While being highly active for the CO oxidation reaction already at low temperatures, Au/CeO2 catalysts suffer from continuous deactivation with time on stream, with the activity and deactivation depending on the initial catalyst activation procedure. In previous X-ray absorption measurements at the Au LIII edge, which focused on changes in the electronic and geometric changes of Au, we found a modest increase of the Au particle size during reaction, with the Au nanoparticles (NPs) present in a dominantly metallic state during reaction, regardless of the pretreatment. Here we aim at expanding on these insights by examining the changes in electronic and chemical composition of the CeO2 support induced by different pretreatment procedures and during subsequent CO oxidation at 80 °C, by following changes at the Ce LIII near edge region in time-resolved operando X-ray absorption measurements. The results indicate a strong dependence of the initial concentration of Ce3+ ions on the pretreatment, while during subsequent reaction this rapidly approaches a steady-state value which depends on the oxidative/reductive character of the reaction gas mixture, but is largely independent of the pretreatment. These results are discussed and related to earlier finding on the electronic properties of Au nanoparticles under identical reaction conditions.

The discovery of the activity of dispersed gold nanoparticles three decades ago paved the way for a new era in catalysis. The unusual behavior of these catalysts sparked many questions about their working mechanism. In particular, Au/CeO2 proved to be an efficient catalyst in several reactions such as CO oxidation, water gas shift, and CO2 reduction. Here, by employing findings from operando X‐ray absorption spectroscopy at the near and extended Au and Ce LIII energy edges, we focus on the fundamental aspects of highly active Au/CeO2 catalysts, mainly in the CO oxidation for understanding their complex structure‐reactivity relationship. These results were combined with findings from in situ diffuse reflectance FTIR and Raman spectroscopy, highlighting the changes of adlayer and ceria defects. For a comprehensive understanding, the spectroscopic findings will be supplemented by results of the dynamics of O2 activation obtained from Temporal Analysis of Products (TAP). Merging these results illuminates the complex relationship among the oxidation state, size of the Au nanoparticles, the redox properties of CeO2 support, and the dynamics of O2 activation.

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