Multi-Frequency and Single-Crystal EPR on V4+ in W-Doped β-Vanadyl(V) Phosphate: Hyperfine Coupling- and g-Tensor Values and Orientation

• Published in: Applied magnetic resonance Vol. 52; no. 2; pp. 169 - 175
• Main Authors: NejatyJahromy, Yaser, Roy, Subrata Chandra, Glaum, Robert, Schiemann, Olav
• Format: Journal Article
• Language: English
• Published: Vienna Springer Vienna 01.02.2021; Springer Nature B.V
• Subjects: Atoms and Molecules in Strong Fields; Catalytic activity; Electron paramagnetic resonance; Electronic structure; Laser Matter Interaction; Magnetic fields; Maleic anhydride; Mathematical analysis; Organic Chemistry; Original Paper; Oxidation; Phosphorus; Physical Chemistry; Physics; Physics and Astronomy; Simulation; Single crystals; Solid solutions; Solid State Physics; Spectra; Spectroscopy/Spectrometry; Spectrum analysis; Superhigh frequencies; Tensors; Valence
• ISSN: 0937-9347; 1613-7507
• DOI: 10.1007/s00723-020-01303-0

Different structure types of vanadyl(V) orthophosphate [i.e. (V V ≡O) 3+ orthophosphate] have been subjects of research due to their catalytic activity in the oxidation of n -butane to maleic anhydride. Electron paramagnetic resonance (EPR) spectroscopy can be exploited to elucidate the electronic structure of such compounds. When tuning the oxidation state of vanadium in (V 1-x W x )OPO 4 , X-band EPR spectra have confirmed the presence of paramagnetic V 4+ ions. However, some of the features in these spectra could not be explained. Here, powder samples of β -(V IV 0.01 V V .98 W VI .01 )OPO 4 are investigated at S-, X- and Q- band, along with X-band EPR measurements on single crystals. Thereby, the discrepancies between the spectra and their simulations could be resolved. In particular, it could be shown that the g and A tensors are not coaxial. The resulting consistent EPR picture and the refined paramagnetic parameters are reported. The work underlines the indispensability of a multi-frequency approach in EPR for unequivocal conclusions.