The CO methanation on Rh/CeO2 and CeO2/Rh model catalysts: a comparative study

Like other reducible oxides, ceria promotes the CO methanation reaction on noble metals, but after high-temperature reduction the promotion is usually reduced and limited to transient conditions. We studied the effect of low- and high-temperature reduction on two types of Rh/ceria model catalysts: “thin film catalysts” consisting of well-defined regular Rh nanoparticles partly embedded in the crystalline ceria support, and “inverse catalysts”, i.e. UHV grown ceria submonolayers on polycrystalline Rh surfaces. The turnover rates on either catalyst were related to the free Rh surface area and to the dimensions of the metal–oxide boundary. On thin film catalysts the rates decrease strongly with reduction temperature up to 723 K while no significant structural changes are detectable by ex situ electron microscopy. On ceria-modified surfaces the reaction is initially favoured after reduction below 573 K, but promotion converts to inhibition with increasing reduction temperature. The changing number of CeIII/CeIV ions on the surface, the oxygen transport to and from the interface, and changes in the free Rh surface area resulting from spreading and reordering of the ceria overlayer are discussed as possible reasons for the observed effects.