Abstract
CO(2) methanation has been studied with Pr-doped Ru/CeO(2) catalysts, and a dual effect of Pr has been observed. For low Pr content (i.e., 3 wt %) a positive effect in oxygen mobility prevails, while for high Pr doping (i.e., 25 wt %) a negative effect in the Ru-CeO(2) interaction is more relevant. Isotopic experiments evidenced that Pr hinders the dissociation of CO(2), which takes place at the Ru-CeO(2) interface. However, once the temperature is high enough (200 °C), Pr improves the oxygen mobility in the CeO(2) support, and this enhances CO(2) dissociation because the oxygen atoms left are delivered faster to the support sink and the dissociation sites at the interface are cleaned up faster. In situ Raman spectroscopy experiments confirmed that Pr improves the creation of oxygen vacancies on the ceria lattice but hinders their reoxidation by CO(2), and both opposite effects reach an optimum balance for 3 wt % Pr doping. In addition, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments showed that Pr doping, regardless of the amount, decreases the population of surface carbon species created on the catalysts surface upon CO(2) chemisorption under methanation reaction conditions, affecting both productive reaction intermediates (formates and carbonyls) and unproductive carbonates.