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Title: On the nanosecond proton dynamics in phosphoric acid–benzimidazole and phosphoric acid–water mixtures

Abstract

Combining1H-NMR,17O-NMR, and high-resolution backscattering QENS hydrodynamic and structural proton transport in phosphoric acid is separated. The rate limiting steps for structural proton diffusion in mixtures of acid with Brønsted bases are found to occur below the nanosecond timescale.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Max Planck Inst. for Solid State Research, Stuttgart (Germany)
  2. Inst. Laue-Langevin (ILL), Grenoble (France)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1407718
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 19; Journal Issue: 42; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Melchior, Jan-Patrick, and Frick, Bernhard. On the nanosecond proton dynamics in phosphoric acid–benzimidazole and phosphoric acid–water mixtures. United States: N. p., 2017. Web. https://doi.org/10.1039/C7CP04116K.
Melchior, Jan-Patrick, & Frick, Bernhard. On the nanosecond proton dynamics in phosphoric acid–benzimidazole and phosphoric acid–water mixtures. United States. https://doi.org/10.1039/C7CP04116K
Melchior, Jan-Patrick, and Frick, Bernhard. Fri . "On the nanosecond proton dynamics in phosphoric acid–benzimidazole and phosphoric acid–water mixtures". United States. https://doi.org/10.1039/C7CP04116K. https://www.osti.gov/servlets/purl/1407718.
@article{osti_1407718,
title = {On the nanosecond proton dynamics in phosphoric acid–benzimidazole and phosphoric acid–water mixtures},
author = {Melchior, Jan-Patrick and Frick, Bernhard},
abstractNote = {Combining1H-NMR,17O-NMR, and high-resolution backscattering QENS hydrodynamic and structural proton transport in phosphoric acid is separated. The rate limiting steps for structural proton diffusion in mixtures of acid with Brønsted bases are found to occur below the nanosecond timescale.},
doi = {10.1039/C7CP04116K},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 42,
volume = 19,
place = {United States},
year = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 2 works
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Works referenced in this record:

Proton conduction mechanisms in the phosphoric acid–water system (H 4 P 2 O 7 –H 3 PO 4 ·2H 2 O): a 1 H, 31 P and 17 O PFG-NMR and conductivity study
journal, January 2017

  • Melchior, Jan-Patrick; Kreuer, Klaus-Dieter; Maier, Joachim
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 1
  • DOI: 10.1039/C6CP04855B

[sup 1]H and [sup 31]P NMR Study of Phosphoric Acid–Doped Polybenzimidazole under Controlled Water Activity
journal, January 2009

  • Schechter, Alex; Savinell, Robert F.; Wainright, J. S.
  • Journal of The Electrochemical Society, Vol. 156, Issue 2
  • DOI: 10.1149/1.3040211

Effect of Benzimidazole Configuration in Polybenzimidazole Chain on Interaction with Phosphoric Acid: A DFT Study
journal, December 2014

  • Shirata, Kei; Kawauchi, Susumu
  • The Journal of Physical Chemistry B, Vol. 119, Issue 2
  • DOI: 10.1021/jp510067n

Transport in Proton Conductors for Fuel-Cell Applications:  Simulations, Elementary Reactions, and Phenomenology
journal, October 2004

  • Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr020715f

Dynamics of the hydrogen and phosphate ions in proton conducting gel/D3PO4 electrolytes: A 2H and 31P nuclear magnetic resonance study
journal, July 2003

  • Jeffrey, K. R.; Zukowska, G. Z.; Stevens, J. R.
  • The Journal of Chemical Physics, Vol. 119, Issue 4
  • DOI: 10.1063/1.1582844

Quasi-elastic neutron scattering and molecular dynamics simulation as complementary techniques for studying diffusion in zeolites
journal, May 2007


779. Anomalous conduction in phosphoric acid hemihydrate, 2H3PO4,H2O
journal, January 1959

  • Greenwood, N. N.; Thompson, A.
  • Journal of the Chemical Society (Resumed)
  • DOI: 10.1039/jr9590003864

Oxygen-17 NMR spectroscopy: Basic principles and applications (part II)
journal, July 2010


Electro-osmotic Drag Coefficient of Water and Methanol in Polymer Electrolytes at Elevated Temperatures
journal, January 1996

  • Weng, D.
  • Journal of The Electrochemical Society, Vol. 143, Issue 4
  • DOI: 10.1149/1.1836626

Nuclear electric quadrupole relaxation
journal, January 1996


First principles molecular dynamics study of proton dynamics and transport in phosphoric acid/imidazole (2:1) system
journal, December 2013


The Activation Energies of Proton Transfer Reactions in Water
journal, November 1964

  • Luz, Z.; Meiboom, S.
  • Journal of the American Chemical Society, Vol. 86, Issue 22
  • DOI: 10.1021/ja01076a008

Proton Conductivity in Phosphoric Acid: The Role of Quantum Effects
journal, October 2016


Proton migration along the membrane surface and retarded surface to bulk transfer
journal, August 1994

