Establishment of Gas–Liquid–Solid Interface on Multilevel Porous Cu<sub>2</sub>O for Potential-Driven Selective CO<sub>2</sub> Electroreduction toward C<sub>1</sub> or C<sub>2</sub> Products
Changjiang Liu, Hu Zang, Xin Liu, Haiyan Lu, Nan Yu, Baoyou Geng
Abstract
Copper-based catalysts demonstrate distinctive multicarbon product activity in the CO 2 electroreduction reaction (CO 2 RR); however, their low selectivity presents significant challenges for practical applications. Herein, we have developed a multilevel porous spherical Cu 2 O structure, wherein the mesopores are enriched with catalytic active sites and effectively stabilize Cu +, while the macropores facilitate the formation of a “gas–liquid–solid” three-phase interface, thereby creating a microenvironment with an increasing water concentration gradient from the interior to the exterior. Potential-driven phase engineering and protonation synergistically optimize the reaction pathway, facilitating a switch between CO and C 2 H 4 . At a low current density of 100 mA cm –2, the faradaic efficiency (FE) for CO reaches an impressive 96.97%. When the current density increases to 1000 mA cm –2, FE C2H4 attains 53.05%. Experiments and theoretical calculations indicate that at lower potentials, the pure Cu 2 O phase diminishes the adsorption of *CO intermediates, while weak protonation inhibits hydrogen evolution reactions, thereby promoting CO production. Conversely, at more negative potentials, the Cu 0 /Cu + interface and strong protonation generate locally elevated concentrations of *CO and *COOH intermediates, which enhance C–C coupling and deep hydrogenation, ultimately improving selectivity toward C 2+ products. This study provides novel insights into the rational design of copper-based catalysts for customizable CO 2 electroreduction products.