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Journal of Applied Electrochemistry

, Volume 36, Issue 11, pp 1253–1260 | Cite as

A DEMS study of the electrocatalytic hydrogenation and oxidation of p-dihydroxybenzene at polycrystalline and monocrystalline platinum electrodes

  • J. Sanabria-Chinchilla
  • M.P. SoriagaEmail author
  • R. Bussar
  • H. Baltruschat
Article

Abstract

The electrochemical hydrogenation and oxidation of p-dihydroxybenzene (hydroquinone) chemisorbed at polycrystalline Pt, well-ordered Pt(111) and disordered Pt(111) electrodes were studied by differential electrochemical mass spectrometry (DEMS). For comparative purposes, benzene was investigated at polycrystalline Pt. Anodic oxidation yielded only CO2 as the volatile (DEMS-detectable) product. However, at least three oxidation cycles were necessary for exhaustive oxidation; this indicates that: (i) non-volatile products were generated in the first cycle, (ii) these products either stayed adsorbed or, in part, were re-adsorbed during a cathodic scan into the double-layer potential region, and (iii) these species were further oxidized on subsequent anodic scans. Electrocatalytic hydrogenation of hydroquinone at polycrystalline Pt followed two parallel (not sequential) paths to generate benzene and cyclohexane: the “branching ratio” was heavily in favor of the latter product. The adsorbate can be displaced by CO at potentials in the double layer region. Since no volatile species was observed during this process, the adsorbate is not already reduced; e.g., to benzene. On well-ordered Pt(111), no cyclohexane was produced and only a minuscule fraction of benzene was observed; however, quantitative desorption of (unidentified) non-volatile organic material took place at the negative potential. The disordered Pt(111) surface behaved more like the polycrystalline rather than the monocrystalline surface. The H2Q-hydrogenation reaction proceeds more readily on Pt with surface steps and kinks.

Keywords

anodic oxidation of hydroquinone chemisorption of hydroquinone differential electrochemical mass spectrometry electrochemical hydrogenation of hydroquinone 

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Notes

Acknowledgements

The present project was funded by the Deustche Forschungsgemeinschaft (DFG). MPS would like to acknowledge the Welch Foundation for additional support. JSC thanks the German Academic Exchange Service (DAAD) for a research fellowship to conduct DEMS experiments in the laboratories of HB.

