Restructured Three‐Coordinated Ni─Se Catalytic Sites for Enhanced Cross‐Condensation of Methanol and Ethanol

Abstract The cross‐condensation of methanol (MeOH) and ethanol (EtOH) offers a promising, carbon‐neutral pathway for the production of higher alcohols (HAS) from both CO 2 and biomass resources. However, this process is often hampered by the low efficiency of C 5+ alcohol (C 5+ OH) synthesis, high catalyst production costs, and limited water tolerance. Here, we report for the first time a low‐cost, high‐performance Ni‐based catalyst synthesized via a precise surface selenization protocol that effectively overcomes these limitations. The optimized catalyst significantly outperforms noble metal catalysts, achieving a total alcohol yield of 62.6% and a high selectivity of 83.8% for HAS (62.0% for C 5+ OH) in the cross‐condensation of MeOH and EtOH. Our characterizations and theoretical simulations indicate that Se doping restructures the Ni surface, creating three‐coordinated Ni─Se sites. These sites promote efficient alcohol dehydrogenation and raise the energy barrier for aldehyde decomposition, thereby greatly increasing the efficiency and selectivity of MeOH and EtOH cross‐condensation to C 5+ OH.