In-situ Raman spectroscopy study of Ru/TiO2 catalyst in the selective methanation of CO

Abstract

Raman spectroscopic technique has been used to characterize a Ru/TiO2 catalyst and to follow in situ their structural changes during the CO selective methanation reaction (S-MET). For a better comprehension of the catalytic mechanism, the in-situ Raman study of the catalysts activation (reduction) process, the isolated CO and CO2 methanation reactions and the effect of the composition of the reactive stream (H2O and CO2 presence) have been carried out. Raman spectroscopy evidences that the catalyst is composed by islands of TiO2¿RuO2 solid solutions, constituting Ru¿TiO2 interphases in the form of RuxTi1 xO2 rutile type solid solutions. The activation procedure with H2 at 300 °C promotes the reduction of the RuO2¿TiO2 islands generating Ruo ¿Ti3+ centers. The spectroscopic changes are in agreement with the strong increase in chemical reactivity as increasing the carbonaceous intermediates observed. The selective methanation of CO proceeds after their adsorption on these Ruo ¿Ti3+ active centers and subsequent C-O dissociation throughout the formation of CHx/CnHx/CnHxO/CHx-CO species. These intermediates are transformed into CH4 by a combination of hydrogenation reactions. The formation of carbonaceous species during the methanation of CO and CO2 suggests that the CO presence is required to promote the CO2 methanation. Similar carbonaceous species are detected when the selective CO methanation is carried out with water in the stream. However, the activation of the catalysts occurs at much lower temperatures, and the carbon oxidation is favored by the oxidative effect of water.