Direct low concentration CO₂ electroreduction to multicarbon products via rate-determining step tuning

Direct converting low concentration CO₂ in industrial exhaust gases to high-value multi-carbon products via renewable-energy-powered electrochemical catalysis provides a sustainable strategy for CO₂ utilization with minimized CO₂ separation and purification capital and energy cost. Nonetheless, the electrocatalytic conversion of dilute CO₂ into value-added chemicals (C₂₊ products, e.g., ethylene) is frequently impeded by low CO₂ conversion rate and weak carbon intermediates’ surface adsorption strength. Here, we fabricate a range of Cu catalysts comprising fine-tuned Cu(111)/Cu₂O(111) interface boundary density crystal structures aimed at optimizing rate-determining step and decreasing the thermodynamic barriers of intermediates’ adsorption. Utilizing interface boundary engineering, we attain a Faradaic efficiency of (51.9 ± 2.8) % and a partial current density of (34.5 ± 6.4) mA·cm⁻² for C₂₊ products at a dilute CO₂ feed condition (5% CO₂ v/v), comparing to the state-of-art low concentration CO₂ electrolysis. In contrast to the prevailing belief that the CO₂ activation step ( \({{CO}}_{2}+{e}^{-}+\, * \,\to {}^{ * }{CO}_{2}^{-}\) ${CO}_2+e^{-}+*\to {}^{*}CO_2^{-}$ ) governs the reaction rate, we discover that, under dilute CO₂ feed conditions, the rate-determining step shifts to the generation of *COOH ( \({}^{ * } {{CO}}_{2}^{-}+{H}_{2}O\to {}^{ * } {COOH}+{{OH}}^{-}({aq})\) ${}^{*}CO_2^{-}+H_{2}O\to {}^{*}COOH+{OH}^{-}\left(aq\right)$ ) at the Cu⁰/Cu¹⁺ interface boundary, resulting in a better C₂₊ production performance.