Lewis Acidic Support Boosts C-C Coupling in the Pulsed Electrochemical CO₂ Reaction

Copper-oxide electrocatalysts have been demonstrated to effectively perform the electrochemical CO₂ reduction reaction (CO₂RR) toward C₂₊ products, yet preserving the reactive high-valent CuO has remained elusive. Herein, we demonstrate a model system of Lewis acidic supported Cu electrocatalyst with a pulsed electroreduction method to achieve enhanced performance for C₂₊ products, in which an optimized electrocatalyst could reach ∼76% Faradaic efficiency for C₂₊ products (FE_C) at ∼-0.99 V versus reversible hydrogen electrode, and the corresponding mass activity can be enhanced by ∼2 times as compared to that of conventional CuO. In situ time-resolved X-ray absorption spectroscopy investigating the dynamic chemical/physical nature of Cu during CO₂RR discloses that an activation process induced by the KOH electrolyte during pulsed electroreduction greatly enriched the Cu^δ+O/Zn^δ+O interfaces, which further reveals that the presence of Zn^δ+O species under the cathodic potential could effectively serve as a Lewis acidic support for preserving the Cu^δ+O species to facilitate the formation of C₂₊ products, and the catalyst structure-property relationship of Cu^δ+O/Zn^δ+O interfaces can be evidently realized. More importantly, we find a universality of stabilizing Cu^δ+O species for various metal oxide supports and to provide a general concept of appropriate electrocatalyst-Lewis acidic support interaction for promoting C₂₊ products.