Modulating the localized electronic distribution of Cu species during reconstruction for enhanced electrochemical CO2 reduction to C2+ products

Abstract

Electrochemical conversion of carbon dioxide (CO₂RR) into high-value multi-carbon (C₂₊) chemicals and fuels is of great significance for carbon neutrality, and so far Cu-based materials are still the dominant electrocatalysts with practical application potential for C₂₊ products during the CO₂RR. However, Cu-based catalysts usually face problems such as an unstable valence state and lattice structure, low efficiency, and a narrow potential window for C₂₊ products which affect the comprehensive performance of the catalysts. Herein, we develop a simple co-precipitation-hydrothermal method for introducing zirconium dioxide (ZrO₂) into copper oxide (CuO) to improve the selectivity of C₂₊ products via in situ reconstruction. The optimized CuO–ZrO₂-1.0 catalyst exhibits a high faradaic efficiency of 82.3% for C₂₊ products with an industrial partial current density over 200 mA cm⁻², which presents a more than 1.7-fold improvement compared to that of CuO, also exceeding that of lots of Cu-based catalysts previously reported. DFT and in situ characterization studies reveal that the introduction of ZrO₂ can induce the electronic distribution and stabilize the Cu⁺ species during the in situ reconstruction process which contributes to moderate adsorption and enhanced coupling of *CO intermediates to obtain C₂₊ products.