Constructing f-p-d Orbital Coupling Using Cu-Doped Frustrated Lewis Acid–Base Pairs in CeO ₂ to Boost CO ₂ Electroreduction

The direct electrocatalytic conversion of carbon dioxide to methane using water as a medium is a reliable way to store intermittent renewable energy and solve environmental problems. However, in such multielectron/proton transfer reactions, the role of water is often overlooked. Specifically, the sluggish kinetics of water dissociation limit the effective proton supply during methane formation. Here, we propose a copper-doped CeO2 catalyst with frustrated Lewis pairs (FLPs), which can effectively reduce carbon dioxide to methane. Combined experimental analysis and theoretical calculations reveal that the synergistic interaction between Cu and FLPs forms an f-p-d gradient orbital coupling system, which significantly promotes water dissociation to generate active protons and optimizes the adsorption behavior of the *H and *COOH intermediates. Even at the large current density of −273 mA cm–2, the Faraday efficiency of Cu/CeO2-FLPs for methane was as high as 78.0%, with a conversion frequency of 15784.1 h–1 in the flow cell. This work provides a strategy for the rational design of efficient multipoint catalytic systems.