The mechanism of proton conduction in phosphoric acid

Linas Vilčiauskas, Mark Tuckerman, Gabriel Bester, Stephen J. Paddison, Klaus Dieter Kreuer

Research output: Contribution to journalArticle

Abstract

Neat liquid phosphoric acid (H 3PO 4) has the highest intrinsic proton conductivity of any known substance and is a useful model for understanding proton transport in other phosphate-based systems in biology and clean energy technologies. Here, we present an ab initio molecular dynamics study that reveals, for the first time, the microscopic mechanism of this high proton conductivity. Anomalously fast proton transport in hydrogen-bonded systems involves a structural diffusion mechanism in which intramolecular proton transfer is driven by specific hydrogen bond rearrangements in the surrounding environment. Aqueous media transport excess charge defects through local hydrogen bond rearrangements that drive individual proton transfer reactions. In contrast, strong, polarizable hydrogen bonds in phosphoric acid produce coupled proton motion and a pronounced protic dielectric response of the medium, leading to the formation of extended, polarized hydrogen-bonded chains. The interplay between these chains and a frustrated hydrogen-bond network gives rise to the high proton conductivity.

Original languageEnglish (US)
Pages (from-to)461-466
Number of pages6
JournalNature Chemistry
Volume4
Issue number6
DOIs
StatePublished - Jun 2012

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Phosphoric acid
Proton conductivity
Protons
Hydrogen bonds
Proton transfer
Hydrogen
Molecular dynamics
Charge transfer
Phosphates
Defects
phosphoric acid
Liquids

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Vilčiauskas, L., Tuckerman, M., Bester, G., Paddison, S. J., & Kreuer, K. D. (2012). The mechanism of proton conduction in phosphoric acid. Nature Chemistry, 4(6), 461-466. https://doi.org/10.1038/nchem.1329

The mechanism of proton conduction in phosphoric acid. / Vilčiauskas, Linas; Tuckerman, Mark; Bester, Gabriel; Paddison, Stephen J.; Kreuer, Klaus Dieter.

In: Nature Chemistry, Vol. 4, No. 6, 06.2012, p. 461-466.

Research output: Contribution to journalArticle

Vilčiauskas, L, Tuckerman, M, Bester, G, Paddison, SJ & Kreuer, KD 2012, 'The mechanism of proton conduction in phosphoric acid', Nature Chemistry, vol. 4, no. 6, pp. 461-466. https://doi.org/10.1038/nchem.1329
Vilčiauskas, Linas ; Tuckerman, Mark ; Bester, Gabriel ; Paddison, Stephen J. ; Kreuer, Klaus Dieter. / The mechanism of proton conduction in phosphoric acid. In: Nature Chemistry. 2012 ; Vol. 4, No. 6. pp. 461-466.
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