Organic Non-Nucleophilic Electrolyte Resists Carbonation during Selective CO Electroreduction.

The spontaneous reaction of CO with water and hydroxide to form (bi)carbonates in alkaline aqueous electrolytes compromises the energy and carbon efficiency of CO electrolyzers. We hypothesized that electrolyte carbonation could be mitigated by operating the reaction in an aprotic solvent with low water content, while also employing an exogenous non-nucleophilic acid as the proton donor to prevent parasitic capture of CO by its conjugate base. However, it is unclear whether such an electrolyte design could simultaneously engender high CO reduction selectivity and low electrolyte carbonation. We herein report selective CO electroreduction with low carbonate formation on a polycrystalline Au catalyst using dimethyl sulfoxide as the solvent and acetic acid/acetate as the proton-donating medium. CO is reduced to CO with over 90% faradaic efficiency at potentials relative to the reversible hydrogen electrode that are comparable to those in neutral aqueous electrolytes. H and C NMR studies demonstrate that only millimolar concentrations of bicarbonates are reversibly formed, that the proton activity of the medium is largely unaffected by exposure to CO, and that low carbonation is maintained upon addition of 1 M water. This work demonstrates that electrolyte carbonation can be attenuated and decoupled from efficient CO reduction in an aprotic solvent, offering new electrolyte design principles for low-temperature CO electroreduction systems.