Influence of the support on rhodium speciation and catalytic activity of rhodium-based catalysts for total oxidation of methane

摘要

The role of the support in Rh-based catalysts for total oxidation of CH(4)was investigated using both amorphous SiO(2)and gamma-Al(2)O(3)as well as ZSM-5 and SSZ-13 zeolites with varying SiO2/Al(2)O(3)ratios. The methane oxidation activity was measured in both the presence and absence of 5 vol% H2O and 20 ppm SO2. The support had a strong impact on Rh speciation (Rh(2)O(3)nanoparticlesvs.single Rh atom sites), which was important for the activity, as the nanoparticle sites were found to be far more active than the single atom sites. A 2 wt% Rh/ZSM-5(SiO2/Al2O3= 280) catalyst with Rh exclusively as Rh(2)O(3)nanoparticles was able to provide oxidation at a 75 degrees C lower temperature than an ion-exchanged 0.294 wt% Rh/ZSM-5(SiO2/Al2O3= 30) catalyst with Rh exclusively as single atoms despite a similar concentration of active sites in the two samples. All the catalysts were inhibited by the presence of water, but this inhibition was particularly strong for an amorphous SiO(2)support and for the most Al-rich zeolites and less severe for Si-rich zeolites. The inhibition from SO(2)was relatively stronger for the more Al-rich supports, which was attributed to an uptake of sulfur at Al sites that was detrimental to the performance of the active phase. In a realistic gas atmosphere containing both H2O and SO2, Si-rich ZSM-5(SiO2/Al2O3= 280) therefore emerged as the best support. This was because the low acidity ensured minimal loss of Rh to the less active single atom sites, avoidance of the detrimental sulfur uptake by the support seen for more Al-rich supports, and avoidance of the strong water-induced inhibition that occurs for amorphous SiO(2)and Al-rich zeolites.