Ultrastable Cu Catalyst for CO2 Electroreduction to Multicarbon Liquid Fuels by Tuning C–C Coupling with CuTi Subsurface

• Published in: Angewandte Chemie International Edition 2021-12, Vol.60 (50), p.26122-26127
• Main Authors: Hu, Fei, Yang, Li, Jiang, Yawen, Duan, Chongxiong, Wang, Xiaonong, Zeng, Longjiao, Lv, Xuefeng, Duan, Delong, Liu, Qi, Kong, Tingting, Jiang, Jun, Long, Ran, Xiong, Yujie
• Format: Article
• Language: English
• Subjects: Amorphous alloys; Butanol; Carbon dioxide; Catalysts; CO2 reduction; Couplings; C–C coupling; Dimerization; electrocatalysis; Electrocatalysts; Electron density; Ethanol; Fuels; Intermediates; Liquid fuels; multicarbon products; Reaction intermediates; Reduction
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202110303

Production of multicarbon (C2+) liquid fuels is a challenging task for electrocatalytic CO2 reduction, mainly limited by the stabilization of reaction intermediates and their subsequent C−C couplings. In this work, we report a unique catalyst, the coordinatively unsaturated Cu sites on amorphous CuTi alloy (a‐CuTi@Cu) toward electrocatalytic CO2 reduction to multicarbon (C2‐4) liquid fuels. Remarkably, the electrocatalyst yields ethanol, acetone, and n‐butanol as major products with a total C2‐4 faradaic efficiency of about 49 % at −0.8 V vs. reversible hydrogen electrode (RHE), which can be maintained for at least 3 months. Theoretical simulations and in situ characterization reveals that subsurface Ti atoms can increase the electron density of surface Cu sites and enhance the adsorption of *CO intermediate, which in turn reduces the energy barriers required for *CO dimerization and trimerization. The coordinatively unsaturated Cu sites on amorphous CuTi alloy enable electrocatalytic CO2 reduction to multicarbon liquid fuels including ethanol, acetone and n‐butanol with a total C2‐4 faradaic efficiency of about 49 % at −0.8 V vs. reversible hydrogen electrode (RHE).