Rejoint of Carbon Nitride Fragments into Multi‐Interfacial Order‐Disorder Homojunction for Robust Photo‐Driven Generation of H2O2

Photocatalytic technology based on carbon nitride (C₃ N₄ ) offers a sustainable and clean approach for hydrogen peroxide (H₂ O₂ ) production, but the yield is severely limited by the sluggish hot carriers due to the weak internal electric field. In this study, a novel approach is devised by fragmenting bulk C₃ N₄ into smaller pieces (CN-NH₄ ) and then subjecting it to a directed healing process to create multiple order-disorder interfaces (CN-NH₄ -NaK). The resulting junctions in CN-NH₄ -NaK significantly boost charge dynamics and facilitate more spatially and orderly separated redox centers. As a result, CN-NH₄ -NaK demonstrates outstanding photosynthesis of H₂ O₂ via both two-step single-electron and one-step double-electron oxygen reduction pathways, achieving a remarkable yield of 16675 µmol h^-1 g^-1 , excellent selectivity (> 91%), and a prominent solar-to-chemical conversion efficiency exceeding 2.3%. These remarkable results surpass pristine C₃ N₄ by 158 times and outperform previously reported C₃ N₄ -based photocatalysts. This work represents a significant advancement in catalyst design and modification technology, inspiring the development of more efficient metal-free photocatalysts for the synthesis of highly valued fuels.