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The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A): insights from NMR crystallography

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The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A) : insights from NMR crystallography. / Dawson, Daniel M.; Walton, Richard I.; Wimperis, Stephen; Ashbrook, Sharon E.

In: Acta Crystallographica Section C: Structural Chemistry, Vol. 73, No. 3, 03.2017, p. 191-201.

Research output: Contribution to journalJournal articlepeer-review

Harvard

Dawson, DM, Walton, RI, Wimperis, S & Ashbrook, SE 2017, 'The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A): insights from NMR crystallography', Acta Crystallographica Section C: Structural Chemistry, vol. 73, no. 3, pp. 191-201. https://doi.org/10.1107/S2053229617000377

APA

Dawson, D. M., Walton, R. I., Wimperis, S., & Ashbrook, S. E. (2017). The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A): insights from NMR crystallography. Acta Crystallographica Section C: Structural Chemistry, 73(3), 191-201. https://doi.org/10.1107/S2053229617000377

Vancouver

Dawson DM, Walton RI, Wimperis S, Ashbrook SE. The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A): insights from NMR crystallography. Acta Crystallographica Section C: Structural Chemistry. 2017 Mar;73(3):191-201. https://doi.org/10.1107/S2053229617000377

Author

Dawson, Daniel M. ; Walton, Richard I. ; Wimperis, Stephen ; Ashbrook, Sharon E. / The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A) : insights from NMR crystallography. In: Acta Crystallographica Section C: Structural Chemistry. 2017 ; Vol. 73, No. 3. pp. 191-201.

Bibtex

@article{b9a3f22d1973432da3bc296b8ecb9d67,
title = "The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A): insights from NMR crystallography",
abstract = "The aluminophosphate (AlPO) JDF-2 is prepared hydro­thermally with methyl­ammonium hydroxide (MAH+·HO-, MAH+ = CH3NH3+), giving rise to a microporous AEN-type framework with occluded MAH+ cations and extra-framework (Al-bound) HO- anions. Despite the presence of these species within its pores, JDF-2 can hydrate upon exposure to atmospheric moisture to give AlPO-53(A), an isostructural material whose crystal structure contains one mol­ecule of H2O per formula unit. This hydration can be reversed by mild heating (such as the frictional heating from magic angle spinning). Previous work has shown good agreement between the NMR parameters obtained experimentally and those calculated from the (optimized) crystal structure of JDF-2. However, several discrepancies are apparent between the experimental NMR parameters for AlPO-53(A) and those calculated from the (optimized) crystal structure (e.g. four 13C resonances are observed, rather than the expected two). The unexpected resonances appear and disappear reversibly with the respective addition and removal of H2O, so clearly arise from AlPO-53(A). We investigate the ambient hydration of JDF-2 using qu­anti­tative 31P MAS NMR to follow the transformation over the course of 3 months. The structures of JDF-2 and AlPO-53(A) are also investigated using a combination of multinuclear solid-state NMR spectroscopy to characterize the samples, and first-principles density functional theory (DFT) calculations to evaluate a range of possible structural models in terms of calculated NMR parameters and energetics. The published structure of JDF-2 is shown to be a good representation of the dehydrated material, but modification of the published structure of AlPO-53(A) is required to provide calculated NMR parameters that are in better agreement with experiment. This modification includes reorientation of all the MAH+ cations and partial occupancy of the H2O sites.",
keywords = "aluminophosphate, AEN framework, zeolites, microporous materials, NMR crystallographY, JDF-2;AlPO-53(A)",
author = "Dawson, {Daniel M.} and Walton, {Richard I.} and Stephen Wimperis and Ashbrook, {Sharon E.}",
note = "# 2017 International Union of Crystallography",
year = "2017",
month = mar,
doi = "10.1107/S2053229617000377",
language = "English",
volume = "73",
pages = "191--201",
journal = "Acta Crystallographica Section C: Structural Chemistry",
issn = "2053-2296",
publisher = "John Wiley and Sons Inc.",
number = "3",

}

RIS

TY - JOUR

T1 - The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A)

T2 - insights from NMR crystallography

AU - Dawson, Daniel M.

