Unprecedented Eighteen‐Faceted BiOCl with a Ternary Facet Junction Boosting Cascade Charge Flow and Photo‐redox

Exposure of anisotropic crystal facets allows the directional transfer of photoexcited electrons (e^- ) and holes (h⁺ ), for spatial charge separation. High-index facets with a high density of low-coordinated atoms always serve as reactive catalytic sites. However, preparation of multi-facets or high-index facets is highly challenging for layered bismuth-based photocatalysts. Herein, we report the preparation of unprecedented eighteen-faceted BiOCl with {001} top facets and {102} and {112} oblique facets via a hydrothermal process. Compared to the conventional BiOCl square plates with {001} top facets and {110} lateral facets, the eighteen-faceted BiOCl has highly enhanced photocatalytic activity for H₂ evolution and hydroxyl radicals (^. OH) production. Theoretical calculations and photodeposition results disclose that the of eighteen-faceted BiOCl has a well-matched {001}/{102}/{112} ternary facet junction, which provides a cascade path for more efficient charge flow than the binary facet junction in BiOCl square plates.