Restructuring of Cu2O to Cu2O@Cu-Metal–Organic Frameworks for Selective Electrochemical Reduction of CO2

Electrochemical reduction of carbon dioxide to hydrocarbons, driven by renewable power sources, is a fascinating and clean way to remedy greenhouse gas emission as a result of overdependence on fossil fuels and produce value-added fine chemicals. The Cu-based catalysts feature unique superiorities; nevertheless, achieving high hydrocarbon selectivity is still inhibited and remains a great challenge. In this study, we report on a tailor-made multifunction-coupled Cu-metal-organic framework (Cu-MOF) electrocatalyst by time-resolved controllable restructuration from Cu₂O to Cu₂O@Cu-MOF. The restructured electrocatalyst features a time-responsive behavior and is equipped with high specific surface area for strong adsorption capacity of CO₂ and abundant active sites for high electrocatalysis activity based on the as-produced MOF on the surface of Cu₂O, as well as the accelerated charge transfer derived from the Cu₂O core in comparison with the Cu-MOF. These intriguing characteristics finally lead to a prominent performance towards hydrocarbons, with a high hydrocarbon Faradaic efficiency (FE) of 79.4%, particularly, the CH₄ FE as high as 63.2% (at -1.71 V). This work presents a novel and efficient strategy to configure MOF-based materials in energy and catalysis fields, with a focus on big surface area, high adsorption ability, and much more exposed active sites.