The interaction of oxygen with high loaded Ru/γ-Al2O3 catalyst

The interaction of oxygen with the Ru/γ-Al₂O₃ catalyst comprising metal particle with sizes of 1-16 nm, was examined over a temperature range 20-400 °C. The catalyst loaded with 10.8 wt.% Ru was prepared by incipient wetness from RuCl₃ precursor. The structure of the Cl-containing catalyst and the catalyst after elimination Cl⁻ ions was characterized using H₂ and O₂ chemisorption, O₂ uptake, BET, XRD and TEM. The Cl⁻ ions in the catalyst decreased the H₂ and O₂ chemisorption capacity of Ru and caused large discrepancies between the mean particle size calculated from gas chemisorption and from TEM. Exposure to O₂ at 100-200 °C caused oxidation of small Ru particles, while larger particles were covered with very thin Ru_xO_y skin (undetected by XRD and TEM). The O/Ru ratio increased up to 200 °C implying high affinity of the small Ru particles to oxygen. Oxidation at 250 °C led to the formation of poorly crystalline RuO₂ particles with a mean size of 4 nm, and coverage of large Ru particles with 1.6 nm thick oxide layer. At 300 and 400 °C crystallization of the RuO₂ phase, as well as significant agglomeration of oxide particles was observed. However, even at 400 °C, metallic Ru was detected by XRD, TEM and SAED suggesting that large metal particles were not fully oxidized under the used conditions. Also, the O₂ uptake at 400 °C was lower than expected for oxidation of Ru metal to RuO₂. For the catalyst after elimination Cl ions the O₂ uptake (O/Ru ratio = 1.50) was higher, than for sample with large amount of Cl ions (O/Ru ratio = 1.34), indicating that the presence of Cl inhibits ruthenium oxidation in the Ru/Al₂O₃ catalyst.