Implanting CoO_x Clusters on Ordered Macroporous ZnO Nanoreactors for Efficient CO₂ Photoreduction

Despite suffering from slow charge-carrier mobility, photocatalysis is still an attractive and promising technology toward producing green fuels from solar energy. An effective approach is to design and fabricate advanced architectural materials as photocatalysts to enhance the performance of semiconductor-based photocatalytic systems. Herein, metal-organic-framework-derived hierarchically ordered porous nitrogen and carbon co-doped ZnO (N-C-ZnO) structures are developed as nanoreactors with decorated CoO_x nanoclusters for CO₂ -to-CO conversion driven by visible light. Introduction of hierarchical nanoarchitectures with highly ordered interconnected meso-macroporous channels shows beneficial properties for photocatalytic reduction reactions, including enhanced mobility of charge carriers throughout the highly accessible framework, maximized exposure of active sites, and inhibited recombination of photoinduced charge carriers. Density functional theory calculations further reveal the key role of CoO_x nanoclusters with high affinity to CO₂ molecules, and the CoO bonds formed on the surface of the composite exhibit stronger charge redistribution. As a result, the obtained CoO_x /N-C-ZnO demonstrates enhanced photocatalysis performance in terms of high CO yield and long-term stability.