AU - Walton, Richard I.

AU - Wimperis, Stephen

AU - Ashbrook, Sharon E.

N1 - # 2017 International Union of Crystallography

PY - 2017/3

Y1 - 2017/3

N2 - The aluminophosphate (AlPO) JDF-2 is prepared hydro­thermally with methyl­ammonium hydroxide (MAH+·HO-, MAH+ = CH3NH3+), giving rise to a microporous AEN-type framework with occluded MAH+ cations and extra-framework (Al-bound) HO- anions. Despite the presence of these species within its pores, JDF-2 can hydrate upon exposure to atmospheric moisture to give AlPO-53(A), an isostructural material whose crystal structure contains one mol­ecule of H2O per formula unit. This hydration can be reversed by mild heating (such as the frictional heating from magic angle spinning). Previous work has shown good agreement between the NMR parameters obtained experimentally and those calculated from the (optimized) crystal structure of JDF-2. However, several discrepancies are apparent between the experimental NMR parameters for AlPO-53(A) and those calculated from the (optimized) crystal structure (e.g. four 13C resonances are observed, rather than the expected two). The unexpected resonances appear and disappear reversibly with the respective addition and removal of H2O, so clearly arise from AlPO-53(A). We investigate the ambient hydration of JDF-2 using qu­anti­tative 31P MAS NMR to follow the transformation over the course of 3 months. The structures of JDF-2 and AlPO-53(A) are also investigated using a combination of multinuclear solid-state NMR spectroscopy to characterize the samples, and first-principles density functional theory (DFT) calculations to evaluate a range of possible structural models in terms of calculated NMR parameters and energetics. The published structure of JDF-2 is shown to be a good representation of the dehydrated material, but modification of the published structure of AlPO-53(A) is required to provide calculated NMR parameters that are in better agreement with experiment. This modification includes reorientation of all the MAH+ cations and partial occupancy of the H2O sites.

AB - The aluminophosphate (AlPO) JDF-2 is prepared hydro­thermally with methyl­ammonium hydroxide (MAH+·HO-, MAH+ = CH3NH3+), giving rise to a microporous AEN-type framework with occluded MAH+ cations and extra-framework (Al-bound) HO- anions. Despite the presence of these species within its pores, JDF-2 can hydrate upon exposure to atmospheric moisture to give AlPO-53(A), an isostructural material whose crystal structure contains one mol­ecule of H2O per formula unit. This hydration can be reversed by mild heating (such as the frictional heating from magic angle spinning). Previous work has shown good agreement between the NMR parameters obtained experimentally and those calculated from the (optimized) crystal structure of JDF-2. However, several discrepancies are apparent between the experimental NMR parameters for AlPO-53(A) and those calculated from the (optimized) crystal structure (e.g. four 13C resonances are observed, rather than the expected two). The unexpected resonances appear and disappear reversibly with the respective addition and removal of H2O, so clearly arise from AlPO-53(A). We investigate the ambient hydration of JDF-2 using qu­anti­tative 31P MAS NMR to follow the transformation over the course of 3 months. The structures of JDF-2 and AlPO-53(A) are also investigated using a combination of multinuclear solid-state NMR spectroscopy to characterize the samples, and first-principles density functional theory (DFT) calculations to evaluate a range of possible structural models in terms of calculated NMR parameters and energetics. The published structure of JDF-2 is shown to be a good representation of the dehydrated material, but modification of the published structure of AlPO-53(A) is required to provide calculated NMR parameters that are in better agreement with experiment. This modification includes reorientation of all the MAH+ cations and partial occupancy of the H2O sites.

KW - aluminophosphate

KW - AEN framework

KW - zeolites

KW - microporous materials

KW - NMR crystallographY

KW - JDF-2;AlPO-53(A)

U2 - 10.1107/S2053229617000377

DO - 10.1107/S2053229617000377

M3 - Journal article

VL - 73

SP - 191

EP - 201

JO - Acta Crystallographica Section C: Structural Chemistry

JF - Acta Crystallographica Section C: Structural Chemistry

SN - 2053-2296

IS - 3

ER -