Surface-enhanced Raman scattering on uniform platinum-group overlayers: preparation by redox replacement of underpotential-deposited metals on gold.

The preparation of Pt-group metal films on roughened gold electrodes by utilizing spontaneous redox replacement of an underpotential-deposited (upd) copper or lead monolayer with a Pt-group metal cation solute is described. The resulting films display intense surface-enhanced Raman scattering (SERS) for adsorbates bound to the overlayer and free from substrate interferences. This strategy provides a useful alternative, at least for platinum, to the constant-current electrodeposition method commonly utilized to prepare SERS-active Pt-group metal films (Zou, S.; Weaver, M. J. Anal. Chem. 1988, 70. 2387). Similarly to related earlier studies, the film uniformity (specifically, the absence or otherwise of residual Au "pinhole" sites) was tested by employing carbon monoxide, and also ethylene, as "probe" chemisorbates, since they yield vibrational frequencies on Au that are blue-shifted from the corresponding bands for adsorbate bound to Pt-group metal sites. While a single redox replacement of upd Cu with Pt(IV) yielded incomplete surface coverage, as expected, the use of multiple (up to eight) replacement cycles produced Pt films displaying remarkably intense CO vibrational bands as well as apparently "pinhole-free" properties, although such imperfections were detected with the ethylene probe. A single upd Cu replacement with Pt(II), however, yielded a remarkably uniform Pt layer, as indicated by pinhole-free characteristics using both the CO and ethylene probes along with the voltammetric behavior. The use of additional redox replacement cycles yielded marked progressive attenuation in the SERS signals. Comparable, although less optimal, SERS behavior was obtained for Pd films prepared similarly from Pd(II). The value of the strategy for exploring catalytic as well as equilibrium adsorptive chemistry on Pt surfaces is also illustrated.