Carbon Dioxide Electroreduction on Gold without Metal or Organic Cations.

Extensive research efforts have been concentrated into the conversion of CO into value-added chemicals as it provides a route to a circular carbon economy. Electroreduction of CO on Au surfaces allows for the selective transformation of CO into CO via carbon dioxide reduction reaction (CORR), and the catalytic activity depends on the concentration and identity of cations present at the electrode-electrolyte interface. Experimental reports performed under typical CORR-operating conditions have widely shown that the CORR is enabled by the presence of metal or organic cations in the cathodic interfacial microenvironment. A remaining question is to address if CORR can occur in the absence of metal or organic cations and, if so, what the mechanism may be. Here, we show that CO can be electrochemically reduced to CO on Au in acidic electrolytes rigorously controlled to avoid the presence of metal and organic cations and systematically suggest the important contributions allowing this reaction to proceed. The formation of CO is confirmed by both qualitative and quantitative methods using potentiodynamic CO-stripping scans and chromatography-assisted constant potential electrolysis. Calculations indicate that HO is able to stabilize the formation of *CO , albeit at more negative potentials than when an alkali metal cation is present. Spectroelectrochemical experiments show that the electric field at the interface is reduced when metal cations are not added, indicating that the decreased field stabilization of intermediates could play an important role in increased overpotential required for the CORR to occur.