In situ vanadium K-edge and tungsten LIII-edge X-ray absorption fine structure of vanadium-substituted heteropolytungstates immobilized in a high-area carbon electrode in acid aqueous electrolytes

D. E. Clinton, D. A. Tryk, I. T. Bae, F. L. Urbach, M. R. Antonio, Daniel Alberto Scherson

Research output: Contribution to journalArticle

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Abstract

Electronic and structural aspects of vanadium-substituted heteropolytungstates immobilized in a high-area carbon (XC-72) as a function of oxidation state have been examined by in situ X-ray absorption near-edge structure (XANES) in an acidic electrolyte. The results obtained for K4PVW11O40 revealed a sizable shift in the V K-edge XANES region, which is characterized by a prominent pre-edge peak, following a one-electron reduction. Such behavior has been attributed to the transfer of an electron to an orbital localized mainly on vanadium. Injection of a second electron gives rise to the near disappearance of the pre-edge peak without major shifts in the position of edge jump, a phenomenon ascribed to an increase in the symmetry of the vanadium site upon reduction to yield a nearly octahedral environment. Similar behavior is observed for Cs6PV3W9O40 when the electrode is polarized in the potential regions where the vanadium ions are reduced to VIV and VIII, respectively. No changes in the in situ W LIII-edge XANES could be discerned for these vanadium-substituted heteropolytungstates in their various oxidation states, for which the spectral features were the same as those of H3PW12O40 adsorbed on XC-72 under otherwise identical conditions.

Original languageEnglish
Pages (from-to)18511-18514
Number of pages4
JournalJournal of physical chemistry
Volume100
Issue number47
Publication statusPublished - 1996 Nov 21
Externally publishedYes

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Vanadium
Tungsten
X ray absorption
vanadium
Electrolytes
tungsten
Carbon
fine structure
electrolytes
Electrodes
acids
Acids
electrodes
carbon
x rays
Electrons
Oxidation
oxidation
electrons
shift

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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In situ vanadium K-edge and tungsten LIII-edge X-ray absorption fine structure of vanadium-substituted heteropolytungstates immobilized in a high-area carbon electrode in acid aqueous electrolytes. / Clinton, D. E.; Tryk, D. A.; Bae, I. T.; Urbach, F. L.; Antonio, M. R.; Scherson, Daniel Alberto.

In: Journal of physical chemistry, Vol. 100, No. 47, 21.11.1996, p. 18511-18514.

Research output: Contribution to journalArticle

Clinton, D. E. ; Tryk, D. A. ; Bae, I. T. ; Urbach, F. L. ; Antonio, M. R. ; Scherson, Daniel Alberto. / In situ vanadium K-edge and tungsten LIII-edge X-ray absorption fine structure of vanadium-substituted heteropolytungstates immobilized in a high-area carbon electrode in acid aqueous electrolytes. In: Journal of physical chemistry. 1996 ; Vol. 100, No. 47. pp. 18511-18514.
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