Electrocatalytic CO2 reduction to generate multicarbon products is of interest for applications in artificial photosynthetic schemes. This is a particularly attractive goal for CO2 reduction by copper electrodes, where a broad range of hydrocarbon products can be generated but where selectivity for C–C coupled products relative to CH4 and H2 remains an impediment. Herein we report a simple yet highly selective catalytic system for CO2 reduction to C≥2 hydrocarbons on a polycrystalline Cu electrode in bicarbonate aqueous solution that uses N-substituted pyridinium additives. Selectivities of 70–80% for C2 and C3 products with a hydrocarbon ratio of C≥2/CH4 significantly greater than 100 have been observed with several additives. 13C-labeling studies verify CO2 to be the sole carbon source in the C≥2 hydrocarbons produced. Upon electroreduction, the N-substituted pyridinium additives lead to film deposition on the Cu electrode, identified in one case as the reductive couplingproduct of N-arylpyridinium. Product selectivitycan also be tuned from C≥2 species to H2 (∼90%) while suppressing methane with certain N-heterocyclicadditives.
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