Three-layered nanoplates and amorphous/crystalline interface synergism boost CO 2 photoreduction on bismuth oxychloride nanospheres.

Structural features like 3D nano-size, ultrathin thickness and amorphous/crystalline interfaces play crucial roles in regulating charge separation and active sites of photocatalysts. However, their co-occurrence in a single catalyst and exploitation in photocatalytic CO 2 reduction (PCR) remains challenging. Herein, nano-sized bismuth oxychloride spheres (BiOCl-NS) confining three-layered nanoplates (∼2.2 nm ultrathin) and an amorphous/crystalline interface are exclusively developed via intrinsic engineering for an enhanced sacrificial-reagent-free PCR system. The results uncover a unique synergism wherein the three-layered nanoplates accelerate electron-hole separation, and the amorphous/crystalline interface exposes electron-localized active sites (Bi-O vac -Bi). Consequently, BiOCl-NS exhibit efficient CO 2 adsorption and activation with the lowering of rate-determining-step energy barriers, leading to remarkable CO production (102.72 μmol g -1 h -1 ) with high selectivity (>99%), stability (>30 h), and apparent quantum efficiency (0.51%), outperforming conventional counterparts. Our work provides a facile structural engineering approach for boosting PCR and offers distinct synergism for advancing diverse materials.