Enhancing CO2 Electroreduction Precision to Ethylene and Ethanol: The Role of Additional Boron Catalytic Sites in Cu-Based Tandem Catalysts.

Abstract

The electrocatalytic conversion of carbon dioxide (CO2) into valuable multicarbon (C2+) compounds offers a promising approach to mitigate CO2 emissions and harness renewable energy. However, achieving precise selectivity for specific C2+ products, such as ethylene and ethanol, remains a formidable challenge. This study shows that incorporating elemental boron (B) into copper (Cu) catalysts provides additional adsorption sites for *CO intermediates, enhancing the selectivity of desirable C2+ products. Additionally, using a nickel single-atom catalyst (Ni-SAC) as a *CO source increases local *CO concentration and reduces the hydrogen evolution reaction. In situ experiments and density functional theory (DFT) calculations reveal that surface-bound boron units adsorb and convert *CO more efficiently, promoting ethylene production, while boron within the bulk phase of copper influences charge transfer, facilitating ethanol generation. In a neutral electrolyte, the bias current density for ethylene production using the B-O-Cu2@Ni-SAC0.05 hybrid catalyst exceeded 300 mA cm-2, and that for ethanol production with B-O-Cu5@Ni-SAC0.2 surpassed 250 mA cm-2. This study underscores that elemental doping in Cu-based catalysts not only alters charge and crystalline phase arrangements at Cu sites but also provides additional reduction sites for coupling reactions, enabling the efficient synthesis of distinct C2+ products.