Monitoring the Reaction Mechanism in Model Biogas Reforming by In Situ Transient and Steady-State DRIFTS Measurements.

In this work, the reforming of model biogas was investigated on a Rh/MgAl2 O4 catalyst. In situ transient and steady-state diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements were used to gain insight into the reaction mechanism involved in the activation of CH4 and CO2 . It was found that the reaction proceeds through of an initial pathway in which methane and CO2 are both dissociated on Rh metallic sites and additionally a bifunctional mechanism in which methane is activated on Rh sites and CO2 is activated on the basic sites of the support surface via a formate intermediate by H-assisted CO2 decomposition. Moreover, this plausible mechanism is able to explain why the observed apparent activation energy of CO2 is much lower than that of CH4 . Our results suggest that CO2 dissociation facilitates CH4 activation, because the oxygen-adsorbed species formed in the decomposition of CO2 are capable of reacting with the CHx species derived from methane decomposition.