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Electrochemical reduction of carbon dioxide (CO₂) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity^,,,,,,. Unfortunately, the reaction suffers from slow kinetics^, owing to the low local concentration of CO₂ surrounding typical CO₂ reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species^,, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO₂ adsorption, but this comes at the cost of increased hydrogen (H₂) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO₂ close to the active CO₂ reduction reaction surface …