Sulfur Doping Evoking Reinforced Electronic Metal‐Support Interactions in Silver‐Modified Carbon Nitride Toward Efficient Photocatalytic Hydrogen Production

ABSTRACT Introducing metal cocatalysts is resultful to resolve intrinsic limitations in carbon nitride for improving photocatalytic performance. Modulating electronic metal‐support interactions (EMSI) offered new guidance for designing efficient metal/carbon nitride photocatalysts and understanding the interfacial electron perturbation mechanisms. Herein, silver nanoparticles (Ag NPs) were anchored on sulfur‐doped tubular carbon nitride (SCN), the strong Ag─S interfacial bonding reinforced the EMSI between Ag NPs and SCN and improved photocatalytic H ₂ evolution (PHE) performance. The optimal SCN‐Ag exhibited an outstanding PHE rate of 10.05 mmol g ^{− 1} h ^{− 1} ( λ ≥ 400 nm) and an apparent quantum yield (AQY) of 25% at 400 nm. The S atoms not only promoted the intrinsic separation of photo‐induced charge carriers in SCN but also modulated the d‐orbital of Ag, optimizing the H* adsorption behavior via strong EMSI. These discoveries provided ponderable understandings on the design of efficient metal‐support photocatalysts for PHE, demonstrating that the strategy of modulating EMSI to optimize photocatalytic activity is effective.