Understanding morphology-dependent CuO -CeO2 interactions from the very beginning

Elucidation of the CuOx-CeO2 interactions is of great interest and importance in understanding complex CuOx-CeO2 interfacial catalysis in various reactions. In the present work, we have investigated structures and catalytic activity in CO oxidation of CuOx species on CeO2 rods, cubes and polyhedra predominantly exposing {110}+{100}, {100} and {111} facets by the incipient wetness impregnation method with the lowest Cu loading of 0.025%. The structural evolution of CuOx species was found to depend on both the Cu loading and the CeO2 morphology. As the Cu loading increases, CuOx species are deposited preferentially on the surface defect of CeO2 and then aggregate and grow, accompanied by the formation of isolated Cu ions, CuOx clusters strongly/weakly interacting with the CeO2, highly dispersed CuO nanoparticles, and large CuO nanoparticles. The isolated Cu+ species and CuOx clusters weakly interacting with the CeO2 were observed mainly on the O-terminated CeO2{100} facets. Meanwhile, more Cu(I) species are stabilized during CO reduction processes in CuOx/c-CeO2 catalysts than in CuOx/r-CeO2 and CuOx/p-CeO2 catalysts. The catalytic activities of various CuOx/CeO2 catalysts in CO oxidation vary with both the CuOx species and the CeO2 morphology. These results comprehensively elucidate the CuOx-CeO2 interactions and exemplify their morphology-dependence.