Variable-Temperature Multinuclear Solid-State NMR Study of Oxide Ion Dynamics in Fluorite-Type Bismuth Vanadate and Phosphate Solid Electrolytes

In this study, we employ a multinuclear, variable-temperature NMR spectroscopy approach to characterise and measure oxide ionic motion in the V- and P-substituted bismuth oxide materials Bi0.913V0.087O1.587, Bi0.852V0.148O1.648 and Bi0.852P0.148O1.648, previously shown to have excellent ionic conduction properties. Two main 17O NMR resonances are distinguished for each material, corresponding to O in the Bi–O and V–O/P–O sublattices. Using variable-temperature (VT) measurements ranging from room temperature to 923 K, the ionic motion experienced by these different sites has then been characterised, with coalescence of the two environments in the V-substituted materials clearly indicating a conduction mechanism facilitated by exchange between the two sublattices. The lack of this coalescence in the P-substituted material indicates a different mechanism, confirmed by 17O T1 (spin-lattice relaxation) NMR experiments to be driven purely by vacancy motion in the Bi–O sublattice. 51V and 31P VT-NMR experiments show high rates of tetrahedral rotation even at room temperature, increasing with heating. An additional VO4 environment appears in 17O and 51V NMR spectra of the more highly V-substituted Bi0.852V0.148O1.648, which we ascribe to differently distorted VO4 tetrahedral units that disrupt the overall ionic motion, consistent both with linewidth analysis of the 17O VT-NMR spectra and experimental results of Kuang et al. showing a lower oxide ionic conductivity in this material compared to Bi0.913V0.087O1.587 (Chem. Mater. 2012, 24, 2162). This study shows solid-state NMR is particularly well suited to understanding connections between local structural features and ionic mobility, and can quantify the evolution of oxide-ion dynamics with increasing temperature.

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Variable-Temperature Multinuclear Solid-State NMR Study of Oxide Ion Dynamics in Fluorite-Type Bismuth Vanadate and Phosphate Solid Electrolytes

Chemistry of Materials ◽

10.1021/acs.chemmater.8b05143 ◽

2019 ◽

Vol 31 (5) ◽

pp. 1704-1714 ◽

Cited By ~ 7

Author(s):

Matthew T. Dunstan ◽

David M. Halat ◽

Matthew L. Tate ◽

Ivana Radosavljevic Evans ◽

Clare P. Grey

Keyword(s):

Solid State ◽

Solid State Nmr ◽

Solid Electrolytes ◽

Variable Temperature ◽

Bismuth Vanadate ◽

Ion Dynamics ◽

Nmr Study ◽

Fluorite Type ◽

Oxide Ion

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Variable-temperature 13C solid-state NMR spectra: Mobility of trimethyltin groups in coordination polymers of the type [(Me3Sn)4M(CN)6]∞ (MFe, Os, Ru)

Spectrochimica Acta Part A Molecular Spectroscopy ◽

10.1016/0584-8539(93)e0020-w ◽

1994 ◽

Vol 50 (12) ◽

pp. 2069-2078 ◽

Cited By ~ 12

Author(s):

Robin K. Harris ◽

M.Maral Sünnetçioğlu ◽

R.Dieter Fischer

Keyword(s):

Solid State ◽

Coordination Polymers ◽

Solid State Nmr ◽

Nmr Spectra ◽

Variable Temperature

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Nuclear magnetic resonance studies of the methylammonium hexahalotellurates

Canadian Journal of Chemistry ◽

10.1139/v92-112 ◽

1992 ◽

Vol 70 (3) ◽

pp. 849-855 ◽

Cited By ~ 2

Author(s):

Mark R. MacIntosh ◽

Marco L. H. Gruwel ◽

Katherine N. Robertson ◽

Roderick E. Wasylishen

Keyword(s):

Line Shape ◽

Nmr Spectra ◽

Room Temperature ◽

Solid Phase ◽

Variable Temperature ◽

Spin Lattice Relaxation ◽

Temperature Phase ◽

H Nmr ◽

Nmr Study ◽

Correlated Motion

A 2H and 14N NMR study of the solid methylammonium hexahalotellurates, (MA)2TeX6 (MA = CH3ND3+ or CD3NH3+, X = Cl, Br, and I), has been undertaken to characterize the dynamics of the methylammonium (MA) ion as a function of temperature. At room temperature, the MA ion in the hexachlorotellurate (solid II) is confined to C3 jumps about the C—N axis while a small angle libration of the C—N axis is occurring. In the room temperature phase, solid I, of (MA)2TeBr6 and (MA)2TeI6 the MA ions are performing overall reorientations on the ps time scale, averaging the 2H nuclear quadrupolar interactions to zero. Variable temperature 2H NMR spin-lattice relaxation times, T1, indicate an activation energy, EA, for "isotropic" reorientations of the CH3ND3+ ion of 5.2 ± 0.5 and 2.6 ± 0.3 kJ mol−1 for X = Br and I, respectively. Deuterium T1 values for C-deuterated MA ion in the hexaiodotellurate indicate an EA for whole-ion reorientation of 3.1 ± 0.3 kJ mol−1. At any given temperature, the correlation time, τc, derived from the T1 results was found to be the same for the two deuterium-labelled hexaiodotellurates. The similarity of both the EA and the τc values implies correlated motion of the methyl and ammonium groups. The 14N T1 results for solid I of (MA)2TeI6 indicate that C—N axis motions, with an EA = 5.6 ± 0.6 kJ mol−1, are more hindered than N—D or C—D bond dynamics. The 2H NMR spectra for (MA)2TeI6 (solid II) and (MA)2TeBr6 (solids II, III, and IV) are characterized by a Pake doublet line shape. The measured peak-to-peak splittings are less than what is predicted by C3 motion about the molecular symmetry axis. It is possible to model these line shapes by postulating that C3 rotations of the methyl and ammonium groups occur as the C—N axis librates in an effective cone about the position of the static molecular axis. For (CH3ND3)2TeBr6 and (CD3NH3)3TeBr6 the peak-to-peak splittings in the 2H NMR spectra were measured as a function of temperature in solid phases II, III, and IV and were found to be similar. Finally, the 2H NMR line shape relaxation for (MA)2TeBr6 (solid III) displays an orientation dependence indicating that rotations about the C—N axis are discrete rather than diffusive in nature. For solid phase II of (MA)2TeCl6, the line shape is observed to relax isotropically, implying that continuous C3 rotations are taking place. Keywords: 2H and 14N NMR, methylammonium hexahalotellurates, molecular motion.

