Orbital hybridization plays a crucial role in catalytic processes,yet elucidating its mechanism remains a significant challenge.Here,we have developed a strategy for the formation of Yb-C bond by unconventional p-d or...Orbital hybridization plays a crucial role in catalytic processes,yet elucidating its mechanism remains a significant challenge.Here,we have developed a strategy for the formation of Yb-C bond by unconventional p-d orbital hybridization,which induced carbon nitride modified by rare-earth metal element Yb.The optimal sample exhibits catalytic performance 11.2 times greater than that of g-C_(3)N_(4)with N vacancies(NvCN).Yb-C bond and N vacancies reduced the energy barrier and optimized the rate-determining step(*COO+*H→*CO+*OH).Additionally,the intense Yb-C interaction created a specific electrons bridge,which accelerated the transfer rate of electrons on the photocatalytic surface.Next,the CO_(2) conversion reaction mechanism was studied by in situ infrared spectroscopy and theoretical calculations,and the unconventional p-d orbital hybridization contributed to the generation of vital intermediate*CO.This study provides a theoretical basis for designing single-atom photocatalysts for the reduction of CO_(2).展开更多
基金financially supported by the National Natural Science Foundation of China(No.52370109)Guangdong Province Scientific Research Platform Project(Nos.2023ZDZX4052,2022ZDZX4046)+3 种基金Shaoguan Science and Technology Projects(No.230616088031998)High Level Talents Introduction Project of"Pearl River Talent Plan"in Guangdong Province(No.2019CX01L308)the Support Scheme of Guangzhou for Leading Talents in Innovation and Entrepreneurship Funding(No.2016015)the Science and Technology Research Program of Chongqing Municipal Education Commission of China(No.KJZDM202400802)
文摘Orbital hybridization plays a crucial role in catalytic processes,yet elucidating its mechanism remains a significant challenge.Here,we have developed a strategy for the formation of Yb-C bond by unconventional p-d orbital hybridization,which induced carbon nitride modified by rare-earth metal element Yb.The optimal sample exhibits catalytic performance 11.2 times greater than that of g-C_(3)N_(4)with N vacancies(NvCN).Yb-C bond and N vacancies reduced the energy barrier and optimized the rate-determining step(*COO+*H→*CO+*OH).Additionally,the intense Yb-C interaction created a specific electrons bridge,which accelerated the transfer rate of electrons on the photocatalytic surface.Next,the CO_(2) conversion reaction mechanism was studied by in situ infrared spectroscopy and theoretical calculations,and the unconventional p-d orbital hybridization contributed to the generation of vital intermediate*CO.This study provides a theoretical basis for designing single-atom photocatalysts for the reduction of CO_(2).
