Redox behavior of europium in the Preyssler heteropolyanion [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12-}

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In aqueous, mineral-acid electrolytes, the cyclic voltammetry of the europium- exchanged Preyssler heteropolyanion, [Eu{sup III}P{sub 5}W{sub 30}O{sub 110}]{sup 12-}, is unique among all the other trivalent-lanthanide-exchanged anions, [Ln{sup III}P{sub 5}W{sub 30}O{sub 110}]{sup 12-} for Ln {triple_bond} Ce-Lu. All [LnP{sub 5}W{sub 30}O{sub 110}]{sup 12-}, including Eu, form heteropoly blues upon reduction. In order to obtain insights about this issue, we conducted in situ Eu L{sub 3}-edge XANES (X-ray absorption near edge structure) spectroelectrochemical experiments on an aqueous solution of [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12-} (5.5 mM) in a supporting electrolyte of 1 M H{sub 2}SO{sub 4} at two extreme potentials. The ... continued below

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10 p.

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Antonio, M.R. & Soderholm, L. August 1, 1997.

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Description

In aqueous, mineral-acid electrolytes, the cyclic voltammetry of the europium- exchanged Preyssler heteropolyanion, [Eu{sup III}P{sub 5}W{sub 30}O{sub 110}]{sup 12-}, is unique among all the other trivalent-lanthanide-exchanged anions, [Ln{sup III}P{sub 5}W{sub 30}O{sub 110}]{sup 12-} for Ln {triple_bond} Ce-Lu. All [LnP{sub 5}W{sub 30}O{sub 110}]{sup 12-}, including Eu, form heteropoly blues upon reduction. In order to obtain insights about this issue, we conducted in situ Eu L{sub 3}-edge XANES (X-ray absorption near edge structure) spectroelectrochemical experiments on an aqueous solution of [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12-} (5.5 mM) in a supporting electrolyte of 1 M H{sub 2}SO{sub 4} at two extreme potentials. The results demonstrate that the Eu{sup III} ion in the colorless Preyssler anion solution at open circuit potential (+0.21 V vs Ag/AgCl) is electroactive and is reduced to Eu{sup II} in the resulting dark blue solution from constant-potential bulk electrolysis at -0.55 V vs Ag/AgCl. This unusual redox behavior of [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12-} may be of technological importance in the area of oxidation catalysis.

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10 p.

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OSTI as DE97008271

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  • Other Information: PBD: [1997]

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  • Other: DE97008271
  • Report No.: ANL/CHM/PP--88535
  • Grant Number: W-31109-ENG-38
  • DOI: 10.2172/516035 | External Link
  • Office of Scientific & Technical Information Report Number: 516035
  • Archival Resource Key: ark:/67531/metadc698184

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  • August 1, 1997

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  • Aug. 14, 2015, 8:43 a.m.

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  • Dec. 15, 2015, 12:11 p.m.

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Antonio, M.R. & Soderholm, L. Redox behavior of europium in the Preyssler heteropolyanion [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12-}, report, August 1, 1997; Illinois. (digital.library.unt.edu/ark:/67531/metadc698184/: accessed October 20, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.