Crystal structure and migration paths of alkaline ions in NaVPO4F.

A sample with a nominal composition 'NaVPO4F' is prepared by mechanochemically assisted solid-state synthesis using quenching. A detailed study of its crystal and local structure is conducted by means of XRD and FTIR and solid-state 31P NMR spectroscopies in comparison with Na3V2(PO4)2F3. It is shown that the as-prepared 'NaVPO4F' has a multiphase composition, including NaVPO4F as the main phase and Na3V2(PO4)2F3 and Na2.57V4P4O17F as the side products. The crystal structure of NaVPO4F is described in the monoclinic C2/c space group. It is characterized by negligible V3+/V4+ oxidation with the corresponding F-/O2- substitution and the presence of structural disordering. Using the Voronoi-Dirichlet partition (VDP) method, the Na+ and Li+ migration pathways in Tavorite-like NaVPO4F and closely related LiVPO4F (with the triclinic structure, P1[combining macron] S.G.) are analyzed. While the Na+ migration is suppressed in both cases, the Na+/Li+ ion exchange in NaVPO4F with the formation of monoclinic LiVPO4F could occur, but is difficult due to the sodium immobility rather than the instability of the lithium derivatives as was concluded from the DFT calculations.

Solid-state NMR and computational insights into the crystal structure of silicocarnotite-based bioceramic materials synthesized mechanochemically.

In this work, we report the results of a detailed structural study of a promising bioceramic material silicocarnotite Ca5(PO4)2SiO4 (SC) synthesized from mechanochemically treated nanosized silicon-substituted hydroxyapatite by annealing at 1000°C. This novel synthetic approach represents an attractive and efficient route towards large-scale manufacturing of the silicocarnotite-based bioceramics. A combination of solid-state nuclear magnetic resonance (NMR), powder X-ray crystallography and density function theory (DFT) calculations has been implemented to characterize the phase composition of the prepared composite materials and to gain insight into the crystal structure of silicocarnotite. The phase composition analysis based on the multinuclear solid-state NMR has been found in agreement with X-ray powder diffraction indicating the minority phases of CaO (5-6wt%) and residual silicon-apatite (7-8wt%), while the rest of the material being a fairly crystalline silicocarnotite phase (86-88wt%). A combination of computational (CASTEP) and experimental methods was used to address the anionic site disorder in the silicocarnotite crystal structure. Distorted [OPO3] pyramids have appeared as an important structural motif in the SC crystal structure. The ratio between regular [PO4] and distorted [OPO3] tetrahedra is found between 2:1 and 3:1 based on XRD experiments and CASTEP calculations. The natural abundance 43Ca magic angle spinning NMR spectra of silicocarnotite are reported for the first time.

Multinuclear NMR study of silica fiberglass modified with zirconia.

Silica fiberglass textiles are emerging as uniquely suited supports in catalysis, which offer unprecedented flexibility in designing advanced catalytic systems for chemical and auto industries. During manufacturing fiberglass materials are often modified with additives of various nature to improve glass properties. Glass network formers, such as zirconia and alumina, are known to provide the glass fibers with higher strength and to slow down undesirable devitrification processes. In this work multinuclear (1)H, (23)Na, (29)Si, and (91)Zr NMR spectroscopy was used to characterize the effect of zirconia on the molecular-level fiberglass structure. (29)Si NMR results help in understanding why zirconia-modified fiberglass is more stable towards devitrification comparing with pure silica glass. Internal void spaces formed in zirconia-silica glass fibers after acidic leaching correlate with sodium and water distributions in the starting bulk glass as probed by (23)Na and (1)H NMR. These voids spaces are important for stabilization of catalytically active species in the supported catalysts. Potentials of high-field (91)Zr NMR spectroscopy to study zirconia-containing glasses and similarly disordered systems are illustrated.

129Xe NMR study of Xe adsorption on multiwall carbon nanotubes.

129Xe NMR spectroscopy has been used to study the adsorption of Xe on multi-wall carbon nanotubes (MWCNT). The results obtained have shown the 129Xe NMR ability to probe the intercrystalline (aggregate) and the inner porosity of CNT. In particular, the effects on porosity of tubes openings by hydrogen exposure and of ball milling were examined. Dramatic changes observed in the 129Xe NMR spectra after moderate ball milling of MWCNTs were attributed to the destruction of the initial intercrystalline pore structure and to the Xe access inside the nanotubes. To examine the exchange dynamics the mixture of as-made and milled MWCNTs was studied with one- and two-dimensional (1D and 2D) 129Xe NMR. The exchange between the interior of milled nanotubes and the aggregate pores of as-made MWCNTs was fast on the NMR acquisition time scale. The Xenon exchange between the interior of the as-made MWCNTs and the large aggregate pores occurred on a longer time scale of 10 ms, as was established by 2D 129Xe NMR exchange spectroscopy. Variable temperature 129Xe NMR data were also discussed and analyzed in terms of the fast exchange approximation.

1H, 51V and 15N nuclear magnetic resonance studies of structure and properties of vanadia supported on TiO chi/SiO2.

1H magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra of TiO chi/SiO2 catalysts suggest the interaction of surface TiO chi species with Si-OH groups of the silica. Simultaneously, Ti-OH groups from surface titania species appear. The distribution of TiO chi species over SiO2 is non-uniform, since a considerable part of surface OH groups remains unreacted with supported titania. Supported vanadia species interact both with Si-OH and Ti-OH groups. 51V NMR spectra suggest the interaction of vanadia with supported titania species and show the non-uniform distribution of titania over the SiO2 surface. Deposition of titania as well as vanadia produces strong electron-accepting (Lewis) sites which interact with the terminal N atom of adsorbed N2O molecules, resulting in a downfield shift of the resonance in 15N NMR spectra. The acid strength of electron-accepting sites is similar in both cases. Only about 10% of the total amount of supported titania and vanadia create Lewis sites.

Characterization of V2O5-AlPO4 catalysts by 51V and 1H magic-angle spinning solid-state nuclear magnetic resonance spectroscopy.

Amorphous aluminum orthophosphate is used as a carrier for preparing a series of V2O5-AlPO4 catalysts with varying vanadia content. The catalysts were characterized by solid-state 51V and 1H magic-angle spinning nuclear magnetic resonance (MAS NMR), electron spin resonance (ESR) and X-ray diffraction (XRD). The XRD patterns of the catalysts remained amorphous at all loadings studied. 51V Solid-state NMR spectra revealed the presence of V2O5 microcrystallites at higher vanadia loadings. The 1H MAS NMR spectra of the catalysts showed a maximum consumption of support hydroxyl groups at 6 wt.-% V2O5 indicating the completion of a monolayer at this composition.