Lithiation‐Enabled High‐Density Nitrogen Vacancies Electrocatalyze CO₂ to C₂ Products

Abstract Electrochemical CO₂ reduction to produce valuable C₂ products is attractive but still suffers with relatively poor selectivity and stability at high current densities, mainly due to the low efficiency in the coupling of two *CO intermediates. Herein, it is demonstrated that high‐density nitrogen vacancies formed on cubic copper nitrite (Cu₃N_x) feature as efficient electrocatalytic centers for CO–CO coupling to form the key OCCO* intermediate toward C₂ products. Cu₃N_x with different nitrogen densities are fabricated by an electrochemical lithium tuning strategy, and density functional theory calculations indicate that the adsorption energies of CO* and the energy barriers of forming key C₂ intermediates are strongly correlated with nitrogen vacancy density. The Cu₃N_x catalyst with abundant nitrogen vacancies presents one of the highest Faradaic efficiencies toward C₂ products of 81.7 ± 2.3% at −1.15 V versus reversible hydrogen electrode (without ohmic correction), corresponding to the partial current density for C₂ production as −307 ± 9 mA cm⁻². An outstanding electrochemical stability is also demonstrated at high current densities, substantially exceeding CuO_x catalysts with oxygen vacancies. The work suggests an attractive approach to create stable anion vacancies as catalytic centers toward multicarbon products in electrochemical CO₂ reduction.