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

High efficiently photocatalytic CO₂ reduction (CO₂RR) into liquid fuels in pure water system remains challenged. Iron polyphthalocyanine (FePPc) with strong light harvesting, unique Fe-N₄ structure, abundant pores, and good stability could serve as a promising catalyst for CO₂ photoreduction. To further improve the catalytic efficiency, herein, symmetry-breaking Fe sites are constructed by coupling with atomically precise M₁Ag₂₄ (M=Ag, Au, Pt) series clusters. Especially, the introduction of Pt₁Ag₂₄ causes the most asymmetric charge distribution of Fe in FePPc (followed by Au₁Ag₂₄ and Ag₂₅), leading to the favorable CO₂ adsorption and activation. In addition, Pt₁Ag₂₄-FePPc exhibits the most effective photogenerated carriers transfer and separation. As a result, Pt₁Ag₂₄-FePPc shows the methanol/ethanol yield of 48.55/32.97 μmol ⋅ g_cat ^-1 ⋅ h^-1 in H₂O-CO₂ 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 Au₁Ag₂₄-FePPc, Ag₂₅-FePPc, and FePPc, respectively. This work provides a concept for precisely construction and regulation symmetry-breaking sites of cluster-based catalysts for effective CO₂ conversion.