Resolving the chemical identity of H₂SO₄ derived anions on Pt(111) electrodes: They're sulfate

Understanding how electrolyte composition controls electrocatalytic reactions requires molecular-level insight into electrode/electrolyte interaction. Perhaps the most basic aspect of this interaction, the speciation of the interfacial ion, is often controversial for even relatively simple systems. For example, for Pt(111) in 0.5 M H₂SO₄ it has long been debated whether the adsorbed anion is SO₄^2-, HSO₄^- or an H₃O⁺⋯SO₄^2- ion pair. Here we apply interface-specific vibrational sum frequency (VSF) spectroscopy and theory to this problem and perform an isotope exchange study: we collect VSF spectra of Pt(111) in H₂SO₄(H₂O) and D₂SO₄(D₂O) as a function of bias and show that at all potentials they are identical. This is the most direct spectroscopic evidence to date that SO₄^2- is the dominant adsorbate, despite the fact that at 0.5 M H₂SO₄ bulk solution is dominated by HSO₄^-. This approach is based on the unique selection rule of the VSF spectroscopy and thus offers a new way of accessing general electrode/electrolyte interaction in electrocatalysis.