Distinct Pathways Determined by Photocatalytic C─H or O─H Bond Activation for Hydroxyl Compounds Conversion Paired With Hydrogen Production

Abstract Selective control of C─H or O─H bond activation in photocatalytic conversion coupled with hydrogen production is a promising yet challenging goal. Here, an efficient photocatalytic system is reported that can produce high‐valued tartaric acid or formaldehyde and simultaneous producing hydrogen. At optimized conditions, the directional conversion of glycolic acid into tartaric acid is achieved with a selectivity of 76.24%, and the selectivity of methanol oxidation into formaldehyde reaches 88.21%. A high hydrogen production rate of 21.43 mmol·g −1 ·h −1 is obtained using glycolic acid as substrate. Mechanism studies reveal that α ‐C─H bond is preferentially activated in glycolic acid adsorbed on the photocatalyst, while O─H bond is preferentially activated in methanol, forming carbon‐centered radical (•CH(OH)COOH) or oxygen‐centered radical (CH 3 O•) for subsequent coupling or oxidation reactions. This work demonstrates the selective control of the photocatalytic conversion process of different hydroxyl compounds, providing a new perspective for achieving organic compounds selective activation coupled with hydrogen production.