The reforming of methane from biogas into syngas has been proposed as a promising method of CO2 utilization. Co-based catalysts are promising candidates for dry methane reforming due to lower cost than the traditional noble metal catalysts such as Pt and Pd. However, the primary constraints limiting the large-scale use of Co-based catalysts are deactivation through carbon deposition (coking) and particle sintering due to weak metal-support interaction. The structure-function properties and catalytic behavior of Co/TiO2 and Co-Ru/TiO2 catalysts were analyzed using two different types of TiO2 supports: the commercial anatase TiO2 and faceted nonstoichiometric rutile TiO2 crystals (TiO2*). The Co and Ru metal particles were deposited on TiO2 supports using a wet-impregnation method with the percentage weight loading of Co and Ru of 5% and 0.5%, respectively. The materials were characterized using SEM, STEM-HAADF, XRD, XPS, and BET. The catalytic performance was studied using the CH4:CO2 ratio of 3:2 to mimic the methane-rich biogas composition. Our results indicate that the addition of Ru to Co catalysts supported on TiO2* reduces carbon deposition and influences oxygen mobility. Co and Co-Ru catalysts supported on TiO2* exhibit superior activity with the highest conversion of CO2 and CH4 of 34.7% and 23.5%, respectively. Despite the improved performance, the Co-Ru/TiO2* catalyst has limited stability due to the proliferation of nanoparticle growth and TiOx layers on the surface of the nanoparticles indicating the prevalence of the strong-metal support interaction.

Influence of high-energy faceted TiO2 supports on Co and Co-Ru catalysts for dry methane reforming

ACS Spring 2022

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