References

  1. 1.
    Somorjai G.A. (1994). Introduction to Surface Chemistry and Catalysis. Wiley, New YorkGoogle Scholar
  2. 2.
    Soriaga M.P., Harrington D.A., Stickney J.L., Wieckowski A. (1966). In: Conway B.E., White R.E., Bockris J.O’M. (eds) Modern Aspects of Electrochemistry. Plenum, New YorkGoogle Scholar
  3. 3.
    Bard A.J., Abruña H.D., Chidsey C.E., Faulkner L.R., Feldberg S., Itaya K., Melroy O., Murray R.W., Porter M.D., Soriaga M.P., White H.S., (1993) J. Phys. Chem. 97: 7147CrossRefGoogle Scholar
  4. 4.
    Soriaga M.P., Hubbard A.T., (1982) J. Am. Chem. Soc. 104: 2735CrossRefGoogle Scholar
  5. 5.
    Soriaga M.P., Binamira-Soriaga E., Hubbard A.T., Bezinger J.B., Pang K.-W.P., (1985) Inorg. Chem. 24:65CrossRefGoogle Scholar
  6. 6.
    Hubbard A.T., (1988) Chem. Rev. 88: 633CrossRefGoogle Scholar
  7. 7.
    Soriaga M.P., (1990) Chem. Rev. 90: 771CrossRefGoogle Scholar
  8. 8.
    Soriaga M.P., Wilson P.H., Hubbard A.T., (1982) J. Electroanal. Chem. 142: 317CrossRefGoogle Scholar
  9. 9.
    Soriaga M.P., Hubbard A.T., (1982) J. Am. Chem. Soc. 104: 3937CrossRefGoogle Scholar
  10. 10.
    Soriaga M.P., White J.H., Hubbard A.T., (1983) J. Phys. Chem. 87: 3048CrossRefGoogle Scholar
  11. 11.
    Soriaga M.P., Hubbard A.T., (1984) J. Phys. Chem. 88: 1089CrossRefGoogle Scholar
  12. 12.
    Soriaga M.P., Chia V.K.F., White J.H., Song D., Hubbard A.T., (1984) J. Electroanal. Chem. 162: 143Google Scholar
  13. 13.
    Chia V.K.F., Soriaga M.P., Hubbard A.T., (1984) J. Electroanal. Chem. 167: 97CrossRefGoogle Scholar
  14. 14.
    Soriaga M.P., White J.H., Song D., Hubbard A.T., (1984) J. Electroanal. Chem. 171:359CrossRefGoogle Scholar
  15. 15.
    White J.H., Soriaga M.P., Hubbard A.T., (1984) J. Electroanal. Chem. 177: 89CrossRefGoogle Scholar
  16. 16.
    Soriaga M.P., Song D., Hubbard A.T., (1985) J. Phys. Chem. 89: 285CrossRefGoogle Scholar
  17. 17.
    Soriaga M.P., Song D., Zapien D.C., Hubbard A.T., (1985) Langmuir 1: 123CrossRefGoogle Scholar
  18. 18.
    Pang K.P., Benziger J.B., Soriaga M.P., Hubbard A.T., (1984) J. Phys. Chem. 88:4583CrossRefGoogle Scholar
  19. 19.
    Krauskopf E.K., Wieckowski A., (1990) J. Electroanal. Chem. 296:159CrossRefGoogle Scholar
  20. 20.
    Soriaga M.P., White J.H., Song D., Chia V.K., Arrhenius P.O., Hubbard A.T., (1985) Inorg. Chem. 24: 3CrossRefGoogle Scholar
  21. 21.
    Gui J.Y., Kahn B.E., Laguren-Davidson L., Lin C.-H., Lu F., Salaita G.N., Stern D.A., Hubbard A.T., (1989) Langmuir 5: 819CrossRefGoogle Scholar
  22. 22.
    Mebrahtu T., Berry G.M., Soriaga M.P., (1988) J. Electroanal. Chem. 247: 241CrossRefGoogle Scholar
  23. 23.
    Soriaga M.P., Stickney J.L., Hubbard A.T., (1983) J. Mol. Cat. 21: 211CrossRefGoogle Scholar
  24. 24.
    Soriaga M.P., Stickney J.L., Hubbard A.T., (1983) J. Electroanal. Chem. 144: 207Google Scholar
  25. 25.
    Mebrahtu T., Berry G.M., Soriaga M.P., (1988) J. Electroanal. Chem. 239: 375CrossRefGoogle Scholar
  26. 26.
    Bravo B., Michelhaugh S.L., Mebrahtu T., Soriaga M.P., (1988) Electrochim. Acta 11: 1507CrossRefGoogle Scholar
  27. 27.
    Gui Y-P., Kuwana T., (1986) Langmuir 2: 471CrossRefGoogle Scholar
  28. 28.
    Baltruschat H.. (1999) In: Wieckowski A. (eds) “Interfacial Electrochemistry”. Marcel Dekker, New YorkGoogle Scholar
  29. 29.
    Baltruschat H., (2004) J. Am. Soc. Mass Spectrom. 15: 1693CrossRefGoogle Scholar
  30. 30.
    Hartung T., Baltruschat H., (1990) Langmuir 6: 953CrossRefGoogle Scholar
  31. 31.
    Hartung T., Schmiemann U., Kamphausen I., Baltruschat H., (1991) Anal. Chem. 63: 44CrossRefGoogle Scholar
  32. 32.
    Schmiemann U., Baltruschat H., (1993) J. Electroanal. Chem. 347:93CrossRefGoogle Scholar
  33. 33.
    Löffler T., Bussar R., Drbalkova E., Janderka P., Baltruschat H., (2003) Electrochim. Acta 48: 3829CrossRefGoogle Scholar
  34. 34.
    Schmiemann U., Jusys Z., Baltruschat H., (1994) Electrochim. Acta 39: 561CrossRefGoogle Scholar
  35. 35.
    Vestral J., Lofflër Th., Müller U., Baltruschat H., (1999) J. Electroanal. Chem. 461:90CrossRefGoogle Scholar
  36. 36.
    Löffler T., Drbalkova E., Janderka P., Königshoven P., Baltruschat H., (2003) J. Electroanal. Chem. 550: 81CrossRefGoogle Scholar
  37. 37.
    Rodríguez J.L., Souto R.M., González S., Pastor E., (1998) Electrochim. Acta 44: 1415CrossRefGoogle Scholar
  38. 38.
    Souto R.M., Rodríguez J.L., Fernández-Mérida L., Pastor E., (2000) J. Electroanal. Chem. 494: 127CrossRefGoogle Scholar
  39. 39.
    Souto R.M., Rodríguez J.L., Pastor G., Pastor E., (2000) Electrochim. Acta 45: 1645CrossRefGoogle Scholar
  40. 40.
    Wagner F.T., Ross P.N., (1983) J. Electroanal. Chem. 150:141CrossRefGoogle Scholar
  41. 41.
    Clavilier J., Rodes A., Achi K.E., Zamakhchari M.A., (1991) J. Chim. Phys. 88: 1291Google Scholar
  42. 42.
    Löffler T., Baltruschat H., (2003) J. Electroanal. Chem. 554–555: 333CrossRefGoogle Scholar
  43. 43.
    Sashikata K., Furuya N., Itaya K., (1991) J. Vac. Sci. Technol. B 9:457CrossRefGoogle Scholar
  44. 44.
    Zhu J.M., Hartung T., Tegtmeyer D., Baltruschat H., Heitbaum J., (1988) J. Electroanal. Chem. 244: 273CrossRefGoogle Scholar
  45. 45.
    Inukai J., Wakisaka M., Yamagishi M., Itaya K., (2004) Langmuir 20: 7507CrossRefGoogle Scholar

Copyright information

© Springer 2006

Authors and Affiliations

  • J. Sanabria-Chinchilla
    • 1
  • M.P. Soriaga
    • 1
    Email author
  • R. Bussar
    • 2
  • H. Baltruschat
    • 2
  1. 1.Department of ChemistryTexas A&M UniversityCollege StationUSA
  2. 2.Institut für Physikalische und Theoretische ChemieUniversität BonnBonnGermany

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