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.