Decoupled Artificial Photosynthesis via a Catalysis-Redox Coupled COF||BiVO4 Photoelectrochemical Device

Artificial photosynthesis is an attractive approach to direct fuel production from sunlight. However, the simultaneous O2 evolution reaction (OER) and CO2 reduction reaction (CDRR) present challenges for product separation and safety. Herein, we propose a strategy to temporally decouple artificial photosynthesis through photoelectrochemical energy storage. We utilized a covalent organic framework (DTCo-COF) with redox-active electron donors (−C–OH moieties) and catalytically active electron acceptors (cobalt-porphyrin) to enable reversible −C–OH/–C═O redox reaction and redox-promoted CO2-to-CO photoreduction. Integrating the COF photocathode with an OER photoanode in a photoelectrochemical device allows the effective storage of OER-generated electrons and protons by −C═O groups. These stored charges can be later employed for CDRR while regenerating −C═O to complete the loop, thus enabling on-demand and separate production of O2 or solar fuels. Our work sets the stage for advancements in decoupled artificial photosynthesis and the development of more efficient solar fuel production technologies.