Non‐Interacting Ni and Fe Dual‐Atom Pair Sites in N‐Doped Carbon Catalysts for Efficient Concentrating Solar‐Driven Photothermal CO2 Reduction

Abstract Solar‐to‐chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO 2 reduction. Herein, a new concentrated solar‐driven photothermal system coupling a dual‐metal single‐atom catalyst (DSAC) with adjacent Ni−N 4 and Fe−N 4 pair sites is designed for boosting gas‐solid CO 2 reduction with H 2 O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO 2 reduction to CO (86.16 μmol g −1 h −1 ), CH 4 (135.35 μmol g −1 h −1 ) and CH 3 OH (59.81 μmol g −1 h −1 ), which are equivalent to 1.70‐fold, 1.27‐fold and 1.23‐fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d‐band center of Fe atom is efficiently regulated in non‐interacting Ni and Fe dual‐atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO 3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO 3 pathways) for solar‐driven photothermal CO 2 reduction to initial CO production.