Interfacial Charge Separation in ZrO₂-Coupled Bismuth Sulfobromide Photocatalysts for CO₂-to-CH₄ Conversion

Photocatalytic CO2 reduction requires efficient charge separation and suitable surface sites for multi-electron transfer. Herein, ZrO2-coupled bismuth sulfobromide heterojunctions were synthesized through a solvothermal method and applied to gas-phase CO2 photoreduction. XRD, TEM, XPS, UV–vis diffuse reflectance spectroscopy, photoluminescence, and transient photocurrent measurements confirmed the formation of a strongly coupled interface between ZrO2 and bismuth sulfobromide. The optimized heterojunction exhibited a CH4 evolution rate of 28.7 μmol g⁻¹ h⁻¹, which was 3.4 times higher than that of pristine bismuth sulfobromide. Isotope labeling with 13CO2 confirmed that methane originated from CO2 reduction rather than surface carbon contamination. The enhanced activity was attributed to improved electron transfer from the sulfobromide phase to ZrO2 and increased stabilization of CO2-derived intermediates at interfacial oxygen sites.

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