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Modification of electrodes with nanostructured films containing dirhodium-substituted polyoxometalates

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Abstract

Layer-by-layer (LBL) electrostatic assembly was used to prepare films comprising generation-4 polyamidoamine dendrimers (G4-PAMAM) and dirhodium polyoxometalates (Rh2POMs) on glassy carbon (GC) electrodes. To employ the propensity of P2Mo18O62 6− (PMo) to directly adsorb on glassy carbon, a new compound, Rh2PMo, was synthesized and characterized. The behavior was compared to that of a previously reported Rh2POM prepared from PW12O40 3− (PW). The LBL assembly of (G4-PAMAM, Rh2PW) n bilayers on GC pretreated by formation of a monolayer of 4-aminobenzoic acid was studied by doing a linear least-squares fit of peak current to n (n=5); the result gave an r 2 of only 0.90. With Rh2PMo, the analogous experiments with n=7 gave an r 2=0.995. Strong adsorption of Rh2PMo onto GC allowed the assembly of Rh2PMoadsorbed|(G4-PAMAM, Rh2PMo) n on conventional GC and on a 10-µm carbon fiber. The latter was used to demonstrate the bifunctional electrocatalytic property of these films through reduction of nitrite and the oxidation of arsenite.

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Acknowledgements

This work was supported in part by the National Institutes of Health through grant 1R15GM64390-01 and by the Miami University Center for Nanotechnology. Support for R.K.P. (Anderson University), by the NSF Research Experience for Undergraduates program through a grant to Miami University, is appreciated.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Miami University Center for Nanotechnology, Miami University, Oxford, OH , 45056, USA

    Anna M. Kijak, Robbyn K. Perdue & James A. Cox

Authors
  1. Anna M. Kijak
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  2. Robbyn K. Perdue
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  3. James A. Cox
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Correspondence to James A. Cox.

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Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003

Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)

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Kijak, A.M., Perdue, R.K. & Cox, J.A. Modification of electrodes with nanostructured films containing dirhodium-substituted polyoxometalates. J Solid State Electrochem 8, 376–380 (2004). https://doi.org/10.1007/s10008-003-0471-z

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