Structure of the (Bi)carbonate Adlayer on Cu(100) Electrodes

(Bi)carbonate adsorption on Cu(100) in 0.1 M KHCO3 has been studied by in situ scanning tunneling microscopy. Coexistence of different ordered adlayer phases with ( 2${\sqrt{2}}$ ×6 2${\sqrt{2}}$ )R45° and (4×4) unit cells was observed in the double layer potential regime. The adlayer is rather dynamic and undergoes a reversible order-disorder phase transition at 0 V vs. the reversible hydrogen electrode. Density functional calculations indicate that the adlayer consists of coadsorbed carbonate and water molecules and is strongly stabilized by liquid water in the adjacent electrolyte.