Skip to content

Research at St Andrews

The effects of extraframework species on the structure-based prediction of 31P isotropic chemical shifts of aluminophosphates

Research output: Contribution to journalArticlepeer-review

Author(s)

School/Research organisations

Abstract

31P NMR spectroscopy is a valuable technique for the characterization of the local structure of aluminophosphates (AlPOs), capable of providing information on the number of crystallographic P sites, their relative populations, and the positions of any dopant atoms in the framework. Assigning the 31P spectra may, however, require multinuclear NMR experiments and/or density functional theory (DFT) calculations, which can be time consuming, computationally costly, and challenging in cases involving disorder or dynamics. To address the issue of computational cost, we recently demonstrated a simple relationship between the local structure around P (primarily in terms of the mean P-O bond length and P-O-Al bond angle) and the 31P isotropic chemical shift, δiso, calculated by DFT for a series of calcined AlPOs. Here, we extend this approach to as-made AlPOs where we show that, at least to a first approximation, the presence of framework-bound anions and/or guest species within the pores of AlPOs can be translated directly to a distortion of the local framework geometry without considering any additional structural parameters. This allows the prediction of a DFT-level 31P δiso even in cases where the structure may be highly disordered or partially incomplete (precluding the use of electronic structure calculations), and we investigate the minimal structural information required to provide meaningful results. The structure-spectrum relationship produced forms the basis for the geometry-based DIStortion COde (DISCO), which can rapidly (on the ms timescale) predict the outcome of a DFT calculation of 31P δiso to within 1.1 ppm.
Close

Details

Original languageEnglish
Pages (from-to)28065-28076
JournalJournal of Physical Chemistry C
Volume121
Issue number50
Early online date27 Nov 2017
DOIs
Publication statusPublished - 21 Dec 2017

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Exploring cation disorder in mixed-metal pyrochlore ceramics using 17O NMR spectroscopy and first-principles calculations

    Fernandes, A., Moran, R. F., McKay, D., Griffiths, B., Herlihy, A., Whittle, K. R., Dawson, D. M. & Ashbrook, S. E., 15 Feb 2021, In: Magnetic Resonance in Chemistry. Early View, 14 p.

    Research output: Contribution to journalArticlepeer-review

  2. Single-step synthesis and interface tuning of core–shell metal–organic framework nanoparticles

    Orr, K. W. P., Collins, S. M., Reynolds, E. M., Nightingale, F., Boström, H. L. B., Cassidy, S. J., Dawson, D. M., Ashbrook, S. E., Magdysyuk, O. V., Midgley, P., Goodwin, A. L. & Yeung, H. H-M., 9 Feb 2021, In: Chemical Science. Advance Article, 9 p.

    Research output: Contribution to journalArticlepeer-review

  3. Thermal dehydrofluorination of GaPO-34 revealed by NMR crystallography

    Dawson, D. M., Macfarlane, L. E., Amri, M., Walton, R. I. & Ashbrook, S. E., 24 Jan 2021, In: Journal of Physical Chemistry C. Articles ASAP

    Research output: Contribution to journalArticlepeer-review

  4. Synthesis of chiral MOF-74 frameworks by post-synthetic modification using an amino acid

    Tanase, S., Gheorghe, A., Dubbeldam, D., Strudwick, B., Woutersen, S., Ashbrook, S. E. & Dawson, D. M., 20 Oct 2020, In: Chemistry - A European Journal. Early View, 10 p.

    Research output: Contribution to journalArticlepeer-review

  5. Site-specific iron substitution in STA-28, a large pore aluminophosphate zeotype prepared using 1,10-phenanthrolines as framework-bound templates

    Watts, A. E., Lozinska, M. M., Slawin, A. M. Z., Mayoral, A., Dawson, D. M., Ashbrook, S. E., Bode, B. E., Dugulan, I., Shannon, M., Cox, P., Turrina, A. & Wright, P. A., 17 Aug 2020, In: Angewandte Chemie International Edition. 59, 35, p. 15186-15190 5 p.

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. Thermal dehydrofluorination of GaPO-34 revealed by NMR crystallography

    Dawson, D. M., Macfarlane, L. E., Amri, M., Walton, R. I. & Ashbrook, S. E., 24 Jan 2021, In: Journal of Physical Chemistry C. Articles ASAP

    Research output: Contribution to journalArticlepeer-review

  2. Electron-induced modification of self-assembled monolayers of aromatic carboxylic acids

    Asyuda, A., de la Morena, R. O., Sauter, E., Turner, K., McDonald, K., Buck, M. & Zharnikov, M., 12 Nov 2020, In: Journal of Physical Chemistry C. 124, 45, p. 25107-25120 14 p.

    Research output: Contribution to journalArticlepeer-review

  3. Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics: insights from solid-state NMR spectroscopy and first-principles calculations

    Moran, R. F., Fernandes, A., Dawson, D. M., Sneddon, S., Gandy, A. S., Reeves-McLaren, N., Whittle, K. R. & Ashbrook, S. E., 9 Jul 2020, In: Journal of Physical Chemistry C. 124, 31, p. 17073–17084

    Research output: Contribution to journalArticlepeer-review

  4. Oligomerization of proline catalyzed by Ni on a Au(111) surface

    Seljamae-Green, R. T., Robinson, T., Fruchtl, H. A. & Baddeley, C. J., 18 Apr 2019, In: Journal of Physical Chemistry C. 123, 15, p. 9935-9943

    Research output: Contribution to journalArticlepeer-review

  5. Phonon-glass and heterogeneous electrical transport in A-site-deficient SrTiO3

    Popuri, S. R., Decourt, R., McNulty, J. A., Pollet, M., Fortes, A. D., Morrison, F. D., Senn, M. S. & Bos, J. W. G., 7 Mar 2019, In: Journal of Physical Chemistry C. 123, 9, p. 5198-5208 11 p.

    Research output: Contribution to journalArticlepeer-review

ID: 251636975

Top