Dual‐Fluorinated Ni Single Atom Catalyst for Efficient Artificial Photosynthetic Diluted CO2 Reduction

Abstract The development of efficient photocatalysts to convert dilute CO 2 from flue gas into high value‐added products is a promising approach to achieving carbon neutrality. In this work, a dual‐fluorinated Ni single atom photocatalyst is reported for the photoreduction of diluted CO 2 to CO. Under a dilute CO 2 (10%) atmosphere, TPB‐SA2F‐Ni achieves the highest reported CO yield (30344.4 µmol g −1 h −1 ) among heterogeneous catalytic systems with a CO selectivity of 98%. Kevin probe force microscopy and photoelectrochemical characterizations indicate that dual‐fluorination strategy enhances photoexcited electron transfer between the photosensitizer and photocatalyst by optimizing the conjugated electronic structure. Pore size distribution and CO 2 adsorption experiments show that the uniform microporous structure induced by the dual‐F site further enhanced the ability of the Ni‐N 2 O 2 active site to capture CO 2 molecules. Density functional theory calculations indicate that the high CO yield of TPB‐SA2F‐Ni stems from a lowered energy barrier for *COOH intermediate formation.