Exploring affordable cocatalysts with high-performance for boosting charge separation and CO2 activation is an effective strategy to reinforce CO2 photoreduction efficiency. Herein, the well-defined Co9S8 cages are exploited as a...

Light-driven valorization conversion of CO2 is an encouraging carbon-negative pathway that shifts energy-reliance from fossil fuels to renewables. Herein, a hierarchical urchin-like hollow-TiO2@CdS/ZnS (HTO@CdS/ZnS) Z-scheme hybrid synthesized by an in situ self-assembly strategy presents superior photocatalytic CO2-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 CO2 to CO in the CH3CN/H2O/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.