 被引用次数：66 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Polyoxometalates: Synthesis and Applications、Covalent Organic Framework Applications

A powerful approach to generate photocatalysts for the highly selective reduction of nitrobenzene using light as the driving force is a combination of photosensitizers and electron-storable components in a cooperative photocatalysis fashion. Herein, a new precious metal-free photocatalyst, {ZnW-TPT}, was prepared by incorporating a Zn-substituted monovacant Keggin polyanion [SiZnW 11 O 39 ] 6– and a photoactive organic bridging link 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT) into a framework. In this structure, the direct coordination bond between [SiZnW 11 O 39 ] 6– and the TPT ligand and the π–π interactions between TPT molecules help separate and migrate photogenerated carriers, which improves the photocatalytic activity of {ZnW-TPT} . The photoelectrochemical properties of {ZnW-TPT} were well studied by solid UV–vis absorption, fluorescence, transient photocurrent response, and electrochemical impedance spectroscopy tests. {ZnW-TPT} efficiently converts using hydrazine hydrate with 99% conversion and 99% selectivity for anilines under mild conditions.