Synergistic Interplay of Ni Single Atoms and Neighboring Mn ₂ Dual Atoms Enabling Selective Photocatalytic Reduction of CO ₂ to Propane

Abstract The photocatalytic conversion of CO 2 and H 2 O into long carbon chain products (C n , n ≥ 3) presents a sustainable strategy for synthesizing high‐value fuels and chemicals. However, the synthesis of long carbon chain products under mild conditions still faces great challenges, largely due to sluggish multi‐electron/proton transfer kinetics and the thermodynamically unfavorable C 1 –C 1 and C 1 –C 2 coupling processes. In this study, we developed tri‐metal active sites composed of Ni single atoms and Mn 2 dual atoms anchored on NH 2 ‐MIL‐125(Ti) (Ni 1 /Mn 2 ‐MIL) for synergistic photocatalytic C 3 H 8 production. The synthesized Ni 1 /Mn 2 ‐MIL catalyst achieved efficient CO 2 photoreduction (CO 2 PR) in pure water, yielding 32.2 µmol g −1 h −1 of C 3 H 8 with 81.3% electron‐based selectivity, significantly outperforming Ni 1 ‐MIL and Mn 2 ‐MIL. Remarkably, the catalyst exhibited exceptional stability over 50 cycles without degradation. Integrated experimental and theoretical investigations revealed that the Ni 1 site activates CO 2 to form CO, while the adjacent Mn 2 site promotes the formation of *COCHO intermediates. Strong electronic interactions between Ni 1 and Mn 2 create charge‐polarized active sites, which mitigate electrostatic repulsion between C 1 and C 2 intermediates, thereby promoting C–C coupling and subsequent formation of the *CH 2 OCOCO intermediates. Consequently, both the selectivity and catalytic efficiency toward C 3 H 8 production are significantly enhanced.