Electrochemical CO₂ reduction in non-aqueous solvents is promising due to the increased CO₂ solubility of organic-based electrolytes compared to aqueous electrolytes. Here the effect of nine different salts in propylene carbonate (PC) on the CO₂ reduction product distribution of polycrystalline Cu is investigated. Three different cations (tetraethylammonium (TEA), tetrabutylammonium (TBA), and tetrahexylammonium (THA)) and three different anions (chloride (Cl), tetrafluoroborate (BF₄), and hexafluorophosphate (PF₆)) were used. Chronoamperometry and in-situ FTIR measurements show that the size of the cation has a crucial role in the selectivity. A more hydrophobic surface is obtained when employing a larger cation with a weaker hydration shell. This stabilizes the CO₂⁻ radical and promotes the formation of ethylene. CO₂ reduction in 0.7 M THACl/PC shows the highest hydrocarbon formation. Lastly, we hypothesize that the hydrocarbon formation pathway is not through C−C coupling, as the CO solubility in PC is very high, but through the dimerization of the COH intermediate.

Herein, we describe a study of the electrochemical reduction of oxalic and glyoxylic acids toward a feasible green and sustainable production of tartaric acid in aqueous and/or acetonitrile solvent using silver and lead electrodes. Our results show that on the silver electrode, for both oxalic acid and glyoxylic acid, the reduction reaction is more favorable toward the dimerization step, leading to tartaric acid, due to the increase in the local pH, while on the lead electrode, the step involving the protonation of the intermediate is more favorable, leading to the formation of glycolate. Techno-economic analysis shows that tartaric acid production from glyoxylic acid and from oxalic acid via electrochemical synthesis can be a potential process at the industrial scale. In the present case, the oxygen evolution reaction was chosen as the reaction at the other electrode for practical reasons, but oxygen is a low-value product. Another anodic reaction with a more valuable oxidation product can be selected to increase the profitability of the overall electrochemical process and thereby decrease the total production costs of tartaric acid.

In industrial electrochemical processes it is of paramount importance to achieve efficient, selective processes to produce valuable chemicals while minimizing the energy input. Although the electrochemical reduction of CO ₂ has received a lot of attention in the past decades, an economically feasible process has not yet been developed. Typically, the electrochemical reduction of CO ₂ is paired to water oxidation, forming oxygen, but an alternative strategy would be coupling the CO ₂ reduction reaction to an oxidation in which a higher-value product is co-produced, significantly improving the economic feasibility for CO ₂ reduction as a whole. Importantly, both reactions need to be chosen wisely to ensure their compatibility and to minimize the voltage requirements for the redox system. In this study, as an example of this approach, we demonstrate such a match: the electroreduction of CO ₂ to CO, paired with the electrooxidation of 1,2-propanediol to lactic acid. Combining these reactions decreases energy consumption by 35%, increases product value of the system, and results in combined faradaic efficiencies of up to 160% when compared to the CO ₂ reduction reaction in which oxygen is formed in the anode.