ACS Publications. Most Trusted. Most Cited. Most Read
Investigations of Proton Conduction in the Monoclinic Phase of RbH2PO4 Using Multinuclear Solid-State NMR

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. C 2009, 113, 41, 17950-17957
    Article

    Investigations of Proton Conduction in the Monoclinic Phase of RbH2PO4 Using Multinuclear Solid-State NMR
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Chemistry, McMaster University, 1280 Main Street, West Hamilton, Ontario L8S 4M1, Canada
    * To whom correspondence should be addressed. E-mail: [email protected]. Phone: (905)-525-9140 x24176. Fax: (905)-522-2509.
    †Current address: Environmental and Molecular Science Laboratories, Pacific Northwest National Laboratory, Richland, WA 99352.
    Other Access Options

    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2009, 113, 41, 17950–17957
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp903408v
    Published September 17, 2009
    Copyright © 2009 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    To understand the nature of the high-temperature phase transition and the origin of proton conductivity in rubidium dihydrogen phosphate RbH2PO4, (RDP), we utilized variable-temperature 1H, 31P, and 87Rb MAS NMR at 11.7 and 21.1 T. The variable-temperature 1H MAS NMR spectra do not show water peaks in the temperature range of 300−400 K, which argues against a partial polymerization and/or decomposition. The 1H DQ MAS NMR spectra acquired at high field (21.1 T) reveal three different proton sites, and dipolar recoupling experiments give estimates of distances. This evidence supports the formation of a superstructure (doubling of the unit cell along the a-axis) in the high-temperature monoclinic phase. The variable-temperature proton spin−lattice relaxation (T1) reveals significant proton dynamics above 340 K, coinciding with the temperature at which an increase of bulk proton conductivity is reported in monoclinic RDP, but well below the macroscopic phase transition. These precursor dynamics foreshadow the onset of superprotonic conductivity. From variable- temperature 31P and 87Rb MAS NMR spectra, it is deduced that significant proton dynamics above 340 K are due to the proton transfer between hydrogen bonds accompanied by reorientation of PO4 tetrahedra.

    Copyright © 2009 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 14 publications.

    1. Anna Martinelli, José M. Otero-Mato, Mounesha N. Garaga, Khalid Elamin, Seikh Mohammad Habibur Rahman, Josef W. Zwanziger, Ulrike Werner-Zwanziger, Luis M. Varela. A New Solid-State Proton Conductor: The Salt Hydrate Based on Imidazolium and 12-Tungstophosphate. Journal of the American Chemical Society 2021, 143 (34) , 13895-13907. https://doi.org/10.1021/jacs.1c06656
    2. Gabrielle Y. Foran, Darren H. Brouwer, and Gillian R. Goward . Quantifying Site-Specific Proton Dynamics in Phosphate Solid Acids by 1H Double Quantum NMR Spectroscopy. The Journal of Physical Chemistry C 2017, 121 (46) , 25641-25650. https://doi.org/10.1021/acs.jpcc.7b06034
    3. Ya. Kobzar, H. Oulyadi, S. Marais, K. Fatyeyeva. Advances in nuclear magnetic resonance spectroscopy: case of proton conductive materials. Journal of Materials Chemistry A 2023, 11 (12) , 6064-6089. https://doi.org/10.1039/D2TA07764G
    4. Sergey V. Sukhomlinov, Guido Kickelbick, Martin H. Müser. Mechanochemical Ionization: Differentiating Pressure-, Shear-, and Temperature-Induced Reactions in a Model Phosphate. Tribology Letters 2022, 70 (4) https://doi.org/10.1007/s11249-022-01644-w
    5. Isabel Fuentes, Andreu Andrio, Francesc Teixidor, Clara Viñas, Vicente Compañ. Enhanced conductivity of sodium versus lithium salts measured by impedance spectroscopy. Sodium cobaltacarboranes as electrolytes of choice. Physical Chemistry Chemical Physics 2017, 19 (23) , 15177-15186. https://doi.org/10.1039/C7CP02526B
    6. Norsyahida Mohammad, Abu Bakar Mohamad, Abdul Amir H. Kadhum, Kee Shyuan Loh. A review on synthesis and characterization of solid acid materials for fuel cell applications. Journal of Power Sources 2016, 322 , 77-92. https://doi.org/10.1016/j.jpowsour.2016.05.021
    7. Erigene Bakangura, Liang Wu, Liang Ge, Zhengjin Yang, Tongwen Xu. Mixed matrix proton exchange membranes for fuel cells: State of the art and perspectives. Progress in Polymer Science 2016, 57 , 103-152. https://doi.org/10.1016/j.progpolymsci.2015.11.004
    8. Liuming Yan, Yidong Hu, Xiaoming Zhang, Baohua Yue. Applications of NMR Techniques in the Development and Operation of Proton Exchange Membrane Fuel Cells. 2016, 149-213. https://doi.org/10.1016/bs.arnmr.2015.11.003
    9. Martin Mangstl, Vinicius R. Celinski, Sebastian Johansson, Johannes Weber, Feng An, Jörn Schmedt auf der Günne. Low temperature synthesis of ionic phosphates in dimethyl sulfoxide. Dalton Trans. 2014, 43 (26) , 10033-10039. https://doi.org/10.1039/C4DT00544A
    10. Ae Ran Lim, Kwang-Sei Lee. Phenomenon of high-temperature phase transition of RbH2PO4 crystals studied by 1H, 31P, and 87Rb NMR. Journal of Physics and Chemistry of Solids 2013, 74 (5) , 779-783. https://doi.org/10.1016/j.jpcs.2013.01.022
    11. Zikun Li, Tongbor Tang. Effects of porous SiO2 on protonic conductivity of RbH2PO4-based composite electrolytes. Solid State Ionics 2012, 211 , 34-41. https://doi.org/10.1016/j.ssi.2012.01.011
    12. Asier Goñi-Urtiaga, Dimitrios Presvytes, Keith Scott. Solid acids as electrolyte materials for proton exchange membrane (PEM) electrolysis: Review. International Journal of Hydrogen Energy 2012, 37 (4) , 3358-3372. https://doi.org/10.1016/j.ijhydene.2011.09.152
    13. Steven P. Brown. Applications of high-resolution 1H solid-state NMR. Solid State Nuclear Magnetic Resonance 2012, 41 , 1-27. https://doi.org/10.1016/j.ssnmr.2011.11.006
    14. Anne-Claire Dupuis. Proton exchange membranes for fuel cells operated at medium temperatures: Materials and experimental techniques. Progress in Materials Science 2011, 56 (3) , 289-327. https://doi.org/10.1016/j.pmatsci.2010.11.001
    Download PDF
    Go to The Journal of Physical Chemistry C
    Get e-Alerts
    Get e-Alerts

    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2009, 113, 41, 17950–17957
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp903408v
    Published September 17, 2009
    Copyright © 2009 American Chemical Society
    Request reuse permissions

    Article Views

    608

    Altmetric

    -

    Citations

    14
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.