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Elucidating structure and dynamics of crystalline α-zirconium phosphates intercalated with water and methanol by multinuclear solid-state MAS NMR: A comprehensive NMR approach

Journal Article · · Magnetic Resonance in Chemistry
DOI:https://doi.org/10.1002/mrc.5262· OSTI ID:1976360
 [1];  [2];  [2];  [2]
  1. Texas A & M University, College Station, TX (United States); OSTI
  2. Texas A & M University, College Station, TX (United States)
+ Show Author Affiliations
Solid-state NMR experiments on 2H, 31P, 13C, and 1H nuclei, including 31P T1, 1H T1, and 1H T1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D2O and/or CD3OD. The 13C{1H} CP MAS NMR experiment performed for compound 1-CD3OD (Zr (HPO4)2.0.2CD3OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature 2H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD3 rotations around the C3-axis. It has been demonstrated that the intercalated species, D2O and CD3OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Here, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.
Research Organization:
Texas A & M University, College Station, TX (United States)
Sponsoring Organization:
Robert A. Welch Foundation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0017864
OSTI ID:
1976360
Alternate ID(s):
OSTI ID: 1853824
Journal Information:
Magnetic Resonance in Chemistry, Journal Name: Magnetic Resonance in Chemistry Journal Issue: 6 Vol. 60; ISSN 0749-1581
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

1H
31P relaxation
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
isotopic exchanges
kinetics of cross-polarization
solid-state 2H and 31P NMR
structural elucidation
zirconium phosphates