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1887
Volume 64, Issue 2
  • ISSN: 2056-5135

Abstract

The adsorption and diffusion of species in activated carbons is fundamental to many processes in catalysis and energy storage. Nuclear magnetic resonance (NMR) gives an insight into the molecular-level mechanisms of these phenomena thanks to the unique magnetic shielding properties of the porous carbon structure, which allows adsorbed (in-pore) species to be distinguished from those in the bulk (ex-pore). In this work we investigate exchange dynamics between ex-pore and in-pore solvent species in microporous carbons using a combination of one-dimensional (1D) and two-dimensional (2D) NMR experiments. We systematically compare the effects of four variables: particle size, porosity, solvent polarity and solvent viscosity to build up a picture of how these factors influence the exchange kinetics. We show that exchange rates are greater in smaller and more highly activated carbon particles, which is expected due to the shorter in-pore–ex-pore path length and faster diffusion in large pores. Our results also show that in-pore–ex-pore exchange of apolar solvents is slower than water, suggesting that the hydrophobic chemistry of the carbon surface plays a role in the diffusion kinetics, and that increased viscosity also reduces the exchange kinetics. Our results also suggest the importance of other parameters, such as molecular diameter and solvent packing in micropores.

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2020-01-01
2024-11-24
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References

  1. R. K. Harris, T. V. Thompson, P. R. Norman, C. Pottage, J. Chem. Soc. Faraday Trans., 1996, 92, (14), 2615 LINK https://doi.org/10.1039/ft9969202615 [Google Scholar]
  2. P. von Ragué Schleyer, C. Maerker, A. Dransfeld, H. Jiao, N. J. R. van Eikema Hommes, J. Am. Chem. Soc., 1996, 118, (26), 6317 LINK https://doi.org/10.1021/ja960582d [Google Scholar]
  3. L. Borchardt, M. Oschatz, S. Paasch, S. Kaskel, E. Brunner, Phys. Chem. Chem. Phys., 2013, 15, (36), 15177 LINK https://doi.org/10.1039/c3cp52283k [Google Scholar]
  4. A. C. Forse, J. M. Griffin, H. Wang, N. M. Trease, V. Presser, Y. Gogotsi, P. Simon, C. P. Grey, Phys. Chem. Chem. Phys., 2013, 15, (20), 7722 LINK https://doi.org/10.1039/c3cp51210j [Google Scholar]
  5. A. C. Forse, J. M. Griffin, V. Presser, Y. Gogotsi, C. P. Grey, J. Phys. Chem. C, 2014, 118, (14), 7508 LINK https://doi.org/10.1021/jp502387x [Google Scholar]
  6. Y.-Z. Xing, Z.-X. Luo, A. Kleinhammes, Y. Wu, Carbon, 2014, 77, 1132 LINK https://doi.org/10.1016/j.carbon.2014.06.031 [Google Scholar]
  7. S. Hwang, J. Kaärger, Magn. Reson. Imaging, 2019, 56, 3 LINK https://doi.org/10.1016/j.mri.2018.08.010 [Google Scholar]
  8. F. Furtado, P. Galvosas, M. Gonçalves, F.-D. Kopinke, S. Naumov, F. Rodríguez-Reinoso, U. Roland, R. Valiullin, J. Kärger, Micro. Meso. Mater., 2011, 141, (1–3), 184 LINK https://doi.org/10.1016/j.micromeso.2010.11.015 [Google Scholar]
  9. T. M. Alam, T. M. Osborn Popp, Chem. Phys. Lett., 2016, 658, 51 LINK https://doi.org/10.1016/j.cplett.2016.06.014 [Google Scholar]
  10. A. C. Forse, J. M. Griffin, C. Merlet, J. Carretero-Gonzalez, A.-R. O. Raji, N. M. Trease, C. P. Grey, Nature Energy, 2017, 2, (3), 16216 LINK https://doi.org/10.1038/nenergy.2016.216 [Google Scholar]
