Hydrazine-Induced Sulfur Vacancies Promote Interfacial Charge Redistribution in ZnS/Gel-Derived TiO2 for Enhanced CO2 Activation and Methanation

Defect engineering in semiconductor heterojunctions offers a promising route for enhancing the selectivity of photocatalytic CO₂ conversion. In this work, a ZnS/gel-derived TiO₂ photocatalyst featuring sulfur vacancies introduced via hydrazine hydrate (N₂H₄) treatment is developed. XRD, HRTEM, and XPS analyses confirm the formation of a crystalline heterointerface and a defect-rich ZnS surface, enabling effective interfacial electronic modulation. The optimized ZnS/gel-derived TiO₂-0.48 composite achieves CH₄ and CO yields of 6.76 and 14.47 μmol·g^-1·h^-1, respectively, with a CH₄ selectivity of 31.8% and an electron selectivity of 65.1%, clearly outperforming pristine TiO₂ and the corresponding single-component catalysts under identical conditions. Photoluminescence quenching, enhanced photocurrent response, and reduced charge-transfer resistance indicate significantly improved interfacial charge separation. Mott-Schottky analysis combined with optical bandgap measurements reveals pronounced interfacial charge redistribution in the composite system. Considering the intrinsic band structure of ZnS and gel-derived TiO₂, a Z-scheme-compatible interfacial charge migration model is proposed, in which photogenerated electrons with strong reductive power are preferentially retained on ZnS, while holes with strong oxidative capability remain on gel-derived TiO₂. This charge migration pathway preserves high redox potentials, facilitating multi-electron CO₂ methanation and water oxidation. Density functional theory calculations further demonstrate that sulfur vacancies stabilize *COOH and *CO intermediates and reduce the energy barrier for *COOH formation from +0.51 eV to +0.21 eV, thereby promoting CO₂ activation and CH₄ formation. These results reveal that sulfur vacancies not only activate CO₂ molecules but also regulate interfacial charge migration behavior. This work provides a synergistic strategy combining defect engineering and interfacial electronic modulation to enhance selectivity and mechanistic understanding in CO₂-to-CH₄ photoconversion.