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

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 (MLCT)-M-3 (metal-to-ligand charge transfer) to (IL)-I-3 (intraligand). The hierarchical organization of (IL)-I-3 MOFs and Co/Cu catalysts facilitates electron transfer for efficient photocatalytic H-2 evolution with a yield of 26 844.6 mu mol g(-1) and CO2 photoreduction with a record HCOOH yield of 4807.6 mu mol 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 (IL)-I-3 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.

Automated summary

This study proposes a method to enhance the sensitizing ability of metal-organic frameworks by promoting electron transfer through hierarchical organization and multi-component synergy, leading to improved photocatalytic activity. This work provides a new approach for enhancing solar energy conversion through the molecular-level engineering of sensitizing centers.