Electrochemical Infrared Characterization of CO Domains on Ruthenium-Decorated Platinum Nanoparticles

Abstract

Spectra obtained by electrochemical infrared reflection absorption spectroscopy (EC−IRAS) for carbon monoxide (CO) adlayers formed by partial CO dosing on various ruthenium-decorated platinum nanoparticle films are reported. The need to achieve a well distributed rather than aggregated metal nanoparticle array is demonstrated, given that such nanoparticle aggregates induce complex dielectric behavior. The strategy here is to use an “organic glue matrix” (short chain SAMs) between the nanoparticles and the gold substrates. The observed promotion in CO electrooxidation by the existence of a Ru island on Pt nanoparticles, of interest to fuel-cell catalysis, showed a strong relationship with Ru surface concentrations, consistent with previous studies on single crystal or polycrystalline bimetallic surfaces. Two distinctive CO infrared bands, one for the Pt−CO and one for Ru−CO domain were found after the dipole coupling of CO within the two CO domains was minimized. Interestingly, those two CO bands showed independent electrooxidation behavior with electrode potential changes. Also, it is shown that the electrooxidation of CO on large Ru islands is less facile than on small Ru islands. In addition, the activity of commercial Pt/Ru alloy nanoparticles to CO stripping was tested and IRAS spectra were reported as a comparison to our Ru-decorated Pt nanoparticles.