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In this work we elucidate the main steps of the CO oxidation mechanism over Au/CeO₂(111), clarifying the course of CO adsorption at a broad variety of surface sites as well as of transmutations of one CO species into another. By combining transient spectroscopy with DFT calculations we provide new evidence that the active centers for CO conversion are single gold atoms. To gain insight into the reaction mechanism, we employ Modulation Excitation (ME) DRIFT spectroscopy in combination with the mathematical tool of Phase Sensitive Detection to identify the active species and perform DFT calculations to facilitate the assignments of the observed bands. The transient nature of the ME-DRIFTS method allows us to sort the observed species temporally, providing further mechanistic insight. Our study highlights the potential of combined transient spectroscopy and theoretical calculations (DFT) to clarify the role of adsorbates observed and to elucidate the reaction mechanism of CO oxidation over supported gold and other noble-metal catalysts.