Isolated FeII on Silica As a Selective Propane Dehydrogenation Catalyst

We report a comparative study of isolated FeII, iron oxide particles, and metallic nanoparticles on silica for non-oxidative propane dehydrogenation. It was found that the most selective catalyst was an isolated FeII species on silica prepared by grafting the open cyclopentadienide iron complex, bis(2,4-dimethyl-1,3-pentadienide) iron(II) or Fe(oCp)2. The grafting and evolution of the surface species was elucidated by 1H NMR, diffuse reflectance infrared Fourier transform spectroscopy and X-ray absorption spectroscopies. The oxidation state and local structure of surface Fe were characterized by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure. The initial grafting of iron proceeds by one surface hydroxyl Si–OH reacting with Fe(oCp)2 to release one diene ligand (oCpH), generating a SiO2-bound FeII(oCp) species, 1-FeoCp. Subsequent treatment with H2 at 400 °C leads to loss of the remaining diene ligand and formation of nanosized iron oxide clusters, 1-C. Dispersion of these Fe oxide clusters occurs at 650 °C, forming an isolated, ligand-free FeII on silica, 1-FeII, which is catalytically active and highly selective (∼99%) for propane dehydrogenation to propene. Under reaction conditions, there is no evidence of metallic Fe by in situ XANES. For comparison, metallic Fe nanoparticles, 2-NP-Fe0, were independently prepared by grafting FeN(SiMe3)22 onto silica, 2-FeN*, and reducing it at 650 °C in H2. The Fe NPs were highly active for propane conversion but showed poor selectivity (∼14%) to propene. Independently prepared Fe oxide clusters on silica display a low activity. The sum of these results suggests that selective propane dehydrogenation occurs at isolated FeII sites.