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Atomically precise thiolate protected Au nanoclusters Au 38 (SC 2 H 4 Ph) 24 on CeO 2 were used for in-situ (operando) extended X-ray absorption fine structure/diffuse reflectance infrared fourier transform spectroscopy and ex situ scanning transmission electron microscopy-high-angle annular dark-field imaging/X-ray photoelectron spectroscopy studies monitoring cluster structure changes induced by activation (ligand removal) and CO oxidation. Oxidative pretreatment at 150 °C "collapsed" the clusters' ligand shell, oxidizing the hydrocarbon backbone, but the S remaining on Au acted as poison. Oxidation at 250 °C produced bare Au surfaces by removing S which migrated to the support (forming Au + -S), leading to highest activity. During reaction, structural changes occurred via CO-induced Au and O-induced S migration to the support. The results reveal the dynamics of nanocluster catalysts and the underlying cluster chemistry.

The Dynamic Structure of Au38(SR)24 Nanoclusters Supported on CeO2 upon Pretreatment and CO Oxidation

The Dynamic Structure of Au₃₈(SR)₂₄ Nanoclusters Supported on CeO₂ upon Pretreatment and CO Oxidation