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

As a reproducible intermediate for hydrogen (H2) and carbon cycling, methanol mixed with water (H2O) in a ratio of 1:1 can multiply the outcome of green H2 generation via Photocatalytic reforming of methanol‐H2O (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 (H2, 35.6 mmol h‐1 g‐1; CO2, 11.5 mmol h‐1 g‐1) under sunlight at 35 °C. We revealed that the surface‐terminating carboxyl groups (–COOH) promote the dark dehydrogenation of methanol on MetCNx to form methoxy (⁎OCH3) and methylol (⁎CH2OH) simultaneously, with the hydroxyl (⁎OH) generated by photostimulated H2O oxidation promotes the C‐H activation of formaldehyde, then leads the whole reaction into the formation of CO2 and three H2. The extended light absorption, enhanced charge separation and transport, and efficient surface reaction improve photocatalytic efficiency.