title: Mechanism of Efficient Proton Conduction in Diphosphoric Acid Elucidated via First-Principles Simulation and NMR.
abstract: Diphosphoric acid (H4P2O7) is the first condensation product of phosphoric acid (H3PO4), the compound with the highest intrinsic proton conductivity in the liquid state. It exists at higher temperature (T > 200 °C) and lower relative humidity (RH ≈ 0.01%) and shows significant ionic conductivity under these conditions. In this work, ab initio molecular dynamics simulations of a pure H4P2O7 model system and NMR spectroscopy on nominal H4P2O7 (which contains significant amounts of ortho- and triphosphoric acid in thermodynamic equilibrium) were performed to reveal the nature and underlying mechanisms of the ionic conductivity. The central oxygen of the molecule is found to be excluded from any hydrogen bonding, which has two interesting consequences: (i) compared to H3PO4, the acidity of H4P2O7 is severely increased, and (ii) the condensation reaction only leads to a minor decrease in hydrogen bond network frustration, which is thought to be one of the features enabling high proton conductivity. A topological analysis of diphosphoric acid's hydrogen bond network shows remarkable similarities to that of phosphonic acid (H3PO3). The hydrogen bonding facilitates protonic polarization fluctuations (Zundel polarization) extending over several molecules (Grotthuss chains), the other important ingredient for efficient structural diffusion of protons. At T = 160 °C, this is estimated to make a conductivity contribution of about 0.1 S/cm, which accounts for half of the total ionic conductivity (σ ≈ 0.2 S/cm). The other half is suggested to result from diffusion of charged phosphate species (vehicle mechanism) that are present in high concentration, resembling conduction in ionic liquids.
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstrasse 1, D-70569 Stuttgart, Germany.|Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Rachel A
authors.initials: RA
authors.lastname: Krueger
authors.affiliation: Department of Chemistry, New York University , New York, New York 10003, United States.|Department of Chemical Engineering, University of Texas , Austin, Texas 78712, United States.
authors.forename: Linas
authors.initials: L
authors.lastname: Vilčiauskas
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstrasse 1, D-70569 Stuttgart, Germany.
authors.forename: Jan-Patrick
authors.initials: JP
authors.lastname: Melchior
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstrasse 1, D-70569 Stuttgart, Germany.|Department of Chemistry, University of Hamburg , D-20146 Hamburg, Germany.
authors.forename: Gabriel
authors.initials: G
authors.lastname: Bester
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstrasse 1, D-70569 Stuttgart, Germany.
authors.forename: Klaus-Dieter
authors.initials: KD
authors.lastname: Kreuer