Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Electrocatalytic Effect on the Oxygen Reduction and Electrochemical Properties of Co(Ⅱ)-dimethyl Bipyridine Perchlorate

Co(Ⅱ)$(dimethyl bipyridine)_3(ClO_4)_2$의 전기화학적 성질과 산소환원에 대한 전극 촉매 효과

  • Published : 19970800
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Abstract

Diffusion Coefficient$(D_0)$ and electrode reaction rate Constant$(K_0)$ of Co$(dimethyl bipyridine)_3(ClO_4)_2$ were determined by cyclic voltammetry and chronoamperometry. It was also investigated that the effects of solvent, concentration, and scan rate, etc. on the diffusion coefficient and the temperature effect on the rate constant. The peak currents and diffusion coefficients were dcreased as increasing the viscosity of solvent. Diffusion coefficient was $5.54{\times}10^{-6 }cm^2/sec$ and the reaction rate constant was $2.39{\times}10^{-3 }/s$ at 25$^{\circ}C$. The thermodynamic parameters such as ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S$ were calculated from plotting the reaction rate constants versus the solution temperatures. This compound was shown the catalytic effect on the oxygen reduction that the reduction peak current of oxygen was greatly enhanced and the peak potential was shifted to +0.2 volt.

Co$(dimethyl bipyridine)_3(ClO_4)_2$의 확산계수$(D_0)$와 전극반응속도상수$(K_0)$를 순환전압전류법과 대시간전류법으로 구하였다. 확산계수에 대한 용매, 농도, 주사속도 등의 영향과 반응속도상수에 대한 온도변화의 영향을 조사하였다. 25$^{\circ}C$에서 확산계수는 $5.54{\times}10^{-6 }cm^2/sec$이었고, 반응속도상수는 $2.39{\times}10^{-3 }/s$ 이었으며, 용매의 점도가 커질수록 봉우리전류값과 확산계수는 감소하였다. 반응속도상수에 대한 온도의 영향으로부터, ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S$ 등의 열역학적 파라미터를 구하였다. 이 화합물은 $O_2$분자의 환원에서 봉우리전류를 크게 증가시키고, 환원전위를 양(+)전위방향으로 이동시키는 열역학적 전극촉매현상을 보였다.

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References

  1. J. Phys. Chem. v.96 Surridge, N. A.;Zvanut, M. E.;Keene, F. R.;Murray, R. W.(etc)
  2. J. Phys. Chem. v.98 Sosnoff, C. S.;Sullivan, M.;Murray, R. W.
  3. J. Phys. Chem. v.98 Terrill, R. H.;Sheehan, P. E.;Long, V. C.;washburn, S.;Murray, R. W.
  4. Inorg. Chem. v.33 Ramprasad, D.;Gilicinski, A. G.;Markley, T. J.;Pez, G. P.
  5. Chem. Rev. v.89 Jones, R. D.;Summerville, D. A.;Basola, F.
  6. Chem. Rev. v.84 Niederhoffer, E. C.;Timmons, J. H.;Martell, A. E.
  7. Chem. Letter Aohi, A.;Miyashita, T.
  8. J. Am. Chem. Soc. v.99 Sprintschink, G.;Kirsch, P. P.;Whittern, D. G.
  9. Inorg. Chem. v.29 Kalyanasundaram, K.;Nazeeruddin, M. K.
  10. J. Am. Chem. Soc. v.116 Doletoglov, A.;Meyer, T. J.
  11. J. Electoroanal. Chem. v.410 Sauthier, M;Deronzier, A.;Bozec, H. L.;Navarro, M.
  12. Inorg. Chim. Acta. v.195 Nagao, N;Tsuchida, M.;Mukaida, M.(etc)
  13. Nature v.374 Zelikovich, l.;Libman, J.;Shanzer, A.
  14. Adv. Mater v.8 Zhu, S. S.;Swager, T. M.
  15. J. Phys. Chem. v.100 Xiang, Y.;Villemure, G.
  16. Science v.273 Arkin, M. R.;Stemp, E. D. A.;Olson, E. J. C.;Barbara, P. F.
  17. Science v.268 Langen, R.;Winkler, J. R.;Gray, H. B.(etc)
  18. Recl. Trav. Chim. Pays-Bas v.114 Hartl, F.;Rossenaar, B. D.;Stor, G. J.;Stufkene, D. J.
  19. J. Am. Chem. Soc. v.117 Larson, S. L.;Derr, D. L.;Elliott, C. M.(etc)
  20. J. Phys. Chem. v.99 Worner, M.;Greiner, G.;Rau, H.
  21. Anal. Sci. & Tech. v.9 Kim, I. K.;Jun, I. C.;Murray, R. W.
  22. J. Am. Chem. Soc. v.118 Pyati, R.;Murray, R. W.
  23. Ph. D. Thesis, Dept. of Chemistry, Univ. of North Carolina, Chapel Hill Electrochemical Investigation of Ultraslow Diffusion in Polymer Solvents and Molecular Scale Diffusion in a Neat Poly(ether) Tailed Redox Probes Poupart, M. W.
  24. Electrochemical Methods Bard A. J.;Faulkner, L. R.
  25. J. Electroanal. Chem. v.185 Kovach, P.;Coudill, W. L.;Peters, D. G.;Wightman, R. M.
  26. Electrochemical Methods Bard A. J.;Faulkner, l. R.
  27. Electrochemical Methods Bard A. J.;Faulkner, L. R.
  28. Anal. Chem. v.37 Nicholoson, R. S.
  29. Electrochemical Methods Bard A. J.;Faulkner, L. R.
  30. Indian J. Chem. v.14A Saxena R. S.;Bhatia, S. K.
  31. Electrochemical Methods Bard, A. J.;Faulkner,l. R.
  32. Electrochemical Methods Bard, A. J.;Faulkner, L. R.
  33. Physical Chemistry(5th ed.) Atkins, P.
  34. Physical Chemistry(5th ed.) Atkins, P.
  35. Physical Chemistry(5th ed.) Atkins, P.