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

Direct converting low concentration CO in industrial exhaust gases to high-value multi-carbon products via renewable-energy-powered electrochemical catalysis provides a sustainable strategy for CO utilization with minimized CO separation and purification capital and energy cost. Nonetheless, the electrocatalytic conversion of dilute CO into value-added chemicals (C products, e.g., ethylene) is frequently impeded by low CO conversion rate and weak carbon intermediates' surface adsorption strength. Here, we fabricate a range of Cu catalysts comprising fine-tuned Cu(111)/CuO(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 for C products at a dilute CO feed condition (5% CO v/v), comparing to the state-of-art low concentration CO electrolysis. In contrast to the prevailing belief that the CO activation step ( ) governs the reaction rate, we discover that, under dilute CO feed conditions, the rate-determining step shifts to the generation of *COOH ( ) at the Cu/Cu interface boundary, resulting in a better C production performance.