Mechanistic Insights into the Formation of Hydroxyacetone, Acetone, and 1,2-Propanediol from Electrochemical CO(2) Reduction on Copper

[Image: see text] Studies focused on the mechanism of CO(2) electroreduction (CO(2)RR) aim to open up opportunities to optimize reaction parameters toward selective synthesis of desired products. However, the reaction pathways for C(3) compound syntheses, especially for minor compounds, remain incompletely understood. In this study, we investigated the formation pathway for hydroxyacetone, acetone, and 1,2-propanediol through CO((2))RR, which are minor products that required long electrolysis times to be detected. Our proposed reaction mechanism is based on a systematic investigation of the reduction of several functional groups on a Cu electrode, including aldehydes, ketones, ketonealdehydes, hydroxyls, hydroxycarbonyls, and hydroxydicarbonyls, as well as the coupling between CO and C(2)-dicarbonyl (glyoxal) or C(2)-hydroxycarbonyl (glycolaldehyde). This study allowed us to derive the fundamental principles of the reduction of functional groups on Cu electrodes. Our findings suggest that the formation of ethanol does not follow the glyoxal pathway, as previously suggested but instead likely occurs via the coupling of CH(3)* and CO. For the C(3) compounds, our results suggest that 1,2-propanediol and acetone follow the hydroxyacetone pathway during CO(2)RR. Hydroxyacetone is likely formed through the coupling of CO and a C(2)-hydroxycarbonyl intermediate, such as a glycolaldehyde-like compound, as confirmed by adding glycolaldehyde to the CO((2))-saturated solution. This finding is consistent with CO(2)RR product distribution, as glycolaldehyde formation during CO(2)RR is limited, which, in turn, limits hydroxyacetone production. Our study contributes to a better understanding of the reaction mechanism for hydroxyacetone, acetone, and 1,2-propanediol synthesis from CO(2)RR and gives insights into these interesting compounds that may be formed electrochemically.