Journal of Applied Electrochemistry

, Volume 36, Issue 11, pp 1237–1240 | Cite as

Electrochemically promoted olefin isomerization reactions at polymer electrolyte fuel␣cell membrane electrode assemblies

Article

Abstract

The isomerization of 2-3-dimethyl-1-butene was enhanced over a thousand fold (vs the open circuit value) by spillover protons generated by low currents (electrochemical promotion) on carbon supported Pd catalysts in a polymer electrolyte fuel cell. There was substantial proton spillover catalyzed shift of the double bond of 2-3-dimethyl-1-butene. With 3-3-dimethyl-1-butene, the proton spillover catalyzed methyl shift occurred at low levels and 2-2-dimethyl-butane was the primary product from the simple reduction reaction. Although the substantial non-Faradaic electrochemical modification of catalysis (NEMCA) of the double bond isomerization of an olefin was further demonstrated, the more challenging electrochemical promotion of an olefin methyl shift at the polymer electrolyte Pd/C cathode was less pronounced.

Keywords

2-3-dimethyl-1-butene electrochemical promotion fuel cells NEMCA olefin isomerization Pd cathode proton spillover Nafion™ 

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Notes

Acknowledgements

This work was supported by the Army Research Office Grant No. W911NF-05-1-0020, and the NASA-UPR Center for Nanoscale Materials grant no. NCC3-1034.

References

  1. 1.
    Vayenas C.G., Bebelis S., Ladas S. (1990). Nature 343:625CrossRefGoogle Scholar
  2. 2.
    International Society for Solid-state Ionics, Extended Abstracts of the 12th International Conference on Solid State Ionics, references therein, Thessaloniki, Greece, June 6–12 (1999)Google Scholar
  3. 3.
    Ploense L., Salazar M., Gurau B., Smotkin E.S. (1997). Yogi. J. Am. Chem. Soc. 119:11550CrossRefGoogle Scholar
  4. 4.
    Ploense L., Salazar M., Gurau B., Smotkin E.S. (2000). Solid State Ionics 136–137:713CrossRefGoogle Scholar
  5. 5.
    I.D. Raistrick, in J.W. Van Zee, R.E. White, K. Kinoshita and H.S. Burney (eds), Diaphragms, Separators, and Ion Exchange Membranes, PV 86–13 (The Electrochemical Society Proceedings Series, Pennington, NJ, 1986), p. 172Google Scholar
  6. 6.
    I.D. Raistrick, U.S. Pat. 4,876,115 (1989)Google Scholar
  7. 7.
    Wilson M.S., Gottesfeld S. (1992). Yogi. J. Appl. Electrochem. 22:1CrossRefGoogle Scholar
  8. 8.
    Newman J., Thomas-Alyea K.E. (2004). Electrochemical Systems. John Wiley & Sons, New York Chapter 22Google Scholar
  9. 9.
    M. Salazar, Cathodic Hydrogenation and Isomerization of Unsaturated Hydrocarbons in a Polymer Electrolyte Fuel Cell, Dissertation (Illinois Institute of Technology, 2000)Google Scholar
  10. 10.
    Bard A.J., Faulkner L.R. (1980). Electrochemical Methods. John Wiley & Sons, New York, pp. 101Google Scholar
  11. 11.
    Viswanathan R., Hou G., Liu R., Bare S.R., Modica F., Mickelson G., Segre C.U., Leyarovska N., Smotkin E.S. (2002). Yogi. J. Phys. Chem. B 106:3458CrossRefGoogle Scholar
  12. 12.
    Vayenas C.G., Bebelis S., Yentekakis I.Y., Lintz H.G. (1992). Catal. Today 11:303CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc. 2006

Authors and Affiliations

  1. 1.Parsons-Research and Development Solutions, LLCMorgantownUSA
  2. 2.Department of ChemistryUniversity of Puerto Rico at Rio PiedrasSan JuanUSA

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