Switching Excited State Distribution of Metal–Organic Framework for Dramatically Boosting Photocatalysis

Abstract Photosensitization associated with electron/energy transfer represents the central science of natural photosynthesis. Herein, we proposed a protocol to dramatically improve the sensitizing ability of metal–organic frameworks (MOFs) by switching their excited state distribution from 3 MLCT (metal‐to‐ligand charge transfer) to 3 IL (intraligand). The hierarchical organization of 3 IL MOFs and Co/Cu catalysts facilitates electron transfer for efficient photocatalytic H 2 evolution with a yield of 26 844.6 μmol g −1 and CO 2 photoreduction with a record HCOOH yield of 4807.6 μmol g −1 among all the MOF photocatalysts. Systematic investigations demonstrate that strong visible‐light‐absorption, long‐lived excited state and ingenious multi‐component synergy in the 3 IL MOFs can facilitate both interface and intra‐framework electron transfer to boost photocatalysis. This work opens up an avenue to boost solar‐energy conversion by engineering sensitizing centers at a molecular level.