The Library

Investigation of proton dynamics and the proton transport pathway in choline dihydrogen phosphate using solid-state NMR

Tools

Cahill, Lindsay S., Rana, Usman Ali, Forsyth, Maria and Smith, Mark E.. (2010) Investigation of proton dynamics and the proton transport pathway in choline dihydrogen phosphate using solid-state NMR. Physical Chemistry Chemical Physics, Vol.12 (No.20). pp. 5431-5438. ISSN 1463-9076

Preview

PDF
WRAP_Smith_9774456-vcs_office-041211-choline_dhp_revised_final.pdf - Accepted Version - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader
Download (558Kb)

Official URL: http://dx.doi.org/10.1039/b916422g

Abstract

Choline dihydrogen phosphate has previously been shown to be a good ionic conductor as well as an excellent host for acid doping, leading to high proton conductivities required for e.g., electrochemical devices including proton membrane fuel cells and sensors. A combination of variable-temperature H-1 solid-state NMR and 2D NMR pulse sequences, including P-31 and C-13 CODEX and H-1 BaBa, show that the proton conduction mechanism primarily involves assisted transport via a restricted three-site motion of the phosphate unit around the P-O bond that is hydrogen bonded to the choline and exchange of protons between these anions. In other words, proton transport at ambient temperatures appears to occur most favorably along the crystallographic b axis, from phosphate dimer to dimer. At elevated temperatures exchange between the protons of the hydroxyl group on the choline cation and the hydrogen-bonded dihydrogen phosphate groups also contributes to the structural diffusion of the protons in this solid state conductor.

Item Type:	Journal Article
Subjects:	Q Science > QC Physics Q Science > QD Chemistry
Divisions:	Administration > Vice Chancellor's Office Faculty of Science > Physics
Library of Congress Subject Headings (LCSH):	Choline -- Transport properties, Protons -- Transport properties, Nuclear magnetic resonance spectroscopy
Journal or Publication Title:	Physical Chemistry Chemical Physics
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Official Date:	2010
Volume:	Vol.12
Number:	No.20
Number of Pages:	8
Page Range:	pp. 5431-5438
Identification Number:	10.1039/b916422g
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	Engineering and Physical Sciences Research Council (EPSRC), Natural Sciences and Engineering Research Council of Canada (NSERC), Advantage West Midlands (AWM), University of Warwick, Australian Research Council (ARC)
Grant number:	EP/F022913 (EPSRC)
References:	1. S. M. Haile, D. A. Boysen, C. R. I. Chisholm and R. B. Merle, Nature, 2001, 410, 910. 2. Q. Li, R. He, J. O. Jensen and N. J. Bjerrum, Fuel Cells, 2004, 4, 147. 3. G. Dotelli, M. C. Gallazzi, G. Perfetti and E. Montoneri, Solid State Ionics, 2005, 176, 2819. 4. M. Yoshizawa-Fujita, K. Fujita, M. Forsyth and D. R. MacFarlane, Electrochem. Commun. 2007, 9, 1202. 5. U. A. Rana, P. M. Bayley, V. Ranganathan, P. Dean, D. R. MacFarlane, M. Forsyth, Chem. Mater., 2009, submitted. 6. S. P. Brown and H. W. Spiess, Chem. Rev., 2001, 101, 4125. 7. G. R. Goward, M. F. H. Schuster, D. Sebastiani, I. Schnell and H. W. Spiess, J. Phys. Chem. B, 2002, 106, 9322. 8. J. W. Traer, E. Montoneri, A. Samoson, J. Past, T. Tuherm and G. R. Goward, Chem. Mater., 2006, 18, 4747. 9. T. Schaller, U. P. Buchele, F.-G. Klarner, D. Blaser, R. Boese, S. P. Brown, H. W. Spiess, F. Koziol, J. Kussmann and C. Ochsenfeld, J. Am. Chem. Soc., 2007, 129, 1293. 10. J. W. Traer, J. F. Britten and G. R. Goward, J. Phys. Chem. B, 2007, 111, 5602. 11. J. W. Traer and G. R. Goward, Magn. Reson. Chem., 2007, 45, S135. 12. S. P. Brown, I. Schnell, J. D. Brand, K. Muellen and H. W. Spiess, Phys. Chem. Chem. Phys., 2000, 2, 1735. 13. G. R. Goward, K. Saalwachter, I. Fischbach and H. W. Spiess, Solid State Nucl. Magn. Reson., 2003, 24, 150. 14. E. R. deAzevedo, W.-G. Hu, T. J. Bonagamba and K. Schmidt-Rohr, J. Am. Chem. Soc., 1999, 121, 8411. 15. C. J. T. Grotthuss, Ann. Chim., 1806, 58, 54. 16. K. Fujita, D. R. MacFarlane, K. Noguchi and H. Ohno, Acta Crystallogr., Sect. E, 2009, 65, o709. 17. G. Ye, N. Janzen and G. R. Goward, Macromolecules, 2006, 39, 3283. 18. I. Schnell and H. W. Spiess, J. Magn. Reson., 2001, 151, 153. 19. J. Jeener, B. H. Meier, P. Bachmann and R. R. Ernst, J. Chem. Phys., 1979, 71, 4546. 20. M. Jansen, Angew. Chem. Int. Ed. Engl., 1991, 30, 1547. 21. M. Forsyth, J. Huang and D. R. MacFarlane, J. Mater. Chem., 2000, 10, 2259. 22. S. J. Pas, J. Huang, M. Forsyth, D. R. MacFarlane and A. J. Hill, J. Chem. Phys., 2005, 122, 064704. 23. J. Huang, A. Hill, M. Forsyth, D. MacFarlane and A. Hollenkamp, Solid State Ionics, 2006, 177, 2569. 24. R. Aronsson, H. E. G. Knape, A. Lunden, L. Nilsson and L. M. Torell, Solid State Ionics, 1981, 5, 445. 25. T. Dippel, K. D. Kreuer, J. C. Lassegues and D. Rodriguez, Solid State Ionics, 1993, 61, 41. 26. G. J. M. P. van Moorsel, E. R. H. van Eck and C. P. Grey, J. Magn. Reson. A, 1995, 113, 159.
URI:	http://wrap.warwick.ac.uk/id/eprint/5883