Optimizing CO₂-Loaded Aqueous Amine Solutions for Higher Electrocatalytic CO₂ Reduction Activity

The activity of aqueous-based carbon dioxide reduction (CO₂R) reactions is often limited by the solubility of CO₂. The addition of amines can increase the total dissolved carbon in water through the formation of bicarbonate and carbamate species, which has been used to a great effect to capture CO₂ from dilute streams. In this study, we explore the effect of 12 primary and secondary amines of varying Brønsted basicity, steric profile, and hydrogen-bonding capabilities on the aqueous CO₂R to CO activity of a molecular Ni(cyclam)Cl₂ catalyst with a Hg electrode. Addition of some of the amines results in greater activity and selectivity for CO production compared to equivalent aqueous solutions without added amines. Under optimal conditions (0.4 M 3-amino-propionitrile), there is an over sevenfold increase in partial current density and greater selectivity for CO compared to equivalent conditions with no amine. Interestingly, the increase in activity did not correlate to any single property across the 12 amines. To elucidate the effect of the amine additives on catalysis, we used vapor-liquid equilibrium modeling (VLE), ¹³C NMR spectroscopy, and computational analysis to determine the carbon speciation of the solutions. These results indicate that for amines without ethylalcohol functionalities, CO₂R activity correlates with carbamate concentration, which is in turn governed by amine basicity and steric effects. However, this correlation does not persist for amines with ethylalcohol functionalities, which can form more stable carbamates through intramolecular-hydrogen bonding. These studies demonstrate that amine additives can enhance aqueous CO₂R activity and selectivity and describe amine properties that lead to these higher performance metrics.