  • Heberle, Joachim; Riesle, Jens; Thiedemann, Gerd
  • Nature, Vol. 370, Issue 6488
  • DOI: 10.1038/370379a0

Self-Dissociative Equilibria in Molten Phosphoric Acid
journal, November 1964

  • Munson, Ronald A.
  • The Journal of Physical Chemistry, Vol. 68, Issue 11
  • DOI: 10.1021/j100793a045

Ionic Conductivity and Glass Transition of Phosphoric Acids
journal, June 2013

  • Wang, Yangyang; Lane, Nathan A.; Sun, Che-Nan
  • The Journal of Physical Chemistry B, Vol. 117, Issue 26
  • DOI: 10.1021/jp403867a

Diffusive Motions in Water and Cold Neutron Scattering
journal, August 1960


Analysis and visualisation of neutron-scattering data
journal, December 1996


Probing phosphoric acid redistribution and anion migration in polybenzimidazole membranes
journal, September 2017


Why nature chose phosphates
journal, March 1987


Acid-Doped Polybenzimidazoles: A New Polymer Electrolyte
journal, January 1995

  • Wainright, J. S.
  • Journal of The Electrochemical Society, Vol. 142, Issue 7
  • DOI: 10.1149/1.2044337

Why do proton conducting polybenzimidazole phosphoric acid membranes perform well in high-temperature PEM fuel cells?
journal, January 2017

  • Melchior, Jan-Patrick; Majer, Günter; Kreuer, Klaus-Dieter
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 1
  • DOI: 10.1039/C6CP05331A

Polymer and Composite Membranes for Proton-Conducting, High-Temperature Fuel Cells: A Critical Review
journal, June 2017

  • Quartarone, Eliana; Angioni, Simone; Mustarelli, Piercarlo
  • Materials, Vol. 10, Issue 7
  • DOI: 10.3390/ma10070687

PA based proton conductors - from monomeric benzimidazole to polybenzimidazole
null, January 2013


Proton Conductivity:  Materials and Applications
journal, January 1996

  • Kreuer, Klaus-Dieter
  • Chemistry of Materials, Vol. 8, Issue 3
  • DOI: 10.1021/cm950192a

Conductivity of PBI Membranes for High-Temperature Polymer Electrolyte Fuel Cells
journal, January 2004

  • Ma, Y. -L.; Wainright, J. S.; Litt, M. H.
  • Journal of The Electrochemical Society, Vol. 151, Issue 1
  • DOI: 10.1149/1.1630037

Proton dynamics of CsH2PO4 studied by quasi-elastic neutron scattering and PFG-NMR
journal, December 2008


Incoherent neutron scattering functions for random jump diffusion in bounded and infinite media
journal, February 1981


Nuclear Magnetic Resonance Study of the Proton Transfer in Water
journal, February 1961

  • Meiboom, S.
  • The Journal of Chemical Physics, Vol. 34, Issue 2
  • DOI: 10.1063/1.1700960

Influence of morphology on physical properties of poly(2,5-benzimidazole) membranes
journal, July 2017


Water distribution in high temperature polymer electrolyte fuel cells
journal, January 2016


The mechanism of proton conduction in phosphoric acid
journal, April 2012

  • Vilčiauskas, Linas; Tuckerman, Mark E.; Bester, Gabriel
  • Nature Chemistry, Vol. 4, Issue 6
  • DOI: 10.1038/nchem.1329

On the complexity of proton conduction phenomena
journal, November 2000


Ion Conduction Mechanisms and Thermal Properties of Hydrated and Anhydrous Phosphoric Acids Studied with 1 H, 2 H, and 31 P NMR
journal, December 2006

  • Aihara, Yuichi; Sonai, Atsuo; Hattori, Mineyuki
  • The Journal of Physical Chemistry B, Vol. 110, Issue 49
  • DOI: 10.1021/jp064452v

The Electrical Conductivity and Viscosity of Concentrated Solutions of Orthophosphoric Acid.
journal, November 1909

  • Smith, Alexander; Menzies, Alan W. C.
  • Journal of the American Chemical Society, Vol. 31, Issue 11
  • DOI: 10.1021/ja01941a002

Mass transport of phosphoric acid in water: A 1H and 31P pulsed gradient spin-echo nuclear magnetic resonance study
journal, May 2000

  • Chung, S. H.; Bajue, S.; Greenbaum, S. G.
  • The Journal of Chemical Physics, Vol. 112, Issue 19
  • DOI: 10.1063/1.481454

NMR Studies of Mass Transport in High-Acid-Content Fuel Cell Membranes Based on Phosphoric Acid and Polybenzimidazole
journal, January 2007

  • Jayakody, J. R. P.; Chung, S. H.; Durantino, L.
  • Journal of The Electrochemical Society, Vol. 154, Issue 2
  • DOI: 10.1149/1.2405726

Why did Nature select phosphate for its dominant roles in biology?
journal, January 2010

  • Bowler, Matthew W.; Cliff, Matthew J.; Waltho, Jonathan P.
  • New Journal of Chemistry, Vol. 34, Issue 5
  • DOI: 10.1039/b9nj00718k

