Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO2 Reduction to CnH2n+1OH (n=1, 2)

Efficient synthesis of CnH2n+1OH (n=1, 2) via photochemical CO2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare‐earth dual single atoms (SAs) catalysts containing ErN6 and NdN6 moieties, fabricated via an atom‐confinement and coordination method. The dual Er‐Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g–1 h–1 and 987.7 μmol g–1 h–1 for CH3CH2OH and CH3OH, respectively. Through a combination of theoretical calculation, X‐ray absorption near edge structural analysis, aberration‐corrected transmission electron microscopy, and in‐situ FT‐IR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C−C bond formation, while Nd SAs provide the necessary *CO for C−C coupling in C2H5OH synthesis under visible light. Furthermore, the experiment and density functional theory calculation elucidate that the variety of electronic states induced by 4f orbitals of the Er SAs and the p−f orbital hybridization of Er−N moieties enable the formation of charge‐transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO2 to CnH2n+1OH (n=1, 2) via a novel rare‐earth‐based dual SAs photocatalysis approach.