Many studies in metal-organic frameworks(MOFs)aiming for high photocatalytic activity resort to self-assembling both energy donor and acceptor building units in skeleton to achieve effective energy transfer,which,howe...Many studies in metal-organic frameworks(MOFs)aiming for high photocatalytic activity resort to self-assembling both energy donor and acceptor building units in skeleton to achieve effective energy transfer,which,however,usually needs tedious synthetic procedure and design of a new MOF.In this work,we demonstrated that building a Förster resonance energy transfer(FRET)pathway can be realized through suitable molecular doping in a given MOF structure without altering the original porous structure,presenting an alternative strategy to design efficient photocatalysts for CO_(2)reduction.In situ electron spin resonance,ultrafast transient absorption spectroscopy,and computational studies reveal that the FRET-induced excitation has dramatically altered the exciton transfer pathway in structure and facilitated electron-hole separation.As a result,the molecular doped MOFs synthesized through one-pot reaction show outstanding selectivity(96%)and activity(1314μmol⋅g^(−1)⋅h^(−1))for CO production versus almost no activity for the pristine MOFs,and this result stands out from existing competitors.Furthermore,the reaction mechanism was proposed and the intermediate signals were detected by in situ diffuse reflectance infrared Fourier transform spectroscopies.This study presents a clear picture of building FRET process in MOFs through molecular doping and provides a new design strategy for MOF-based photocatalysts.展开更多
基金National Key Research and Development Program of China,Grant/Award Number:2018YFA0208600National Natural Science Foundation of China,Grant/Award Numbers:21871267,22071246,22272178CAS-Iranian Vice Presidency for Science and Technology Joint Research Project,Grant/Award Number:121835KYSB20200034。
文摘Many studies in metal-organic frameworks(MOFs)aiming for high photocatalytic activity resort to self-assembling both energy donor and acceptor building units in skeleton to achieve effective energy transfer,which,however,usually needs tedious synthetic procedure and design of a new MOF.In this work,we demonstrated that building a Förster resonance energy transfer(FRET)pathway can be realized through suitable molecular doping in a given MOF structure without altering the original porous structure,presenting an alternative strategy to design efficient photocatalysts for CO_(2)reduction.In situ electron spin resonance,ultrafast transient absorption spectroscopy,and computational studies reveal that the FRET-induced excitation has dramatically altered the exciton transfer pathway in structure and facilitated electron-hole separation.As a result,the molecular doped MOFs synthesized through one-pot reaction show outstanding selectivity(96%)and activity(1314μmol⋅g^(−1)⋅h^(−1))for CO production versus almost no activity for the pristine MOFs,and this result stands out from existing competitors.Furthermore,the reaction mechanism was proposed and the intermediate signals were detected by in situ diffuse reflectance infrared Fourier transform spectroscopies.This study presents a clear picture of building FRET process in MOFs through molecular doping and provides a new design strategy for MOF-based photocatalysts.
