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Electrochemically Induced Oscillations of C2H4 Oxidation Over Thin Sputtered Rh Catalyst Films

The electrochemically promoted induction of self-sustained catalytic rate and potential oscillations during C2H4 oxidation was studied over sputtered Rh thin (40 nm catalyst films interfaced with ZrO2 (8 mol% Y2O3). The reaction rate oscillates simultaneously with the catalyst potential, and always in the opposite direction. The electrochemically induced oscillatory rate is typically 60 times larger than the open-circuit catalytic rate and 1000 times larger than the electrochemical rate of O2− supply to the catalyst. The phenomenon is completely reversible and only observed under anodic polarization where the rate oscillates between the values corresponding to metallic Rh and surface Rh2O3. The oscillations are caused by the electrochemically controlled backspillover of O2− to the catalyst surface and the concomitant, via repulsive lateral interactions, decomposition of surface rhodium oxide followed by surface reoxidation to Rh2O3 by gaseous O2.

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  1. 1

    M.M. Slin’ko and N.I. Jaeger, in: Studies in Surface Science and Catalysis, B. Delmon and J.T. Yates eds. (Elsevier, Amsterdam, 1994).

  2. 2

    K. Krischer M. Eiswirth G. Ertl (1991) Surf. Sci. 251–252 900

  3. 3

    M. Bär M. Falcke C. Zülicke H. Engel M. Eiswirth G. Ertl (1992) Surf. Sci. 269–270 471

  4. 4

    C.G. Vayenas B. Lee J.N. Michaels (1980) J. Catal 66 37

  5. 5

    I.V. Yentekakis S. Neophytides C.G. Vayenas (1988) J. Catal. 111 152

  6. 6

    A.K. Galwey P. Gray J.F. Griffiths S.M. Hasko (1985) Nature 313 668

  7. 7

    T. Lamb R.P. Scott P. Watts B. Holland S. Gentry A. Jones (1977) J. Chem. Soc. Chem. Commun. 23 882

  8. 8

    R.C. Yeates J.E. Turner A.J. Gellman G.A. Somorjai (1985) Surf. Sci. 149 175

  9. 9

    K.E. Keck B. Kasemo (1986) Surf. Sci. 167 313

  10. 10

    I.V. Yentekakis C.G. Vayenas (1988) J. Catal. 111 170

  11. 11

    C.G. Vayenas S. Bebelis C. Pliangos S. Brosda D. Tsiplakides (2001) Electrochemical Activation of Catalysis. Promotion, Electrochemical Promotion, and Metal-Support Interaction Kluwer Academic/Plenum Publishers New York

  12. 12

    C.G. Vayenas C. Georgakis J.N. Michaels J. Tormo (1981) J. Catal. 67 348

  13. 13

    C.G. Vayenas J.N. Michaels (1982) Surf. Sci. 120 L405

  14. 14

    D.J. Kaul E.E. Wolf (1986) Chem. Eng. Sci. 41 1101

  15. 15

    S.D. Dhalewadikar N.M. E A. Varma (1986) Chem. Eng. Sci. 41 1743

  16. 16

    E.A. Baranova A. Thursfield S. Brosda G. Fôti C. Comninellis C.G. Vayenas (2005) J. Electrochem. Soc. 152 IssueID2 E40

  17. 17

    G. Fóti S. Wodiunig C. Comninellis (2000) Current topics in Electrochemistry 7 1

  18. 18

    G. Fóti I. Bolzonella C. Comninellis (2003) NoChapterTitle C.G. Vayenas (Eds) Modern Aspects of Electrochemistry Kluwer Academic/Plenum Publisher New York, Boston, Dordrecht, London, Moscow 310

  19. 19

    C.G. Vayenas S. Brosda C. Pliangos (2003) J. Catal. 216 487

  20. 20

    C. Pliangos I.V. Yentekakis X.E. Verykios C.G. Vayenas (1995) J. Catal. 154 124

  21. 21

    C. Pliangos I.V. Yentekakis V.G. Papadakis C.G. Vayenas X.E. Verykios (1997) Applied Catalysis B: Environmental 14 161

  22. 22

    C.G. Vayenas M.M. Jaksic S.I. Bebelis S.G. Neophytides (1996) NoChapterTitle J.O.M. Bockris B.E. Conway R.E. White (Eds) Modern Aspects of Electrochemistry Plenum Press New York 57

  23. 23

    U.F. Franck R. FitzHugh (1961) Z. Elektrochem. 65 156

  24. 24

    B. Rush J. Newman (1995) J. Electrochem. Soc. 142 IssueID11 3770

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Correspondence to C. G. Vayenas.

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Baranova, E.A., Thursfield, A., Brosda, S. et al. Electrochemically Induced Oscillations of C2H4 Oxidation Over Thin Sputtered Rh Catalyst Films. Catal Lett 105, 15–21 (2005).

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Key words

  • ethylene oxidation
  • Rh thin film catalysts
  • electrochemical promotion
  • Yttria-stabilized zirconia
  • oscillatory phenomena