Structure and Proton Dynamics in Catalytic Layer of HT-PEFC
journal, April 2016


The nanosecond proton dynamics of phosphoric acid – from the solid to the melt – investigated by neutron backscattering
journal, December 2013


Ab initio molecular dynamics simulation of the solvation and transport of hydronium and hydroxyl ions in water
journal, July 1995

  • Tuckerman, M.; Laasonen, K.; Sprik, M.
  • The Journal of Chemical Physics, Vol. 103, Issue 1
  • DOI: 10.1063/1.469654

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)
journal, March 2010


Recent Backscattering Instrument Developments at the ILL and SNS
journal, February 2010

  • Frick, Bernhard; Mamontov, Eugene; Eijck, Lambert van
  • Zeitschrift für Physikalische Chemie, Vol. 224, Issue 1-2
  • DOI: 10.1524/zpch.2010.6091

The diffusion mechanism of an excess proton in imidazole molecule chains: first results of an ab initio molecular dynamics study
journal, December 2001


Proton-conducting polymer electrolytes based on phosphoric acid
journal, October 1999


Investigation of proton-conducting solids
journal, August 1981


The glass transition temperatures of phosphoric acids
journal, October 1976


The Grotthuss mechanism
journal, October 1995


On the conductivity of phosphoric acid electrolyte
journal, January 1989

  • Chin, Der-Tau; Chang, Howard H.
  • Journal of Applied Electrochemistry, Vol. 19, Issue 1
  • DOI: 10.1007/BF01039396

Incoherent neutron scattering study of protonic conductors
journal, June 1992


Imidazole and pyrazole-based proton conducting polymers and liquids
journal, April 1998


Relaxation Effects in Nuclear Magnetic Resonance Absorption
journal, April 1948


Density, electrical conductivity, and vapor pressure of concentrated phosphoric acid
journal, July 1969

  • MacDonald, David I.; Boyack, James R.
  • Journal of Chemical & Engineering Data, Vol. 14, Issue 3
  • DOI: 10.1021/je60042a013

Heat capacity and glass transition in P2O5–H2O solutions: support for Mishima's conjecture on solvent water at low temperature
journal, January 2011

  • Corti, Horacio R.; Nores-Pondal, Federico J.; Angell, C. Austen
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 44
  • DOI: 10.1039/c1cp22185j

Multinuclear NMR Study of the Effect of Acid Concentration on Ion Transport in Phosphoric Acid Doped Poly(benzimidazole) Membranes
journal, October 2012

  • Suarez, Sophia; Kodiweera, N. K. A. C.; Stallworth, P.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 41
  • DOI: 10.1021/jp304761t

High temperature proton exchange membranes based on polybenzimidazoles for fuel cells
journal, May 2009


A neutron diffraction and computer modeling study of the interatomic structure of phosphoric acid
journal, January 1999

  • Tromp, R. Hans; Spieser, Stephane H.; Neilson, George W.
  • The Journal of Chemical Physics, Vol. 110, Issue 4
  • DOI: 10.1063/1.477824

Influence of ionic solutes upon the conductivity of molten phosphoric acid
journal, September 1967

  • Munson, Ronald A.; Lazarus, Michael E.
  • The Journal of Physical Chemistry, Vol. 71, Issue 10
  • DOI: 10.1021/j100869a018

Observing proton motion on the nanoscale in polymeric electrolyte membranes with quasielastic neutron scattering
journal, December 2014


Mechanism of Efficient Proton Conduction in Diphosphoric Acid Elucidated via First-Principles Simulation and NMR
journal, December 2015

  • Krueger, Rachel A.; Vilčiauskas, Linas; Melchior, Jan-Patrick
  • The Journal of Physical Chemistry B, Vol. 119, Issue 52
  • DOI: 10.1021/acs.jpcb.5b09684

Proton conductivity in fused phosphoric acid; A 1H/31P PFG-NMR and QNS study
journal, May 1993


Proton conductivity and diffusion in molten phosphinic acid (H3PO2): The last member of the phosphorus oxoacid proton conductor family
journal, March 2012


Transport in Proton Conductors for Fuel-Cell Applications: Simulations, Elementary Reactions, and Phenomenology
journal, December 2004

  • Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard
  • ChemInform, Vol. 35, Issue 50
  • DOI: 10.1002/chin.200450274

Relaxation Effects in Nuclear Magnetic Resonance Absorption
conference, July 2014

  • Bloembergen, N.; Purcell, E. M.; Pound, R. V.
  • A Volume in Honor of the 70th Birthday of Nicolaas Bloembergen, Resonances
  • DOI: 10.1142/9789814540223_0039

    Works referencing / citing this record:

    Fractal diffusion in high temperature polymer electrolyte fuel cell membranes
    journal, May 2018

    • Hopfenmüller, Bernhard; Zorn, Reiner; Holderer, Olaf
    • The Journal of Chemical Physics, Vol. 148, Issue 20
    • DOI: 10.1063/1.5018717