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.

Aqueous electrolytes are most commonly used for the CO₂ reduction reaction (CO₂RR), but suffer from a low CO₂ solubility that limits the reaction. Electrochemical CO₂ reduction in nonaqueous electrolytes can provide a solution, due to the higher CO₂ solubility of organic solvent-based electrolytes. Herein, the product distribution of the electrochemical CO₂ reduction on polycrystalline Cu in 0.7 m tetraethylammonium chloride in propylene carbonate with different water additions (0, 10, and 90 v%), and for different operating conditions (10, 25, 40, and 60 °C), is investigated. It is found that CO₂ reduction on Cu in a propylene carbonate solution results in H₂, CO, and formic acid formation only, even though Cu is known to produce C₂₊ products such as ethylene and ethanol in aqueous electrolytes. Increasing the operating temperature increases the CO₂RR kinetics and shows an improvement in CO formation and decrease in H₂ formation. However, increasing the operating temperature also increases water transport through the membrane, resulting in an increase of H₂ formation over time when operating at 60 °C.

Recently, deep eutectic solvents (DES) have been considered as possible electrolytes for the electrochemical reduction of CO2 to value-added products such as formic and oxalic acids. The applicability of pure DES as electrolytes is hindered by high viscosities. Mixtures of DES with organic solvents can be a promising way of designing superior electrolytes by exploiting the advantages of each solvent type. In this study, densities, viscosities, diffusivities, and ionic conductivities of mixed solvents comprising DES (i.e., reline and ethaline), methanol, and propylene carbonate were computed using molecular simulations. To provide a quantitative assessment of the affinity and mass transport of CO2 and oxalic and formic acids in the mixed solvents, the solubilities and self-diffusivities of these solutes were also computed. Our results show that the addition of DES to the organic solvents enhances the solubilities of oxalic and formic acids, while the solubility of CO2 in the ethaline-containing mixtures are in the same order of magnitude with the respective pure organic components. A monotonic increase in the densities and viscosities of the mixed solvents is observed as the mole fraction of DES in the mixture increases, with the exception of the density of ethaline-propylene carbonate which shows the opposite behavior due to the high viscosity of the pure organic component. The self-diffusivities of all species in the mixtures significantly decrease as the mole fraction of DES approaches unity. Similarly, the self-diffusivities of the dissolved CO2 and the oxalic and formic acids also decrease by at least 1 order of magnitude as the composition of the mixture shifts from the pure organic component to pure DES. The computed ionic conductivities of all mixed solvents show a maximum value for mole fractions of DES in the range from 0.2 to 0.6 and decrease as more DES is added to the mixtures. Since for most mixtures studied here no prior experimental measurements exist, our findings can serve as a first data set based on which further investigation of DES-containing electrolyte solutions can be performed for the electrochemical reduction of CO2 to useful chemicals.

Carbon dioxide (CO2) is currently considered as a waste material due to its negative impact on the environment. However, it is possible to create value from CO2 by capturing and utilizing it as a building block for commodity chemicals. Electrochemical conversion of CO2 has excellent potential for reducing greenhouse gas emissions and reaching the Paris agreement goal of zero net emissions by 2050. To date, carbon capture and utilization technologies (i.e., capture and conversion) have been studied mostly independently. In this communication, we report a methodology based on the integration of CO2 capture and conversion by the direct utilization of a CO2 capture media as the electrolyte for electrochemical conversion of CO2. This has a high potential for reducing capital and operational cost when compared to traditional methodologies (i.e., capture, desorption, and then utilization). A mixture of chemical and physical absorption solvents allowed for the captured CO2 to be converted to formate with faradaic efficiencies of up to 50% and with carbon conversion of ca. 30%. By increasing the temperature in the electrochemical reactor from 20 to 75 °C, the reaction rate toward formate increased by a factor of 10, reaching up to 0.7 mmol/m2·s. The direct conversion of captured CO2 was also demonstrated for carbon monoxide formation with faradaic efficiencies of up to 45%.

Electrochemical processes are a promising technology for industrial production of chemicals. One of the major drawbacks of electrochemical systems is the low mass transfer of reactants toward the active surface area of the electrode. In this paper, an approach is presented to enhance the mass transfer and increase the overall performance of the reactions. The strategy comprises introduction of a pulsed electrolyte flow in the electrochemical flow cell. This pulsating behavior results in an improved mass transfer of electroactive species due to a higher instantaneous velocity driven by the pulsations. Though the net residence time of the reactants will not be altered due to the pulsation, the resulting enhancement of mass transfer leads to an increase of the conversion. The oxidation of 1,2-propanediol to lactic acid and pyruvic acid mediated by 4-Acetamido-(2,2,6,6-Tetramethylpiperidin-1-yl) oxidanyl (ACT-TEMPO) was chosen to study the influence of the pulsed flow. Under the pulsating regime, a yield increase of lactic acid of a factor of two and a 15-20% gain in selectivity to a total of 95% toward lactic acid can be achieved by tuning the process parameters.

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.