Localized mass transport channels for electro-upgrade of dilute CO2 toward high-yield C2+ products

Electrocatalytic upgrade of CO ₂ offers a promising approach for the recycling of global CO ₂ emissions, facilitating the achievement of carbon neutrality. Nevertheless, the purification of CO ₂ is costly and direct utilization of practical dilute CO ₂ is urgently important yet rather difficult. The main challenge for continuous electrocatalysis of dilute CO ₂ is to balance the reaction kinetics and mass transport of CO ₂ to the catalytic sites, which is hindered by the large mass transport resistance. Herein, we propose coordinating the local environment and active catalyst by constructing covalent organic frameworks (COF) on single-atomic In-doped Cu ₂ O (In ₁ @Cu ₂ O) for a high tolerance of CO ₂ inlet concentrations (15–100%). The optimized amounts of COF functionalized by the trifluoromethyl group act as the local CO ₂ /CO diffusion channels via steric confinement effects and C∙∙∙F electronic effects. Besides, the formation of key intermediates for C ₂₊ products is greatly facilitated by the promoted COOH adsorption. Hence, a total current of 81.7 A is realized in a 4×100 cm ² electrolyzer stack with over 770 mmol/h C ₂₊ products at an inlet of dilute CO ₂ . Such new electrode architecture sheds light on the high-yield electrochemical conversion using dilute CO ₂ at the potential industrial scale for practical applications.