Restructured Three‐Coordinated Ni─Se Catalytic Sites for Enhanced Cross‐Condensation of Methanol and Ethanol
Juwen Gu, Qian Zhang, Yujian Fan, Guangyu Chen, Jiawei Li, Songbai Qiu, Tiejun Wang, Tian Sheng, Yujie Xiong
Abstract
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.