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Isopolytungstate Adsorption on Platinum: Manifestations of Underpotential Deposition

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Abstract

Metatungstate isopolyanion adsorption on smooth polycrystalline Pt and carbon-supported dispersed platinum in sulfuric acid medium is studied by cyclic voltammetry. Manifestations of both reversible and irreversible adsorption are found, with the features typical for heteropolytungstates of the same Keggin structure. When (NH4)6H2W12O40 is added to sulfuric acid solution, H underpotential deposition (UPD) charge starts to redistribute: it decreases at high hydrogen coverage but increases at higher potentials, with appearance of additional reversible redox feature in “double layer region.” The total charge value in diluted metatungstate solutions remains the same as for pure Pt. However, this value decreases with metatungstate concentration. At any fixed (NH4)6H2W12O40 concentration, the total charges in the hydrogen region are practically the same in 0.1 and 0.5 M sulfuric acid. Strongly bonded metatungstate species can be kept at the surface after the transfer to supporting solution. These irreversibly adsorbed species are redox-inactive and demonstrate stronger suppression of H UPD. Excursion to oxygen adsorption region does not result in complete desorption, but redistribution of charge takes place again. Our observations can be assigned (by analogy with Keggin anions adsorption on Au and Ag) to slow adsorbate–metal bonding, with subsequent increase of the number of bonded oxygen atoms. General trends are qualitatively the same for both Pt materials, but dispersed Pt on glassy carbon favors irreversible adsorption. The data confirm that adsorbed metatungstate can undergo reversible reduction at potentials more positive than the equilibrium potential of its first W(V/VI) redox transition (molecular UPD). Comparative electrocatalytic tests are presented for nitrate electroreduction on bare Pt, Pt modified with irreversibly adsorbed metatungstate, and Pt in metatungstate solution. The latter system, containing both forms of tungstate adsorbate, demonstrates high steady-state electrocatalytic activity at potentials below ca. 0.1 V reversible hydrogen electrode (RHE).

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References

  1. M. Sadakane, E. Steckhan, Chem. Rev. 98, 219 (1998)

    Article  CAS  Google Scholar 

  2. D.L. Long, R. Tsunashima, L. Cronin, Angew. Chem. Int. Ed 49, 1736 (2010)

    Article  CAS  Google Scholar 

  3. D. Martel, A. Kuhn, P.J. Kulesza, M.T. Galkowski, M.A. Malik, MA Electrochim. Acta 46, 4197 (2001)

    Article  CAS  Google Scholar 

  4. M.I. Borzenko, M. Chojak, P. Kulesza, G.A. Tsirlina, O.A. Petrii, Electrochim. Acta. 48, 3797 (2003)

    Article  CAS  Google Scholar 

  5. P. Satyananda Kishore, B. Viswanathan, T.K. Varadarajan, J. Phys. Chem. 113, 12918 (2009)

    Google Scholar 

  6. L. Lee, J.X. Wang, R.R. Adzic, I.K. Robinson, A.A. Gewirth, J. Amer. Chem. Soc. 123, 8838 (2001)

    Article  CAS  Google Scholar 

  7. C.M. Teague, X. Li, M.E. Biggin, L. Lee, J. Kim, A.A. Gewirth, J. Phys. Chem. B 108, 1974 (2004)

    Article  CAS  Google Scholar 

  8. J. Kim, A.A. Gewirth, Langmuir 19, 8934 (2003)

    Article  CAS  Google Scholar 

  9. M. Ge, B. Zhong, W.G. Klemperer, A.A. Gewirth, J. Am. Chem. Soc. 1996(118), 5812 (1996)

    Article  Google Scholar 

  10. Y. Wang, I.A. Weinstock, Dalton Trans. 39, 6143 (2010)

    Article  CAS  Google Scholar 

  11. L.G.S. Pereira, F.R. dos Santos, M.E. Pereira, V.A. Paganin, E.A. Ticianelli, Electrochim. Acta 51, 4061 (2006)

    Article  CAS  Google Scholar 

  12. W. Tze, M.I. Borzenko, G.A. Tsirlina, O.A. Petrii, Russ. J. Electrochem 38, 1250 (2002)

    Article  Google Scholar 

  13. J.R. Ferrell III, Mei-Chen Kuo, J.A. Turner, A.M. Herring, Electrochim. Acta 53, 4927 (2008)

    Article  CAS  Google Scholar 

  14. R.P. Brooker, P. Baker, H.R. Kunz, L.J. Bonville, R. Parnas, J. Electrochem. Soc. 156, B1317 (2009)

    Article  CAS  Google Scholar 

  15. B.R. Limoges, R.J. Stanis, J.A. Turner, A.M. Herring, Electrochim. Acta 50, 1169 (2005)

    Article  CAS  Google Scholar 

  16. R. Wlodarczyk, M. Chojak, K. Miecznikowski, A. Kolary, P.J. Kulesza, R. Marassi, J. Power Sources 159, 802 (2006)

    Article  CAS  Google Scholar 

  17. M. Chojak, A. Kolary-Zurowska, R. Wlodarczyk, K. Miecznikowski, K. Karnicka, B. Palys, R. Marassi, P.J. Kulesza, Electrochim Acta 52(5574) (2007)

