Fundamental aspects of ceria supported au catalysts probed by in situ/operando spectroscopy and TAP reactor studies

Unravelling the mystery of Au/CeO2 catalysts! Challenged by the complex nature of Au/CeO2 catalysts, operando X-ray absorption spectroscopy in the near and extended Au LIII and Ce LIII energy edges is employed to decipher different aspects of the electronic and geometric features of Au NPs/clusters and CeO2 support. These results combined with findings from ex-situ XPS, in situ FTIR/Raman spectroscopy and temporal analysis of products (TAP) reactor, provide a more fundamental insight into the performance of these catalysts. 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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