The electrochemical production of carbon monoxide (CO) from carbon dioxide (CO2) has conventionally relied on gas-phase CO2 electrolysis with complex upstream capture and downstream gas separation processes. Reactive capture of CO2 – an integrated approach that combines CO2 capture and electrochemical conversion – uses chemisorbed CO2 directly as the feedstock and thereby avoids CO2 purification and associated costs.To date, reactive capture has relied on hydroxide-based capture solutions (e.g. potassium hydroxide (KOH)) suitable for direct air capture (DAC) processes or amines (e.g. monoethanolamine (MEA)) that have been conventionally used for point source capture. However, in hydroxide-based systems that capture CO2 in the form of carbonate, the CO Faradaic efficiency (FE) is limited to 50% due to the interaction between in-situ regenerated CO2 and local hydroxides that reduce CO2 availability at the cathode. Amine-based reactive capture can overcome this selectivity challenge when CO2 is captured in the form of carbamate and bicarbonate; compared to carbonate, these forms of chemisorbed CO2 require less electron-coupled protons to regenerate in-situ CO2, and thus yield more CO2 at the cathode. However, conventional amines are volatile and have poor oxygen tolerance, rendering them inapplicable to oxygen-rich CO2-lean conditions.Here, we report amino acid salt (AAS)-based reactive capture of CO2 that exceeds the CO energy efficiency (EE) achieved in amine- and hydroxide- based systems. The AAS capture solution, potassium glycinate (K-GLY), contains amino functional groups for efficient CO2 capture while offering advantages including oxygen tolerance, low vapor pressure, and low toxicity. We synthesized a nickel single atom (Ni-N/C) catalyst to improve conversion efficiency, optimized the capture solution composition to reduce the electrolysis overpotential at high current densities, and elevated the operating temperature and pressure to increase availability of dissolved in-situ CO2 at the cathode. We achieve CO production with 64% CO FE and a measured full cell voltage of 2.74 V at 50 mA cm-2, resulting in an CO EE of 31% and an energy intensity of 40 GJ tCO-1. The feasibility of the full reactive capture process was demonstrated with both simulated flue gas and direct air input.
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