Density functional theory analysis of methanation reaction of CO2 on Ru nanoparticle supported on TiO2 (1 0 1)

• CO2 methanation reaction on Ru/TiO2 catalyst was analyzed by DFT analysis.
• The overall potential energy diagram of methanation reaction was obtained.
• CO hydrogenation and CH4 formation have high reaction energy barrier.
• These energy barriers decreased in comparison with that on bulk Ru surface.
• The size and structure of Ru cluster affected the catalytic activity of Ru/TiO2.

The methanation reaction of CO2 on a Ru nanoparticle supported on TiO2 catalyst has been investigated by density functional theory (DFT) using the generalized gradient approximation with periodic boundary conditions. Two plausible reaction paths were found for the transformation of CO2 to CH4 on TiO2-supported Ru nanoparticles. The origin of the high activity of the catalyst is discussed based on the overall reaction energy diagram obtained from DFT calculations. The CO2 is readily and stably adsorbed on Ru cluster at moderate temperature as compared with that on bulk Ru surface. It is due to the difference of the Ru structure between the Ru nanoparticle and the bulk Ru surface. The elementary reactions of the hydrogenation of adsorbed CO and of the production of CH4 are possible to become the rate-determining steps over the methanation reaction, because these two reactions have a higher potential energy barrier than that of other elementary reactions in the overall reaction path. These potential energy barriers for the hydrogenation of CO and the production of CH4 on TiO2-supported Ru nanoparticles were lower than those on bulk Ru surface, which explains the high activity of the Ru nanoparticle-loaded TiO2 catalyst. The lowering of these potential energy barriers can be caused by weak charge transfer between Ru atoms and adsorbed species on the TiO2-supported Ru nanoparticles. As the results, the catalytic activity of the Ru nanoparticles supported on TiO2 catalyst is characterized by the structure of Ru nanoparticles and by the weak charge transfer between Ru atoms and adsorbed species.

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