Particle size effect in methane activation over supported palladium nanoparticles

A synthesis method for producing MgAl oxide supported uniform palladium nanoparticles with varying diameters has been developed. The method consists of reductive-thermal decomposition of a PdMgAl hydrotalcite-like compound, formed via co-precipitation of metal nitrate salts and sodium carbonate. The hydrotalcite–like precursors were characterized by XRD, TG-MS and SEM, and were found to contain a well-defined crystalline structure and a uniform distribution of all constituent elements. The resulting catalysts were characterized by XRD, TEM, Chemisorption of CO and in situ IR measurements of CO, and were found to consist of partially oxide-embedded Pd nanoparticles with diameters ranging from d = 1.7 to 3.3 nm and correspond dispersions of 67–14%. Furthermore, the particle size was found to be inversely related to Pd loading. The palladium catalysts were studied for methane activation via chemisorption at 200 and 400 °C followed by a temperature programmed surface hydrogenation. The most disperse catalyst (d = 1.7 nm) possessed an intrinsic methane adsorption capacity, which was an order of magnitude larger than that of other catalysts in the series, indicating a strong structure sensitivity in this reaction. Additionally, the methane adsorption capacity of the hydrotalcite-derived Pd catalysts was nearly two orders of magnitude higher than that of catalysts derived through other synthesis pathways such as colloidal deposition or sonochemical reduction.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (250 K)Download as PowerPoint slideHighlights► A series of supported Pd catalysts was prepared from Hydrotalcite precursors. ► The particle size of Pd Nanoparticles have been tuned from 1.7 to 3.8 nm. ► The methane chemisorptions capacity was largely enhanced for particles <2 nm. ► For 2 nm the capacity scaled with the Pd loading.