Benzyl alcohol promoted electrocatalytic reduction of carbon dioxide and C2 production by Cu2O/Cu

Oxide-derived copper (OD-Cu)-based materials containing Cuδ+ (0 < δ ≤ 1) have been considered as promising electrocatalysts for electrochemical CO2 reduction reaction (ECO2RR) to produce valuable C2 products, which, however, suffer from poor stability, mainly due to the inevitable reduction of Cuδ+. We report here that the benzyl alcohol (BA) introduced in catholyte presents a markedly positive effect on the durability and C2 selectivity enhancement of ECO2RR when OD-Cu-based material is adopted as cathode electrocatalyst. The critical evidence of ECO2RR intermediates has been provided by in situ Raman and FTIR spectroscopy, which reveals the surface mechanisms of BA-assisted ECO2RR over OD-Cu catalysts. On the one hand, the introduction of BA increases the CO2 supply for ECO2RR by slowing down its neutralizing reaction, which results in the increased intermediate species coverage on the catalytic surface therefore the delayed self-reduction of Cuδ+; On the other hand, the interaction between BA and the intermediate species *CO during ECO2RR brings an enhanced selectivity of C2 products (FE C2 = 85.5 % at −1.38 V vs RHE). Besides, an energy-savings and economic electrolyzer can be achieved by coupling anodic BA oxidation reaction to benzoic acid and ECO2RR to C2 products with much lowered cell voltages.