Substituent Modulated Electronic Properties of Cu(Ⅰ)Active Site in Metal-Organic Halides for Boosting Hydrogen Evolution Reaction  

作　　者：Jing Wu Pingping Wang Yuzhe Fu Yi Shen Bin Wang Feng Hu Mengkai Zuo Wei Huang Dayu Wu 

机构地区：[1]Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology,Advanced Catalysis&Green Manufacturing Collaborative Innovation Center,Schoolof Petrochemical Engineering,Changzhou University,Changzhou,Jiangsu 213164,China

出　　处：《Chinese Journal of Chemistry》2024年第22期2845-2852,共8页中国化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(92161121).

摘　　要：Development of heterogeneous molecular photocatalysts for promising light-driven hydrogen evolution reaction(HER)is highly demanding but still challenging.Here,we report the blue-greenish emitting dinuclear metal–organic halides as photocatalyst by incorporating site-specific single copper(Ⅰ)atoms that exhibit an efficient carbon-negative H_(2) production.Interestingly,the electronic properties,including the spin and charge density of central Cu(Ⅰ)active site,can be triggered by substituent modulation in metal–organic halides,which greatly affect the exciton dissociation kinetics and thus the HER reactivity.The optimized spin density in these heterogeneous photocatalysts drastically boosts the hydrogen production rate from 1250 to 3130μmol·g^(–1)·h^(–1).Our molecular strategy provides a platform that rationally facilitates electronic modulation of copper(Ⅰ)atoms,tunes the macroscopic optoelectronic properties of photocatalysts and boosts carbon-negative HER activity,extending the boundaries of conventional molecular-based photocatalysts.

关 键 词：Metal-organic halides PHOTOCATALYSIS Hydrogen evolution Microenvironment modulation Hybrid copper(Ⅰ)halids Ligand effects Substituent effects Spin density 

分 类 号：O62[理学—有机化学]