Mechanistic Insights into CO2 Methanation over Ru-Substituted CeO2

CO<inf>2</inf> methanation is an important probe reaction to understand CO<inf>2</inf> interactions with catalytic surfaces. The importance of this reaction is further increased by its association with CO<inf>2</inf> utilization. This study reports the mechanistic aspects of CO<inf>2</inf> methanation over combustion synthesized Ru-substituted CeO<inf>2</inf> catalyst. Temperature-programmed reaction experiments were carried out to understand the interaction of CO<inf>2</inf>, H<inf>2</inf>, and their stoichiometric mixture with the catalyst surface. In situ FTIR spectroscopy was used to identify the intermediates of the reaction. It was observed that CO<inf>2</inf> adsorption took place on the surface of Ce<inf>0.95</inf>Ru<inf>0.05</inf>O<inf>2</inf> and the formation of surface carbonate intermediates took place only when H<inf>2</inf> was present in the gas phase. In the absence of H<inf>2</inf>, CO<inf>2</inf> did not show any indication for chemisorption. This behavior was explained in terms of the reaction between CO<inf>2</inf> and the surface hydroxyls leading to the formation of a vacancy. Upon dissociation, carbonates led to chemisorbed CO which eventually formed methane upon reaction with gas-phase H<inf>2</inf>. The exact identity of carbonate species and the pathway for the methanation step were ambiguous following purely experimental studies. Density functional theory calculations were carried out to augment the experimental observations. Complete energy landscapes developed on the basis of differentiation of oxidized and reduced forms of the catalyst showed that the reaction followed a pathway consisting of surface carbonate species formed by the interaction of oxide surface and chemisorbed CO, and a sequential methanation via the surface methoxy species formation. The study provides physical insights into the role of the oxidation state of the catalyst and the surface anionic vacancies in governing the reaction pathway.