Affiliation:
1. Department of Materials Science and Engineering Centre for Atomic Engineering of Advanced Materials Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education Key Laboratory of Functional Inorganic Material Chemistry of Anhui Province Anhui University Hefei 230601 China
2. CAS Key Laboratory of Materials for Energy Conversion Department of Materials Science and Engineering iChEM University of Science and Technology of China Hefei Anhui 230026 China
3. Anhui Tongyuan Environment Energy Saving Co. Ltd. Hefei 230041 China
Abstract
AbstractHigh 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 ⋅ gcat−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.