Electrochemical CO Oxidation at Platinum on Carbon Studied through Analysis of Anomalous in Situ IR Spectra

[Image: see text] The oxidation of adsorbed CO is a key reaction in electrocatalysis. It has been studied extensively on both extended model surfaces and on nanoparticles; however, correlation between the two is far from simple. Molecular insight into the reaction is often provided using in situ IR spectroscopy; however, practical challenges mean in situ studies on nanoparticles have yet to provide the same level of detail as those on model surfaces. Here we use a new approach to in situ IR spectroscopy to study the mechanism of CO adlayer oxidation on a commercial carbon-supported Pt catalyst. We observe bipolar IR absorption bands but develop a simple model to enable fitting. Quantitative analysis of band behavior during the oxidation prepeak using the model agrees well with previous analysis based on conventional absorption bands. A second linear CO band is observed during the main oxidation region and is assigned to the distinct contribution of CO on step as opposed to terrace sites. Analysis of the step and terrace CO bands during oxidation shows that oxidation begins on the terraces of the nanoparticles before CO on steps is removed. Further correlation of this behavior with the current shows that step CO is only lost in the first of the two main oxidation peaks.