A first principles analysis of the location and affinity of protons in the secondary structure of phosphotungstic acid

Michael John Janik, Robert J. Davis, Matthew Neurock

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Nonlocal gradient corrected density functional theory was used to determine the optimal positions of the protons and their relative affinity in the secondary structure of phosphotungstic acid. First, a body centered cubic structure associated with the hexahydrate was incorporated into the model. The desorption energies of the first and second water molecules from a bridging H 5O 2 + species were calculated to be 109 and 55 kJ mol -1, respectively. The H 3O + or H + species remaining after dehydration are preferentially located between two oxygen atoms of adjacent Keggin units. The preferred position is between two terminal O d atoms or between a terminal O d atom and a bridging O c atom, depending on the alignment of the Keggin units. The energy advantage of sharing a proton between two Keggin units is in the range of 43 to 71 kJ mol -1. Three-dimensional periodic calculations indicate that anhydrous phosphotungstic acid can form a regular lattice in which all protons are shared between the heteropolyanions.

Original languageEnglish (US)
Pages (from-to)12292-12300
Number of pages9
JournalJournal of Physical Chemistry B
Volume108
Issue number33
DOIs
StatePublished - Aug 19 2004

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Phosphotungstic Acid
affinity
Protons
Atoms
acids
protons
atoms
dehydration
oxygen atoms
desorption
Dehydration
alignment
density functional theory
Density functional theory
Desorption
gradients
energy
Oxygen
water
Molecules

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Nonlocal gradient corrected density functional theory was used to determine the optimal positions of the protons and their relative affinity in the secondary structure of phosphotungstic acid. First, a body centered cubic structure associated with the hexahydrate was incorporated into the model. The desorption energies of the first and second water molecules from a bridging H 5O 2 + species were calculated to be 109 and 55 kJ mol -1, respectively. The H 3O + or H + species remaining after dehydration are preferentially located between two oxygen atoms of adjacent Keggin units. The preferred position is between two terminal O d atoms or between a terminal O d atom and a bridging O c atom, depending on the alignment of the Keggin units. The energy advantage of sharing a proton between two Keggin units is in the range of 43 to 71 kJ mol -1. Three-dimensional periodic calculations indicate that anhydrous phosphotungstic acid can form a regular lattice in which all protons are shared between the heteropolyanions.",
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A first principles analysis of the location and affinity of protons in the secondary structure of phosphotungstic acid. / Janik, Michael John; Davis, Robert J.; Neurock, Matthew.

In: Journal of Physical Chemistry B, Vol. 108, No. 33, 19.08.2004, p. 12292-12300.

Research output: Contribution to journalArticle

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AU - Janik, Michael John

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AU - Neurock, Matthew

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AB - Nonlocal gradient corrected density functional theory was used to determine the optimal positions of the protons and their relative affinity in the secondary structure of phosphotungstic acid. First, a body centered cubic structure associated with the hexahydrate was incorporated into the model. The desorption energies of the first and second water molecules from a bridging H 5O 2 + species were calculated to be 109 and 55 kJ mol -1, respectively. The H 3O + or H + species remaining after dehydration are preferentially located between two oxygen atoms of adjacent Keggin units. The preferred position is between two terminal O d atoms or between a terminal O d atom and a bridging O c atom, depending on the alignment of the Keggin units. The energy advantage of sharing a proton between two Keggin units is in the range of 43 to 71 kJ mol -1. Three-dimensional periodic calculations indicate that anhydrous phosphotungstic acid can form a regular lattice in which all protons are shared between the heteropolyanions.

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