Converting low-concentration carbon dioxide(CO_(2))into value-added chemicals meets the demand of carbonneutral technologies,yet efficient and stable catalysts for CO_(2)absorption and activation are urgently desired....Converting low-concentration carbon dioxide(CO_(2))into value-added chemicals meets the demand of carbonneutral technologies,yet efficient and stable catalysts for CO_(2)absorption and activation are urgently desired.Singleatom(-site)catalysts(SACs)supported by molecule-based porous materials offer new catalyst platforms that enable the integration of enrichment,activation,and conversion through multisite cooperation.Herein,we report the synthesis of the first N-heterocyclic olefin(NHO)coordinated Pd SAC through a facile precursor-partial metallization of a methyl-modified porous imidazolium-based polymer,which exhibits the highest turnover frequency of 117.7±1.4 h^(−1) for Pd-catalyzed one-pot tri-component reactions of propargylamines,aryl iodides,and CO_(2)in simulated flue gas,and is approximately 58 times higher than that of N-heterocyclic carbene coordinated analogues and outperforms all reported catalysts.Various spectroscopic technologies and density functional theory calculations unveiled the NHO-assisted dual-site catalysis through the formation of NHO–CO_(2)adducts and intramolecular cyclization intermediates.These findings showcase the significant potential of coupling inorganic single atoms and functional organic sites for multicomponent catalytic reactions.展开更多
基金financially supported by the National Natural Science Foundation of China(grant nos.22161021,22261002,21890382,and 22375079)the Key Project of Jiangxi Provincial Department of Science and Technology(grant nos.S2023ZRZDL0164,20232ACB203016,and S2023ZRMSL0668)+2 种基金the Key Laboratory of Jiangxi University for Functional Materials Chemistry(grant no.FMC21702)the Education Department of Jiangxi Province(grant nos.GJJ201427 and SZUGSHX2022-1043)C.-T.H.acknowledges the support of Jiangxi Province(grant no.20224ACB214001).
文摘Converting low-concentration carbon dioxide(CO_(2))into value-added chemicals meets the demand of carbonneutral technologies,yet efficient and stable catalysts for CO_(2)absorption and activation are urgently desired.Singleatom(-site)catalysts(SACs)supported by molecule-based porous materials offer new catalyst platforms that enable the integration of enrichment,activation,and conversion through multisite cooperation.Herein,we report the synthesis of the first N-heterocyclic olefin(NHO)coordinated Pd SAC through a facile precursor-partial metallization of a methyl-modified porous imidazolium-based polymer,which exhibits the highest turnover frequency of 117.7±1.4 h^(−1) for Pd-catalyzed one-pot tri-component reactions of propargylamines,aryl iodides,and CO_(2)in simulated flue gas,and is approximately 58 times higher than that of N-heterocyclic carbene coordinated analogues and outperforms all reported catalysts.Various spectroscopic technologies and density functional theory calculations unveiled the NHO-assisted dual-site catalysis through the formation of NHO–CO_(2)adducts and intramolecular cyclization intermediates.These findings showcase the significant potential of coupling inorganic single atoms and functional organic sites for multicomponent catalytic reactions.
