Enabling Reaction Selectivity of Platinum Catalysts by Photoinduced Electronic Effects  

作　　者：Kowsalya Devi Rasamani Xinyan Dai Matthew Messner Cunming Liu Xiaoyi Zhang Yugang Sun 

机构地区：[1]Department of Chemistry,Temple University,Philadelphia,Pennsylvania 19122,USA

出　　处：《Precision Chemistry》2023年第4期248-255,共8页精准化学（英文）

摘　　要：Reaction selectivity is crucial to producing target molecules of importance with minimum waste.This work reports an efficient and green strategy to improve reaction selectivity in visible-light-mediated chemical transformations by employing Pt/SiOx photocatalysts,which is ascribed to light-induced surface electronic modification in the small Pt nanocrystals.This strategy has been successfully applied to synthesize commercially valuable but thermodynamically unfavorable arylhydroxylamines with high selectivity via partial hydrogenation of the respective nitroarenes.Surface modification of the small Pt nanocrystals with triethanolamine(TEA)molecules further optimizes the Pt electronic structure to favor the reaction selectivity.The light-induced surface electronic structure alterations and the TEA chemical modification act synergistically to prevent the readsorption of desorbed electron-rich arylhydroxylamines.This prevents the complete hydrogenation of arylhydroxylamines to respective anilines,leading to high arylhydroxylamine selectivity of 81−91%.In addition,photoillumination of Pt nanocrystals always accelerates the reaction kinetics significantly regardless of their surface modification.

关 键 词：selective photocatalysis enhanced plasmonic absorption hot-electron-driven chemistry photoinduced adsorption/desorption dielectric scattering resonance selective hydrogenation 

分 类 号：O64[理学—物理化学]