Kinetic studies of adsorbed CO electrochemical oxidation on Pt(335) at full and sub-saturation coverages

Abstract

Electrochemical measurements were performed to characterize the kinetics of adsorbed CO oxidation on the surface of the stepped Pt(s)-[4(111)×(100)]Pt(335) single crystal electrode. For CO adsorbed to full coverage at 0.1 V (versus the reversible hydrogen electrode, RHE) in 0.5 M H₂SO₄ at ambient temperature (23 °C), oxidation of the layer gave 7.6 × 10¹⁴ ± 0.3 CO/cm² as the saturation CO coverage, just below the average value reported for CO on Pt(335) in ultra high vacuum (8.3 × 10¹⁴ ± 0.6 CO/cm²). In potential step measurements carried out between 0.75 and 0.9 V, the peak region in the current–time transient was consistent with the surface reaction between adsorbed CO and adsorbed oxide as rate limiting. Plotting the log of the rate constant for the surface reaction versus potential gave a Tafel slope of 79 mV per decade, consistent with responses for CO electrochemical oxidation on structurally related stepped Pt electrodes. For CO coverages below saturation, current–time transients were more stable in 0.05 M H₂SO₄ than in the higher concentration electrolyte. Numerically solving the rate equations to the Langmuir–Hinshelwood model of adsorbed CO electrochemical oxidation reproduced the main features in current-time transients measured at 0.7 V in 0.05 M H₂SO₄ for sub-saturation CO coverages. The results provide new insights into CO oxidation on Pt at sub-saturation coverage and confirm that anions play a role in CO surface chemistry.