Morphology effect of ceria supports on gold nanocluster catalyzed CO oxidation

Abstract

The interfacial perimeter is generally viewed as the catalytically active site for a number of chemical reactions over oxide-supported nanogold catalysts. Here, well-defined CeO₂ nanocubes, nanorods and nanopolyhedra are chosen to accommodate atomically precise clusters (e.g. Au₂₅(PET)₁₈) to give different Au cluster–CeO₂ interfaces. TEM images show that Au particles of ∼1.3 nm are uniformly anchored on the ceria surface after annealing in air at 120 °C, which can rule out the size hierarchy of nanogold in CO oxidation studies. The gold nanoclusters are only immobilized on the CeO₂(200) facet in Au₂₅/CeO₂-C, while they are selectively loaded on CeO₂(002) and (111) in the Au₂₅/CeO₂-R and Au₂₅/CeO₂-P catalysts. X-ray photoelectron spectroscopy (XPS) and in situ infrared CO adsorption experiments clearly demonstrate that the gold species in the Au₂₅/CeO₂ samples are similar and partially charged (Au^δ+, where 0 < δ < 1). It is observed that the catalytic activity decreases in the order of Au/CeO₂-R ≈ Au/CeO₂-P > Au/CeO₄-C in the CO oxidation. And the apparent activation energy over Au₂₅/CeO₂-C (60.5 kJ mol⁻¹) is calculated to be about two-fold of that over the Au₂₅/CeO₂-R (28.6 kJ mol⁻¹) and Au₂₅/CeO₂-P (31.3 kJ mol⁻¹) catalysts. It is mainly tailored by the adsorbed [O] species on the ceria surface, namely, Au₂₅/CeO₂(002) and Au₂₅/CeO₂(111) which were more active than the Au₂₅/CeO₂(200) system in the CO oxidation. These insights at the molecular level may provide guidelines for the design of new oxide-supported nanogold catalysts for aerobic oxidations.