Applied Catalysis B: Environmental, Vol.194, 22-31, 2016
Methane combustion over bimetallic Ru-Re/gamma-Al2O3 catalysts: Effect of Re and pretreatments
In this paper, we have presented the results of the studies on methane combustion over bimetallic RuRe/gamma-Al2O3 catalysts containing 1 or 3 wt.% of Re, and their comparison with those obtained over 5% Ru/gamma-Al2O3 catalyst. The catalytic activity was examined on reduced catalysts and then aged in air at 500 degrees C under O-2-rich conditions. All catalysts were characterized by various methods such as BET, XRD, TEM, HAADF-STEM, EDS and H-2-TPR in order to correlate their activity with their physiochemical properties. A positive effect of the ageing treatment on the catalytic performance was observed for the both bimetallic Ru-Re catalysts but not for the Ru catalyst. The methane oxidation rate over the aged Ru-Re catalysts was about 5-10 times higher compared to that of the aged Ru catalyst. Characterization data show that at ageing temperature of 500 C small Ru or RuRe particles were transformed into larger RuO2 particles and/or highly dispersed ReOx species strongly interacting with gamma-alumina. The mean crystallite size of RuO2 decreased from 25 to 14nm when the Re loading had been changed from 1 to 3 wt.%, while in the monometallic Ru catalyst it was higher and amounted to 30 nm. Among the reduced catalysts, the 5%Ru-1%Re catalyst exhibited the highest activity for combustion of methane. Also, for this sample apparent activation energy (104 kJ mol(-1)) was lower as compared to that of the monometallic Ru catalyst (116 kJ mol(-1)), indicating that Re slightly lowers the methane activation barrier. For the Ru as well as bimetallic Ru-Re catalysts an instability of methane conversion as a function of time (80 h) at a given temperature (500 degrees C) was observed. The instability was associated with slow formation of larger RuO2 crystallites (40-45 nm) during the course of the reaction. In summary, the addition of Re improves the catalytic activity of the Ru/gamma-Al2O3 catalysts for methane combustion but thermal stability of the bimetallic samples is similar to that of the unpromted Ru catalyst. (C) 2016 Elsevier B.V. All rights reserved.