CO oxidation over ceria supported Au22 nanoclusters: Shape effect of the support

Abstract Gold (Au) nanoclusters have recently emerged as ideal models for understanding Au catalysis, because the nanosized Au particles have precise atomic numbers and uniform size. In this work, we studied for the first time the support shape effect on the catalysis of Au nanoclusters by using CO oxidation as a model reaction. Au 22 (L 8 ) 6 (L = 1,8-bis(diphenylphosphino) octane) nanoclusters were supported on CeO 2 rods or cubes, then pretreated at different temperatures (up to 673 K), allowing the gradual removal of the organic phosphine ligands. CO oxidation test over these differently pretreated samples shows that CeO 2 rods are much better supports than cubes for Au 22 nanoclusters in enhancing the reaction rate. In situ IR spectroscopy coupled with CO adsorption indicates that the shape of CeO 2 support can impact the nature and quantity of exposed Au sites, as well as the efficiency of organic ligand removal. Although CeO 2 rods are helpful in exposing a greater percentage of total Au sites upon ligands removal, the percentage of active Au sites (denoted by Au δ + , 0  δ 2 cubes. The in situ extended X-ray absorption spectroscopy (EXAFS) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) results show that the Au nanoclusters bound more strongly to the CeO 2 rods than to the cubes where the Au nanoclusters show more sintering. Considering the typical redox mechanism for CO oxidation over supported Au nanoclusters and nanoparticles, it is concluded that the reactivity of the lattice oxygen of CeO 2 is the determining factor for CO oxidation over Au 22 /CeO 2 . CeO 2 rods offer more reactive lattice oxygen and abundant oxygen vacancies than the cubes and thus make the rods a superior support for Au nanoclusters in catalyzing low temperature CO oxidation.