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Structure Resolution of Ba5Al3F19and Investigation of Fluorine Ion Dynamics by Synchrotron Powder Diffraction, Variable-Temperature Solid-State NMR, and Quantum Computations

Inorganic Chemistry ◽

10.1021/ic102534d ◽

2011 ◽

Vol 50 (6) ◽

pp. 2644-2653 ◽

Cited By ~ 32

Author(s):

Charlotte Martineau ◽

Franck Fayon ◽

Matthew R. Suchomel ◽

Mathieu Allix ◽

Dominique Massiot ◽

...

Keyword(s):

Solid State ◽

Powder Diffraction ◽

Solid State Nmr ◽

Variable Temperature ◽

Ion Dynamics ◽

Synchrotron Powder Diffraction ◽

Quantum Computations

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Correction and comment on “Variable-temperature 13C solid-state NMR spectra: mobility of trimethyltin groups in coordination polymers of the type [(Me3Sn)4M(CN)6]∞ (M = Fe, Os, Ru)” [Spectrochim. Acta Part A 50 (1994) 2069]

Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy ◽

10.1016/0584-8539(95)01402-0 ◽

1995 ◽

Vol 51 (8) ◽

pp. 1389-1390

Author(s):

Robin K Harris ◽

M Maral Sünnetçioglu ◽

R Dieter Fischer

Keyword(s):

Solid State ◽

Coordination Polymers ◽

Solid State Nmr ◽

Nmr Spectra ◽

Variable Temperature

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Solid-state motion of OTeF5− compounds: detection by 19F NMR and IR spectroscopy and correlation with the X-ray structure of an orthorhombic crystalline modification of [C14H19N2+][OTeF5−] (C14H19N2+ = protonated 1,8-bis(dimethylamino)naphthalene)

Canadian Journal of Chemistry ◽

10.1139/v89-313 ◽

1989 ◽

Vol 67 (11) ◽

pp. 2023-2029 ◽

Cited By ~ 26

Author(s):

Patti J. Kellett ◽

Oren P. Anderson ◽

Steven H. Strauss ◽

Kent D. Abney

Keyword(s):

Solid State ◽

Nmr Spectra ◽

Room Temperature ◽

Variable Temperature ◽

Structural Parameters ◽

Crystalline Modification ◽

X Ray Diffraction ◽

Orthorhombic Space Group ◽

X Ray ◽

Triclinic Modification

An orthorhombic crystalline modification of [(PS)H+][OTeF5−] was studied by single crystal X-ray diffraction ((PS)H+ = protonated 1,8-bis(dimethylamino)naphthalene): orthorhombic, space group Cmcm, a = 8.607(2), b = 14.048(3), c = 13.365(2) Å, Z = 4, T = −130 °C. The structural parameters for the anion and cation in this modification (Mod-B) are very similar to those for the previously reported triclinic modification of this salt (Mod-A). However, variable temperature IR spectra for Mod-B suggest that the OTeF5− anion is exhibiting a two-site O/Fax interchange above −70 °C. Solid-state 19F NMR spectra suggest that this interchange may be as rapid as 104–105 s−1 at room temperature. Keywords: crystal structure of protonated 1,8-bis(dimethylamino)naphthalene)pentafluorotellurate(VI), polymorphism, solid state 19FNMR.

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Variable temperature solid-state NMR spectral and relaxation analyses of the impregnation of polyethylene glycol (PEG) into coniferous wood

RSC Advances ◽

10.1039/c9ra01848d ◽

2019 ◽

Vol 9 (27) ◽

pp. 15657-15667 ◽

Cited By ~ 3

Author(s):

Masakazu Nishida ◽

Tomoko Tanaka ◽

Tsunehisa Miki ◽

Ichinori Shigematsu ◽

Kozo Kanayama

Keyword(s):

Polyethylene Glycol ◽

Solid State ◽

Solid State Nmr ◽

Nmr Spectra ◽

Variable Temperature ◽

Relaxation Times ◽

Japanese Cypress ◽

Coniferous Wood

To investigate the behaviours of polyethylene glycol (PEG) and its interaction with biomass constituents in coniferous wood (Japanese cypress), variable temperature solid-state NMR spectra and relaxation times were measured from 20–80 °C.

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