Origin of the synergistic effect between TiO2 crystalline phases in the Ni/TiO2-catalyzed CO2 methanation reaction

The catalytic performances of TiO2-supported Ni catalysts for the methanation of CO2 have been investigated using different crystalline phases of TiO2 (rutile and anatase). The catalytic activity of Ni depends appreciably on the nature of the support. The rate for CO2 hydrogenation decreases in the order of 10Ni/10Ni/TiO2-rutile >> 10Ni/TiO2-anatase. The use of a mixture of catalysts containing 70% 10Ni/TiO2-anatase + 30% 10Ni/TiO2-rutile allows for a significant increase of the reaction rate related to 100% 10Ni/TiO2-rutile. Importantly, it has been demonstrated that the two catalysts do not need to be in direct contact for the synergetic effect to occur. DRIFTS operando analysis during the methanation reaction shows that adsorbed CO accumulates on 10Ni/TiO2-anatase and not on 10Ni/TiO2-rutile, and that the role of the 10Ni/TiO2-rutile is to assist the hydrogenation of this adsorbed CO on the 10Ni/TiO2-anatase. Increased CO2 methanation is also observed by adding Ni-free 10Ni/TiO2-anatase to 10Ni/TiO2-rutile, indicating that COx hydrogenation can also occur on bare 10Ni/TiO2-anatase if activated hydrogen can be supplied by another source. H-2-TPD analyses and catalytic tests performed after dilution of the catalysts have shown that hydrogen spillover (mediated by surface or gasphase species) is at the origin of the synergy observed between the two catalysts for the Sabatier reaction. (C) 2021 Elsevier Inc. All rights reserved.

Automated summary

The catalytic performances of TiO2-supported Ni catalysts for the methanation of CO2 are investigated, showing that the crystalline phases of TiO2 significantly affect the activity of Ni. Mixing rutile and anatase TiO2 can increase the reaction rate significantly without direct contact between the two catalysts. The synergy between the two catalysts is attributed to hydrogen spillover mediated by surface or gas-phase species.