Effect of the Pt/Ru intermetallic boundary on the carbon monoxide electrooxidation: Excess electrocatalytic activity

Abstract

The carbon monoxide oxidation reaction was studied on smooth Pt, Ru and Pt/Ru (Ru partially covered by Pt islands) rotating disc electrodes on acid solution saturated with CO gas (PCO = 1 atm) through steady state measurements. The current density vs. overpotential plot of the Pt/Ru electrode shows a profile qualitatively similar to the sum of both curves corresponding to pure Pt and Ru. On this basis, the excess electrocatalytic activity was defined as the difference between the current densities of the bimetallic electrode and those corresponding to the pure metals, which allowed evaluating the contribution of the intermetallic region to the reaction. It was verified that this property depends on overpotential, defining two ranges of positive excess values, 0.6 - 0.82 and 0.88 - 1.0, separated by the range 0.82 - 0.88, where the contribution of the boundary region is negligible. A simple model was developed, which explains the experimental results on the basis of the spillover of the adsorbed reaction intermediates, while the reaction between adsorbed species on both sides of the intermetallic edge is not feasible.