Mild‐condition Photocatalytic Reforming of Methanol‐water by a Hierarchical, Asymmetry Carbon Nitride

Abstract As a reproducible intermediate for hydrogen (H 2 ) and carbon cycling, methanol mixed with water (H 2 O) in a ratio of 1 : 1 can multiply the outcome of green H 2 generation via Photocatalytic reforming of methanol‐H 2 O (PRMW). Hitherto, low‐energy and mild‐condition PRMW remains a serious challenge. Here, the amino acid‐derived carbon nitrides (ACN) were synthesized supramolecular precursor strategy for PRMW and achieved excellent performance (H 2 , 35.6 mmol h −1 g −1 ; CO 2 , 11.5 mmol h −1 g −1 ) under sunlight at 35 °C. It was revealed that the surface‐terminating carboxyl groups (−COOH) promote the dark dehydrogenation of methanol on MetCN x to form methoxy (*OCH 3 ) and methylol (*CH 2 OH) simultaneously, with the hydroxyl (*OH) generated by photostimulated H 2 O oxidation promotes the C−H activation of formaldehyde, then leads the whole reaction into the formation of CO 2 and three H 2 . The extended light absorption, enhanced charge separation and transport, and efficient surface reaction improve photocatalytic efficiency.