Vanadyl species, paramagnetic

It is apparent from the chemical shifts (g-values), the hyperfine coupling constants (A-values), and the linewidths that the free radicals and vanadyl species are in very similar environments in both samples. It was not possible to obtain meaningful values for the absolute numbers of spins per gram for either species, but estimates of the relative concentrations obtained by measuring peak heights indicate that the vanadyl and free-radical concentrations do not differ significantly between the two asphaltenes. It thus appears that heat treatment of Cold Lake asphaltenes to 320°C does not alter the nature or abundance of paramagnetic centers. 

The incorporation of V ion (3 d ) in a tetrahedral fi amework may be directly investigated by EPR spectroscopy, especially that the (VO) ion is a well characterized paramagnetic centre. Slinkin et al. have observed that heating Al-MFI with vanadium oxide resulted in the appearance of a hyperfine pattern assigned to vanadyl species occluded in -or graphted at- the zeolite framework. 

Analysis of vanadium-loaded model materials (such as EuY, amorphous aluminosilicate gels and EuY-gel mixtures) by electron paramagnetic resonance (EPR) has provided information concerning metal oxidation state and stereochemistry (67). EPR data has indicated that when vanadyl cations are introduced in the form of vanadyl naphthenate, they were stabilized in a zeolite with the faujasite structure as pseudo-octahedral V02+ even after calcination at 540°C. Upon steaming, these V02+ cations were then converted almost entirely to V+5 species (67). The formation of EuV04 was verified but the concentration of this vanadate was never proportional to the total rare-earth content of the zeolite. In EuY-gel mixtures the gel preferentially sorbed vanadium where it was stabilized mainly in the form of V205. 

Components of fluidized cracking catalysts (FCC), such as an aluminosilicate gel and a rare-earth (RE) exchanged zeolite Y, have been contaminated with vanadyl naphthenate and the V thus deposited passivated with organotin complexes. Luminescence, electron paramagnetic resonance (EPR) and Mossbauer spectroscopy have been used to monitor V-support interactions. Luminescence results have indicated that the naphthenate decomposes during calcination in air with generation of (V 0)+i ions. After steam-aging, V Og and REVO- formation occurred. In the presence of Sn, Tormation Of vanadium-tin oxide species enhance the zeolite stability in the presence of V-contaminants. 

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