Rational Design of Co(Ⅱ)-Pyridine-Decorated Reduced Phosphomolybdate Photocatalysts for Efficient Aniline Oxidation under Mild Conditions  

作　　者：Xiaohui Liu Hui Li Na Xu Yanyan Guo Xiaoyan Zhang Xiuli Wang 

机构地区：[1]College of Chemistry and Materials Engineering,Bohai University,Liaoning Professional Technology Innovation Center of Liaoning Province for Conversion Materialsof SolarCell,Jinzhou,Liaoning 121013,China

出　　处：《Chinese Journal of Chemistry》2024年第23期2970-2978,共9页中国化学(英文版)

基　　金：financially supported by the National Natural Science Foundation of China(Nos.22101030,21971024);the Doctoral Research Fund of Bohai University(Nos.0520bs022,0521bs011,0522xn032).

摘　　要：The conversion of aniline to nitrosobenzene(NSB),a key step in the synthesis of important chemicals,demands the development of environmentally friendly photocatalysts that operate under mild conditions.This process is driven by the need for sustainable methods,given toxic nature of aniline and its central role in the production of dyes,pharmaceuticals,and agricultural chemicals.This study reports on the synthesis of three reduced phosphomolybdate compounds with Co(Ⅱ)centers and polypyridine ligands,which show great potential as photocatalysts for the mild oxidation of aniline to NSB.The synthesis uses 30%H_(2)O_(2)as the oxidant and the compounds as the sole catalysts,achieving high conversion rates and selectivity without additional additives or photosensitizers.The integration of multidentate ligands with{P4Mo6}clusters significantly reduces the band gap,facilitating visible-light-driven photocatalysis.The adsorption interaction between coordinated water molecules and Co ions and H_(2)O_(2)is found to enhance the conversion rate of aniline,a finding supported by DFT analyses.

关 键 词：POLYOXOMETALATES Photocatalysis Aniline oxidation N ligands Heterogeneous catalysis 

分 类 号：O62[理学—有机化学]