An electrochemical device converts carbon dioxide to a formic acid reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each have reactant introduced thereto. Two membranes, a cation exchange polymer electrolyte membrane and an anion exchange polymer electrolyte membrane, are interposed between the anode and the cathode, forming a central flow compartment where a carbon dioxide reduction product, such as formic acid, can be recovered. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and formate ion selectivity is at least 50% at a cell potential difference of 3.0 V. In some embodiments, at least one polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.
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