Quasi-graphitic carbon shell-induced Cu confinement promotes electrocatalytic CO₂ reduction toward C₂₊ products

For steady electroconversion to value-added chemical products with high efficiency, electrocatalyst reconstruction during electrochemical reactions is a critical issue in catalyst design strategies. Here, we report a reconstruction-immunized catalyst system in which Cu nanoparticles are protected by a quasi-graphitic C shell. This C shell epitaxially grew on Cu with quasi-graphitic bonding via a gas–solid reaction governed by the CO (g) - CO₂ (g) - C (s) equilibrium. The quasi-graphitic C shell-coated Cu was stable during the CO₂ reduction reaction and provided a platform for rational material design. C₂₊ product selectivity could be additionally improved by doping p-block elements. These elements modulated the electronic structure of the Cu surface and its binding properties, which can affect the intermediate binding and CO dimerization barrier. B-modified Cu attained a 68.1% Faradaic efficiency for C₂H₄ at −0.55 V (vs RHE) and a C₂H₄ cathodic power conversion efficiency of 44.0%. In the case of N-modified Cu, an improved C₂₊ selectivity of 82.3% at a partial current density of 329.2 mA/cm² was acquired. Quasi-graphitic C shells, which enable surface stabilization and inner element doping, can realize stable CO₂-to-C₂H₄ conversion over 180 h and allow practical application of electrocatalysts for renewable energy conversion.