  18. E.D. Mishina, G.A. Tsirlina, E.V. Timofeeva, N.E. Sherstyuk, M.I. Borzenko, N. Tanimura, S. Nakabayashi, O.A. Petrii, J. Phys. Chem. B 108, 17096 (2004)

    Article  CAS  Google Scholar 

  19. G. Tsirlina, E. Mishina, E. Timofeeva, N. Tanimura, N. Sherstyuk, M. Borzenko, S. Nakabayashi, O. Petrii, Faraday Discussions 140, 245 (2008)

    Article  CAS  Google Scholar 

  20. B. Keita, L. Nadjo, D. Belanger, C.P. Wilde, M. Hilaire, J. Electroanal. Chem. 384, 155 (1995)

    Article  Google Scholar 

  21. J.P. Launay, Inorg. Nucl. Chem. 38, 807 (1976)

    Article  CAS  Google Scholar 

  22. H. Sadayuki, N. Kiyomi, E. Kazuo, Polyhedron 29, 2595 (2010)

    Article  Google Scholar 

  23. B. Keita, L. Nadjo, G. Krier, J.F. Muller, J. Electroanal. Chem. 223, 287 (1987)

    Article  CAS  Google Scholar 

  24. S.P.E. Smith, J.B. Christian, Electrochim. Acta 53, 2994 (2008)

    Article  CAS  Google Scholar 

  25. J.B. Christian, S.P.E. Smith, M.S. Whittingham, H.D. Abruna, Electrochem. Commun. 9, 2128 (2007)

    Article  CAS  Google Scholar 

  26. M.I. Borzenko, G.N. Botukhova, G.A. Tsirlina, O.A. Petrii, Electrochim. Acta 53, 3854 (2008)

    Article  CAS  Google Scholar 

  27. B.J. Smith, V.A. Patrick, Australian J. Chem. 53, 965 (2000)

    Article  CAS  Google Scholar 

  28. O.V. Sherstyuk, S.N. Pron’kin, A.L. Chuvilin, A.N. Salanov, E.R. Savinova, G.A. Tsirlina, O.A. Petrii, Russ. J. Electrochem. 36, 741 (2000)

    Article  CAS  Google Scholar 

  29. L.M. Plyasova, I.Y. Molina, A.N. Gavrilov, S.V. Cherepanova, O.V. Cherstiouk, N.A. Rudina, E.R. Savinova, G.A. Tsirlina, Electrochim. Acta 51, 4477 (2006)

    Article  CAS  Google Scholar 

  30. T. Nagel, N. Bogolowski, G. Samjeske, H. Baltruschat, J. Solid State Electrochem. 7, 614 (2003)

    Article  CAS  Google Scholar 

  31. V.K. Laurinavichutea, S.Y. Vassiliev, L.M. Plyasova, I. Molina, A.A. Khokhlov, L.V. Pugolovkin, M.I. Borzenko, G.A. Tsirlina, Electrochim. Acta 54, 5439 (2009)

    Article  Google Scholar 

  32. O.A. Petrii, T.Y. Safonova, J. Elecytroanal. Chem. 331, 897 (1992)

    Article  CAS  Google Scholar 

  33. O.A. Petrii, T.Ya. Safonova (1994) In “The 2nd Int. Symp. ‘Electrochemistry practice and theory’”, Lodz (1994) p. 18–23.

  34. T.Y. Safonova, O.A. Petrii, J. Elecytroanal. Chem. 448(211) (1998)

  35. E.V. Timofeeva, M.I. Borzenko, G.A. Tsirlina, E.V. Astaf’ev, O.A. Petrii, J. Solid State Electrochem. 8, 778 (2004)

    Article  CAS  Google Scholar 

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Acknowledgments

The authors are grateful to Marina I. Borzenko for valuable comments and to Sergey Yu. Vassiliev for his help with STM sample characterization. This work was supported by RFBR, project 11-03-00902a.

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Division of the Russian Academy of Sciences, Prospekt Ak. Lavrentieva 5, Novosibirsk, 630090, Russia

    Olga V. Cherstiouk & Alexander N. Simonov

  2. Department of Electrochemistry, Moscow University, Leninskie Gory, 3, str.1, Moscow, 199991, Russia

    Galina A. Tsirlina

Authors
  1. Olga V. Cherstiouk
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  2. Alexander N. Simonov
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  3. Galina A. Tsirlina
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Correspondence to Galina A. Tsirlina.

Additional information

This paper is dedicated to Professor Radoslav R. Adzic, with the highest respect to his uniquely valuable contribution to interfacial electrochemistry, including the concepts of commensuration and lattice formation in adlayers and coadsorption phenomena.

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Cherstiouk, O.V., Simonov, A.N. & Tsirlina, G.A. Isopolytungstate Adsorption on Platinum: Manifestations of Underpotential Deposition. Electrocatalysis 3, 230–237 (2012). https://doi.org/10.1007/s12678-012-0114-1

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