Reactivity of Copper Electrodes towards Functional Groups and Small Molecules in the Context of CO2 Electro-Reductions

The direct electro-reduction of CO2 to functional molecules like ethene is a highly desirable variant of CO2 utilization. The formation of, for example, ethene from CO2 is a multistep electrochemical process going through various intermediates. As these intermediates are organic species, the CO2 reducing electro-catalyst has to be competent for a variety of organic functional group transformations to yield the final product. In this work, the activity of an in situ-grown nano-structured copper catalyst towards a variety of organic functional group conversions was studied. The model reagents were selected from the product spectrum of actual CO2 reduction reaction (CO2RR) experiments and from proposals in the literature. The CO2 bulk electrolysis benchmark was conducted at 170 mAcm−2 current density with up to 43% Faradaic Efficiency (FE) for ethene and 23% FE for ethanol simultaneously. To assure relevance for application-oriented conditions, the reactivity screening was conducted at elevated current densities and, thus, overpotentials. The found reactivity pattern was then also transferred to the CO reduction reaction (CORR) under benchmark conditions yielding additional insights. The results suggest that at high current density/high overpotential conditions, also other ethene formation pathways apart from acetaldehyde reduction such as CH2 dimerization are present. A new suggestion for a high current density mechanism will be presented, which is in agreement with the experimental observations and the found activity pattern of copper cathodes toward organic functional group conversion.