Electrochemical reduction of CO2 (CO2RR) is a promising technology to couple excess renewable power with CO2 emissions mitigation. One of the main challenges in CO2 electroreduction is low CO2 solubility in aqueous electrolytes (34 mM), which has motivated ongoing research of novel electrolytes for improved CO2 solubility. Nanoparticle Organic Hybrid Materials (NOHMs)-based electrolytes have significantly enhanced CO2 solubilities compared to conventional aqueous electrolytes and distinct reactivity for the CO2RR, making them promising for combined CO2 capture and conversion. They have tunable transport properties, excellent thermal and electrochemical stability and the ability to mediate electrodeposition reactions. To elucidate the role of NOHMs in the CO2 conversion mechanism, EC-AFM was employed to discern the surface topology and electrochemical environments near the electrode surface in electrolytes based on NOHMs with an amine-functionalized polymeric canopy during operando CO2RR. Coupled with bulk electrolysis and SEM analysis, this study provides insights into the mechanism of CO2RR in this system, guiding the design of NOHMs and other novel electrolytes for reactive CO2 capture and conversion.
