Abstract
To obtain insight into the importance of metal-support interactions (MSI) in the CO2 reforming of CH4, the reaction was studied using pure TiO2, high-purity Pt powder, and two model TiOx/Pt systems. The latter two TiOx/Pt catalysts, prepared by oxidation of Ti nonylate deposited on the Pt powder surface, contained either one (θ=1) or ten (θ=10) theoretical monolayers of TiO2. The H2 and CO chemisorption capacities showed respective decreases of 1/3 and 1/2 on the latter two catalysts although the N2 BET surface areas were essentially unchanged. XRD analysis of either TiOx/Pt sample detected no TiOx structures. Specific rates (μ mol/(s gcat)), areal rates (μ mol/(s m2)) and turnover frequencies (s-1) for the CO2 reforming of CH4 decreased in the order TiOx/Pt (θ=10)TiOx/Pt( θ=1)>>Pt powder>TiO2. Neither pure Pt powder nor pure TiO2 showed appreciable activity for CH4-CO2 reforming; thus the dramatic increase in activity is attributed to the creation of new sites in the metal-support interfacial region which promote CH4 dissociation, CO2 dissociation and reduction, and subsequent CHxO decomposition. In addition, temperature-programmed hydrogenation of used catalyst samples clearly showed that TiOx overlayers on the Pt surface suppress carbon deposition during reaction via an ensemble effect, thus improving activity maintenance.
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Bradford, M., Vannice, M. Metal-support interactions during the CO2 reforming of CH4 over model TiOx/Pt catalysts. Catalysis Letters 48, 31–38 (1997). https://doi.org/10.1023/A:1019022903491
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DOI: https://doi.org/10.1023/A:1019022903491