To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcohols, such as ethylene and ethanol, from electrochemical CO 2 reduction (CO 2 R). There are variety of factors that impact CO 2 R activity and selectivity, including the catalyst surface structure, morphology, composition, the choice of electrolyte ions and pH, and the electrochemical cell design. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO 2 R catalysis on Cu, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices. First, we describe the various experimental probes and complementary theoretical methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO 2 R on Cu. We then analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochemical CO 2 R.

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Understanding the surface reactivity of CO, which is a key intermediate during electrochemical CO 2 reduction, is crucial for the development of catalysts that selectively target desired products for the conversion of CO 2 to fuels and chemicals. In this study, a customdesigned electrochemical cell is utilized to investigate planar polycrystalline copper as an electrocatalyst for CO reduction under alkaline conditions. Seven major CO reduction products have been observed including various hydrocarbons and oxygenates which are also common CO 2 reduction products, strongly indicating that CO is a key reaction intermediate for these further-reduced products. A comparison of CO and CO 2 reduction demonstrates that there is a large decrease in the overpotential for C−C coupled products under CO reduction conditions. The effects of CO partial pressure and electrolyte pH are investigated; we conclude that the aforementioned large potential shift is primarily a pH effect. Thus, alkaline conditions can be used to increase the energy efficiency of CO and CO 2 reduction to C−C coupled products, when these cathode reactions are coupled to the oxygen evolution reaction at the anode. Further analysis of the reaction products reveals common trends in selectivity that indicate both the production of oxygenates and C−C coupled products are favored at lower overpotentials. These selectivity trends are generalized by comparing the results on planar Cu to current state-of-the-art high-surface-area Cu catalysts, which are able to achieve high oxygenate selectivity by operating at the same geometric current density at lower overpotentials. Combined, these findings outline key principles for designing CO and CO 2 electrolyzers that are able to produce valuable C−C coupled products with high energy efficiency.