The electrochemical oxidation of SOMs such as methanol and glucose is a critical process and has relevant applications in fuel cells and sensors. A key challenge in SOM oxidation is the poisoning of the surface by carbon monoxide (CO) and other partially oxidized intermediates, which is attributed to the presence of Pt-Pt pair sites. A promising pathway for overcoming this challenge is to develop catalysts that selectively oxidize SOMs via ‘direct’ pathways that do not form CO as a primary intermediate. In this report, we utilize an ambient, template-based approach to prepare bimetallic platinum-based alloy nanowires with tunable compositions. Monte Carlo method simulations of the surface structure of the bimetallic alloys with varying coverage of oxygen adsorbates and varying degrees of oxygen adsorption strength reveal that oxygen adsorption under electrochemical conditions enriches the surface with Pt and a large fraction of Pt-Pt sites remain on the surface even when the platinum content is reduced below 50%. Electrochemical properties and the catalytic performance measurements of the bimetallic nanowires for the oxidation of methanol and glucose reveal that the mechanistic pathways that produce CO are suppressed by the addition of relatively small quantities of other transition metals into the alloy. The suppression of CO formation with small quantities of other metals suggest that the presence of Pt-M pair sites may be more important in determining the mechanism of SOM oxidation rather than Pt-Pt pair site density.

Influence of surface structure and Pt-Pt pair site density on the electrocatalytic oxidation of small organic molecules with platinum-based nanowire catalysts

ACS Spring 2022

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