Modulation of Polymeric Carbon Nitrides through Supramolecular Preorganization for Efficient Photocatalytic Hydrogen Generation

Supramolecular pre‐assembly by design is an effective strategy to adapt the physicochemical properties of polymeric carbon nitrides (PCNs) to improve their solar conversion performance. A new supramolecular preorganization protocol, which employs H2O as the self‐assembly medium and sodium persulfate as a modifier, is proposed to modulate the textural and photoelectronic features of PCNs for efficient visible‐light H2 evolution. Sodium persulfate is revealed to precisely tailor the final carbon nitride polymers with unusual porous layered structures and promoted charge separation and migration kinetics. As a result, the modulated PCNs with optimized structures show a greatly enriched activity for photocatalytic H2 generation compared to the analogous materials derived from melamine without the modifier.