Precise Defect Engineering on Graphitic Carbon Nitrides for Boosted Solar H₂ Production

Abstract Defect engineering has been regarded as an “all‐in‐one strategy” to alleviate the insufficient solar utilization in g‐C₃N₄. However, without appropriate modification, the defect benefits will be partly offset due to the formation of deep localized defect states and deteriorated surface states, lowering the photocarrier separation efficiency. To this end, the defective g‐C₃N₄ is designed with both S dopants and N vacancies via a dual‐solvent‐assisted synthetic approach. The precise defect control is realized by the addition of ethylene glycol (EG) into precursor formation and molten sulfur into the pyrolysis process, which simultaneously induced g‐C3N4. with shallow defect states. These shallow defect energy levels can act as a temporary electron reservoir, which are critical to evoke the migrated electrons from CB with a moderate trapping ability, thus suppressing the bulky photocarrier recombination. Additionally, the optimized surface states of DCN‐ES are also demonstrated by the highest electron‐trapping resistance (R_trapping) of 9.56 × 10³ Ω cm² and the slowest decay kinetics of surface carriers (0.057 s⁻¹), which guaranteed the smooth surface charge transfer rather than being the recombination sites. As a result, DCN‐ES exhibited a superior H₂ evolution rate of 4219.9 µmol g⁻¹ h⁻¹, which is 29.1‐fold higher than unmodified g‐C₃N₄.