Tailoring the Hydrophobic Interface of Core–Shell HKUST‐1@Cu2O Nanocomposites for Efficiently Selective CO2 Electroreduction

The electrochemical reduction of carbon dioxide (CO2) to ethylene creates a carbon‐neutral approach to converting carbon dioxide into intermittent renewable electricity. Exploring efficient electrocatalysts with potentially high ethylene selectivity is extremely desirable, but still challenging. In this report, a laboratory‐designed catalyst HKUST‐1@Cu2O/PTFE‐1 is prepared, in which the high specific surface area of the composites with improved CO2 adsorption and the abundance of active sites contribute to the increased electrocatalytic activity. Furthermore, the hydrophobic interface constructed by the hydrophobic material polytetrafluoroethylene (PTFE) effectively inhibits the occurrence of hydrogen evolution reactions, providing a significant improvement in the efficiency of CO2 electroreduction. The distinctive structures result in the remarkable hydrocarbon fuels generation with high Faraday efficiency (FE) of 67.41%, particularly for ethylene with FE of 46.08% (−1.0 V vs RHE). The superior performance of the catalyst is verified by DFT calculation with lower Gibbs free energy of the intermediate interactions with improved proton migration and selectivity to emerge the polycarbon（C2+） product. In this work, a promising and effective strategy is presented to configure MOF‐based materials with tailored hydrophobic interface, high adsorption selectivity and more exposed active sites for enhancing the efficiency of the electroreduction of CO2 to C2+ products with high added value. Elaborate design of core–shell catalyst HKUST‐1@Cu2O/PTFE‐1 with hydrophobic interface exhibits outstanding electrocatalytic activities for hydrocarbon fuels with high Faraday efficiency of 67.41% in CO2 electroreduction, benefiting from the improved CO2 adsorption, the abundance of synergistic active sites and blocking the supply of protons and electrons to inhibit HER.