  11. S. Macura, Y. Huang, D. Suter, R. R. Ernst, J. Magn. Reson., 1981, 43, (2), 259 LINK https://doi.org/10.1016/0022-2364(81)90037-8 [Google Scholar]
  12. M. H. Levitt, “Spin Dynamics – Basics of Nuclear Magnetic Resonance”, John Wiley and Sons Ltd, Chichester, UK, 2001, 686 pp [Google Scholar]
  13. A. D. Bain, Prog. Nucl. Magn. Reson. Spectrosc., 2003, 43, (3–4), 63 LINK https://doi.org/10.1016/j.pnmrs.2003.08.001 [Google Scholar]
  14. J. M. Griffin, A. C. Forse, H. Wang, N. M. Trease, P.-L. Taberna, P. Simon, C. P. Grey, Faraday Discuss., 2014, 176, 49 LINK https://doi.org/10.1039/c4fd00138a [Google Scholar]
  15. N. Fulik, F. Hippauf, D. Leistenschneider, S. Paasch, S. Kaskel, E. Brunner, L. Borchardt, Energy Storage Mater., 2018, 12, 183 LINK https://doi.org/10.1016/j.ensm.2017.12.008 [Google Scholar]
  16. L. Cervini, O. D. Lynes, G. R. Akien, A. Kerridge, N. S. Barrow, J. M. Griffin, Energy Storage Mater., 2019, 21, 335 LINK https://doi.org/10.1016/j.ensm.2019.05.010 [Google Scholar]
  17. C. Merlet, A. C. Forse, J. M. Griffin, D. Frenkel, C. P. Grey, J. Chem. Phys., 2015, 142, (9), 094701 LINK https://doi.org/10.1063/1.4913368 [Google Scholar]
  18. I. P. P. Cansado, F. A. M. M. Gonçalves, P. J. M. Carrott, M. M. L. Ribeiro Carrott, Carbon, 2007, 45, (12), 2454 LINK https://doi.org/10.1016/j.carbon.2007.07.004 [Google Scholar]
  19. R. J. Anderson, T. P. McNicholas, A. Kleinhammes, A. Wang, J. Liu, Y. Wu, J. Am. Chem. Soc., 2010, 132, (25), 8618 LINK https://doi.org/10.1021/ja9109924 [Google Scholar]
  20. Z.-X. Luo, Y.-Z. Xing, Y.-C. Ling, A. Kleinhammes, Y. Wu, Nature Commun., 2015, 6, 6358 LINK https://doi.org/10.1038/ncomms7358 [Google Scholar]
  21. H. Wang, A. C. Forse, J. M. Griffin, N. M. Trease, L. Trognko, P.-L. Taberna, P. Simon, C. P. Grey, J. Am. Chem. Soc., 2013, 135, (50), 18968 LINK https://doi.org/10.1021/ja410287s [Google Scholar]
  22. R. L. Vold, G. L. Hoatson, J. Magn. Reson., 2009, 198, (1), 57 LINK https://doi.org/10.1016/j.jmr.2009.01.008 [Google Scholar]
  23. S. O. Diallo, Phys. Rev. E, 2015, 92, (1), 012312 LINK https://doi.org/10.1103/physreve.92.012312 [Google Scholar]
  24. C. Cadar, I. Ardelean, Magn. Reson. Chem., 2019, 57, (10), 829 LINK https://doi.org/10.1002/mrc.4819 [Google Scholar]
  25. I. N. Tsimpanogiannis, O. A. Moultos, L. F. M. Franco, M. B. de, M. Spera, M. Erdős, I. G. Economou, Mol. Simul., 2019, 45, (4–5), 425 LINK https://doi.org/10.1080/08927022.2018.1511903 [Google Scholar]
  26. M. Holz, S. R. Heil, A. Sacco, Phys. Chem. Chem. Phys., 2000, 2, (20), 4740 LINK https://doi.org/10.1039/b005319h [Google Scholar]
  27. Y. D. Fomin, V. N. Ryzhov, E. N. Tsiok, J. Chem. Phys., 2015, 143, (18), 184702 LINK https://doi.org/10.1063/1.4935197 [Google Scholar]
  28. T. Shimoyama, K. Tashima, M. Ruike, Coll. Surf. A: Physicochem. Eng. Asp., 2017, 533, 255 LINK https://doi.org/10.1016/j.colsurfa.2017.08.040 [Google Scholar]
  29. M. Fukano, T. Fujimori, J. Ségalini, E. Iwama, P.-L. Taberna, T. Iiyama, T. Ohba, H. Kanoh, Y. Gogotsi, P. Simon, K. Kaneko, J. Phys. Chem. C, 2013, 117, (11), 5752 LINK https://doi.org/10.1021/jp311896q [Google Scholar]
  30. J. Griffin, ‘Observing Solvent Dynamics in Porous Carbons by Nuclear Magnetic Resonance’, Dataset, Research Directory, Lancaster University, UK, 2019 LINK https://dx.doi.org/10.17635/lancaster/researchdata/314 [Google Scholar]
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