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Title: 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
ORCiD logo [1];  [1];  [1];  [1]
  1. Texas A & M University, College Station, TX (United States)
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Abstract Solid‐state NMR experiments on 2 H, 31 P, 13 C, and 1 H nuclei, including 31 P T 1 , 1 H T 1 , and 1 H T 1ρ 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 D 2 O and/or CD 3 OD. The 13 C{ 1 H} CP MAS NMR experiment performed for compound 1‐CD 3 OD (Zr (HPO 4 ) 2 . 0.2CD 3 OD) 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 2 H solid‐echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD 3 rotations around the C 3 ‐axis. It has been demonstrated that the intercalated species, D 2 O and CD 3 OD, 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. Thus, 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 Univ., College Station, TX (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Robert A. Welch Foundation
Grant/Contract Number:
SC0017864; A-0030; DE‐SC0017864
OSTI ID:
1976360
Alternate ID(s):
OSTI ID: 1853824
Journal Information:
Magnetic Resonance in Chemistry, Vol. 60, Issue 6; ISSN 0749-1581
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

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