Hierarchical Hollow-TiO 2 @CdS/ZnS Hybrid for Solar-Driven CO 2 -Selective Conversion.

Light-driven valorization conversion of CO ₂ is an encouraging carbon-negative pathway that shifts energy-reliance from fossil fuels to renewables. Herein, a hierarchical urchin-like hollow-TiO ₂ @CdS/ZnS (HTO@CdS/ZnS) Z-scheme hybrid synthesized by an in situ self-assembly strategy presents superior photocatalytic CO ₂ -to-CO activity with nearly 100% selectivity. Specifically, benefitting from the reasonable architectural and interface design, as well as surface modification, this benchmarked visible-light-driven photocatalyst achieves a CO output of 62.2 μmol·h ^-1 and a record apparent quantum yield of 6.54% with the Co(bpy) ₃ ²⁺ (bpy = 2,2'-bipyridine) cocatalyst. It rivals all the incumbent selective photocatalytic conversion of CO ₂ to CO in the CH ₃ CN/H ₂ O/TEOA reaction systems. Specifically, the addition of HTO and stabilized ZnS enables the photocatalyst to effectively upgrade optical and electrical performances, contributing to efficient light-harvesting and photogenerated carrier separation, as well as interfacial charge transfer. The tremendous enhancement of photocatalytic performance reveals the superiority of the Z-scheme heterojunction assembled from HTO and CdS/ZnS, featuring the inner electric field derived from the band bending of HTO@CdS/ZnS make CdS resistant to photocorrosion. This study allows access to inspire studies on rationally modeling and constructing diverse heterostructures for the storage and conversion of renewables and chemicals.