Plasmon-induced hot energy in metal nanostructures holds great promise for photocatalytic organic conversions.However,maintaining the high-energy state of hot electrons within these structures remains challenging,even...Plasmon-induced hot energy in metal nanostructures holds great promise for photocatalytic organic conversions.However,maintaining the high-energy state of hot electrons within these structures remains challenging,even in hybrid metal-semiconductor heterojunctions.The rapid relaxation of hot electrons(<1 ps)due to a thick-shell and loosely bound semiconductor layer limits their extraction efficiency and utilization effectiveness during photocatalysis.Herein,we fabricated a novel metalsemiconductor heterojunction(P2-Au)with ultrathin-shell semiconductor layer by combing ultra-small metal chalcogenide semiconductor clusters(P2)with gold nanorods(Au NRs),which exhibits high-efficiency extraction of hot electrons and photocatalytic application.The robust binding of P2 cluster,with its smaller volume and larger energy level splitting compared to large-sized quantum dots,not only significantly increases the yield of hot electrons but also enables their rapid extraction and sustains long-lived(>2 ns)high-energy states.As a proof of concept,the composite photocatalyst achieves near-infrared-lightdriven C(sp^(3))-S cross-coupling reactions for the first time.This protocol effectively produces over 50 alkylthioethers from a wide scope range of non-active alkyl bromides and chlorides,aryl and alkyl thiols.This work provides a new strategy for highefficiency extraction of hot electrons within plasmonic metal nanostructures and paves the way for hot electron-driven photocatalytic organic transformations.展开更多
基金supported by the National Natural Science Foundation of China(U22A20432,92261205,22071165,22201103)the 111 Project(D20015)+2 种基金the Guangzhou Municipal Science and Technology Bureau(2024A04J3490)supported by the State Key Laboratory of Bioactive Molecules and Druggability Assessment(202402025)the Fundamental Research Funds for the Central Universities。
文摘Plasmon-induced hot energy in metal nanostructures holds great promise for photocatalytic organic conversions.However,maintaining the high-energy state of hot electrons within these structures remains challenging,even in hybrid metal-semiconductor heterojunctions.The rapid relaxation of hot electrons(<1 ps)due to a thick-shell and loosely bound semiconductor layer limits their extraction efficiency and utilization effectiveness during photocatalysis.Herein,we fabricated a novel metalsemiconductor heterojunction(P2-Au)with ultrathin-shell semiconductor layer by combing ultra-small metal chalcogenide semiconductor clusters(P2)with gold nanorods(Au NRs),which exhibits high-efficiency extraction of hot electrons and photocatalytic application.The robust binding of P2 cluster,with its smaller volume and larger energy level splitting compared to large-sized quantum dots,not only significantly increases the yield of hot electrons but also enables their rapid extraction and sustains long-lived(>2 ns)high-energy states.As a proof of concept,the composite photocatalyst achieves near-infrared-lightdriven C(sp^(3))-S cross-coupling reactions for the first time.This protocol effectively produces over 50 alkylthioethers from a wide scope range of non-active alkyl bromides and chlorides,aryl and alkyl thiols.This work provides a new strategy for highefficiency extraction of hot electrons within plasmonic metal nanostructures and paves the way for hot electron-driven photocatalytic organic transformations.
