Titrating Pt Surface with CO Molecules.

Identification and quantification of the surface sites on Pt nanoparticles are essential for developing more active electrocatalysts for many practical devices such as fuel cells and electrochemical fuel generators. In this work, we studied CO adsorption from dissolved CO in an HSO electrolyte solution on a polycrystalline Pt film electrode held at a constant potential in the underpotential hydrogen deposition region using attenuated total reflectance-surface-enhanced IR absorption spectroscopy (ATR-SEIRAS). Slowing down the adsorption rate by limiting the CO addition rate to the solution allows the individual CO molecules arriving at the Pt surface to rearrange, move to, and occupy their most energetically favorable sites. By using ATR-SEIRAS spectroscopy to follow the stepwise CO adsorption process, one can identify and quantify the Pt surface sites along with uncovering the CO adsorption energetic sequence. This method of slow CO adsorption on the Pt surface is analogous to the chemical titrations used for quantitative chemical analyses.