Supercritical CO ₂ ‐Directed Semi‐Metallic (010) Plane on CaTiO ₃ for Enhanced Photocatalytic CO ₂ Reduction

ABSTRACT Photocatalytic CO ₂ reduction offers a promising route for carbon recycling and solar energy conversion. Here, we develop a supercritical CO ₂ surface reconstruction strategy to engineer (010)‐faceted CaTiO ₃ nanosheets with semi‐metallic properties and H ₂ O‐assisted surface stabilization. The optimized catalyst exhibits significantly enhanced CO ₂ photoreduction, with CO and CH ₄ yields of 16.93 and 9.76 µmol/g/h, respectively. Mechanistic studies reveal that the enhanced performance arises from multiple synergistic effects. The electron‐rich (010) plane promotes CO ₂ adsorption and activation. Incorporated H ₂ O molecules stabilize the structure and provide proton sources. The semi‐metallic nature facilitates charge separation while an upshifted d‐band center lowers energy barriers for key reaction steps (*CO → *COH, *CH → *CH ₂ ). This work provides atomic‐level insights into facet‐engineered perovskite photocatalysts and offers a rational design strategy for high‐performance CO ₂ reduction materials.