Characterization of oxygenated species at water/Pt(111) interfaces from DFT energetics and XPS simulations

Abstract

Determining the atomic-scale structure of oxygenated species at water/Pt(111) interfaces under electrochemical oxygen reduction reaction (ORR) conditions has been a significant, long-term challenge for both experimentalists and theorists. Numerous techniques have elucidated important information about this system, but significant uncertainties relating to the structure and hydration state of adsorbed oxygenated species remain. To resolve some of these questions, an approach based on careful calibration of Density Functional Theory (DFT)-determined energetics, as well as detailed simulation of X-ray Photoelectron Spectroscopy (XPS) signatures, is developed. The combined energetic and XPS analysis of various oxygenated species demonstrates that non-hydrated OH, which has been suggested, by analysis of O 1s core-level binding data from state-of-the-art XPS studies, to be an abundant surface species at water/Pt(111) interfaces during ORR, is in fact unlikely to exist at potentials relevant to ORR, although it might be found in other conditions. The OH is more likely to be present in a fully hydrated state, and the experimentally observed features can be assigned to other oxygen arrangements. This insight about the nature of OH binding at water-Pt interfaces has implications not only for the general understanding of electrified water/Pt interfaces, but also for the design of ORR catalysts with improved performance on the basis of first principles calculations.