Precisely Regulating Asymmetric Charge Distribution by Single‐Atom Central Doped Ag‐Based Series Clusters for Enhanced Photoreduction of CO2 to Alcohol Fuels

Abstract High efficiently photocatalytic CO 2 reduction (CO 2 RR) into liquid fuels in pure water system remains challenged. Iron polyphthalocyanine (FePPc) with strong light harvesting, unique Fe‐N 4 structure, abundant pores, and good stability could serve as a promising catalyst for CO 2 photoreduction. To further improve the catalytic efficiency, herein, symmetry‐breaking Fe sites are constructed by coupling with atomically precise M 1 Ag 24 (M=Ag, Au, Pt) series clusters. Especially, the introduction of Pt 1 Ag 24 causes the most asymmetric charge distribution of Fe in FePPc (followed by Au 1 Ag 24 and Ag 25 ), leading to the favorable CO 2 adsorption and activation. In addition, Pt 1 Ag 24 ‐FePPc exhibits the most effective photogenerated carriers transfer and separation. As a result, Pt 1 Ag 24 ‐FePPc shows the methanol/ethanol yield of 48.55/32.97 μmol ⋅ g cat −1 ⋅ h −1 in H 2 O‐CO 2 system under visible light irradiation, ~1.65/1.25‐fold, 1.83/1.37‐fold, and 3.60/1.61‐fold higher than that of Au 1 Ag 24 ‐FePPc, Ag 25 ‐FePPc, and FePPc, respectively. This work provides a concept for precisely construction and regulation symmetry‐breaking sites of cluster‐based catalysts for effective CO 2 conversion.