Molecular Engineering of Methylated Sulfone‐Based Covalent Organic Frameworks for Back‐Reaction Inhibited Photocatalytic Overall Water Splitting

Abstract Solar‐to‐hydrogen (H 2 ) and oxygen (O 2 ) conversion via photocatalytic overall water splitting (OWS) holds great promise for a sustainable fuel economy, but has been challenged by the backward O 2 reduction reaction (ORR) with favored proton‐coupled electron transfer (PCET) dynamics. Here, we report that molecular engineering by methylation inhibits the backward ORR of molecular photocatalysts and enables efficient OWS process. As demonstrated by a benchmark sulfone‐based covalent organic framework (COF) photocatalyst, the precise methylation of its O 2 adsorption sites effectively blocks electron transfer and increases the barrier for hydrogen intermediate desorption that cooperatively obstructs the PCET process of ORR. Methylation also repels electrons to the neighboring photocatalytic sulfone group that promotes the forward H 2 evolution. The resultant DS‐COF achieves an impressive inhibition of about 70 % of the backward reaction and a three‐fold enhancement of the OWS performance with a H 2 evolution rate of 124.7 μmol h −1 g −1 , ranking among the highest reported for organic‐based photocatalysts. This work provides insights for engineering photocatalysts at the molecular level for efficient solar‐to‐fuel conversion.