V‐Doped Cu2Se Hierarchical Nanotubes Enabling Flow‐Cell CO2 Electroreduction to Ethanol with High Efficiency and Selectivity

Abstract CO 2 electrocatalytic reduction (CO 2 ER) to multicarbon (C 2+ ) products is heavily pursued because of their commercial values, and the efficiency and selectivity have both attracted tremendous attention. A flow‐cell is a device configuration that can greatly enhance the conversion efficiency but requires catalysts to possess high electrical conductivity and gas permeability; meanwhile, the catalysts should enable the reaction pathway to specific products. Herein, it is reported that V‐doped Cu 2 Se nanotubes with a hierarchical structure can be perfectly compatible with flow‐cells and fulfil such a task, achieving CO 2 electroreduction to ethanol with high efficiency and selectivity. As revealed by the experimental characterization and theoretical calculation, the substitutional vanadium doping alters the local charge distribution of Cu 2 Se and diversifies the active sites. The unique active sites promote the formation of bridge *CO B and its further hydrogenation to *COH, and, as such, the subsequent coupling of *COH and *CO L eventually generates ethanol. As a result, the optimal Cu 1.22 V 0.19 Se nanotubes can electrocatalyze CO 2 to ethanol with a Faradaic efficiency of 68.3% and a partial current density of −207.9 mA cm −2 for the single liquid product of ethanol at −0.8 V in a flow‐cell. This work provides insights into the materials design for steering the reaction pathway toward C 2+ products, and opens an avenue for flow‐cell CO 2 ER toward a single C 2+ liquid fuel.