Efficient CO2 photoreduction enabled by the energy transfer pathway in metal‐organic framework

Abstract 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 CO2 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 (1314 μmol·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.