Probing electrode/electrolyte interfacial structure in the potential region of hydrogen evolution by Raman spectroscopy

The detailed interfacial structure in the potential region of severe hydrogen evolution, to date, is far from clear due to lack of both experimental data and correlated theoretic models. It has been shown that it is possible to surmount, to some extent, the disturbance of the spectroelectrochemical measurement by strong hydrogen bubbling in the potential region of severe hydrogen evolution by using a surface enhancement effect and a thin-layer cell configuration. Using this approach, we have obtained surface enhanced Raman scattering (SERS) spectra of water at an Ag electrode at very negative potentials at various concentrations of NaClO4. To explain the abnormal reversal of the peak intensity ratio of the bending to the stretching vibration, a preliminary model of the electrode/electrolyte interface is presented. The water molecule is oriented with one hydrogen attached to the surface and the oxygen towards an adsorbed cation which is partially dehydrated owing to the very strong electrostatic force. Raman spectra of hydrogen bound at a Pt electrode in solutions of varying pH from 0 to 14 at potentials of mild hydrogen evolution have also been presented for the first time. The spectra reveal that the Pt-hydrogen interaction is influenced by both the potential and the interfacial structure. These primary studies may initiate more molecular-level research of electrochemical interfaces in the potential region of hydrogen evolution.