Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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The Electrocatalytic Reduction of Dioxygen by Bis-Cobalt Phenylporphyrins in Alkaline Solution

알칼리 수용액에서 Bis-Cobalt Phenylporphyrin 유도체들에 의한 산소의 전극 촉매적 환원

  • Yong-Kook ChoI (Department of Chemistry, Chonnam National University) ;
  • Hyun-Ju Moon (Department of Chemistry, Chonnam National University) ;
  • Seung-Won Jeon (Du-San Research & Development Center) ;
  • Ki-Hyung Chjo (Department of Chemistry, Chonnam National University)
  • 최용국 (전남대학교 자연과학대학 화학과) ;
  • 문현주 (전남대학교 자연과학대학 화학과) ;
  • 전승원 (두산 Research & Development 센타) ;
  • 조기형 (전남대학교 자연과학대학 화학과)
  • Published : 1993.04.20
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Abstract

The electrocatalytic reduction of dioxygen is investigated by cyclic voltammetry and chronoamperometry at glassy carbon electrode and carbon microelectrode coated with a variety of cobalt phenylporphyrins. The n value obtained at carbon microelectrode is slightly different from that determined at glassy carbon electrode. Dioxygen reduction catalyzed by the monormeric porphyrin Co(II)-TPP mainly occurs through the $2e^-$ reduction pathway resulting in the formation of hydrogen peroxide, electrocatalytic process carries out $4e^-$ reduction pathway of dioxygen to $H_2O$ at the electrodes coated with bis-cobalt phenylporphyrins. The electrocatalytic reduction of dioxygen is irreversible and diffusion controlled.

Cofacial bis-cobalt tetraphenylporphyrin 유도체 화합물들이 수식된 유리질 탄소 전극과 microelectrode에서 순환 전압 전류법 및 시간 전류법에 의해 산소의 환원 반응을 조사하였다. Microelectrode를 사용하여 시간-전류법에 의해 얻은 전자수 n값들은 유리질 탄소 전극을 사용하여 순환 전압 전류법들에 의해 얻은 결과들과 다소 다른 값으로 나타났다. 알카리성 용액에서 monomer인 cobalt tetraphenylporphyrin 화합물이 수식된 전극에서 산소의 호나원 반응 경로는 중간 생성물인 $H_2O_2$로 가는 2 전자반응으로 진행되었고, dimer인 cofacial bis-cobalt tetraphenylporphyrin 유도체 화합물들이 수식된 전극에서는 최종 생성물인 $H_2O$로 가는 4 전자 반응으로 진행되었다. 이와 같은 산소의 환원 반응은 전체적으로 비가역적으로 확산 지배적인 반응으로 주어졌다.

Keywords

References

  1. J. Electroanal. Chem. v.127 R. Sen;J. Zagal;E. Yeager
  2. J. Electrochem. Soc. v.131 R. A. Bull;F. R. Fan;A. J. Bard
  3. J. Electroanal. Chem. v.196 S. Zecevic;B. Simic-Glavaski;E. Yeager
  4. J. Electroanal. Chem. v.2 D. T. Sawyer;L. V. Interrante
  5. Acc. Chem. Res. v.12 J. Wilshire;D. T. Sawyer
  6. Nature v.201 R. Jasinski
  7. J. Electrochem. Soc. v.113 A. Kozawa;V. E. Zilionis;R. J. Brodd
  8. J. Electrochem. Soc. v.139 F. Anson
  9. J. Electroanal. Chem. v.88 T. Kuwana;M. Fujihira;K. Sunnakawa;T. Ossa
  10. J. Electrochem. Soc. v.127 J. Zagal;P. Bindra;E. Yeager
  11. J. Am. Chem. Soc. v.103 T. Geiger;F. C. Anson
  12. Inorg. Chem. v.16 D. Sawyer;E. Seo
  13. Inorg. Chem. v.16 R. K. Sen;J. Zagal;Yeager
  14. Electrochim. Acta v.15 I. Morcos;E. Yeager
  15. J. Electrochem. Soc. v.125 R. Zurilla;R. Sen;E. Yeager
  16. J. Electrochem. Soc. v.106 M. Davies;M. Clark;E. Yesger;F. Hovorka
  17. J. Electroanal. Chem. v.112 P. Fischer;J. Heitbaum
  18. J. Electrochem. Soc. v.126 J. C. Huang;R. K. Sen;E. Yeager
  19. Phys. Chem. v.85 J. A. R. van Veen;J. G. F. Collegan;J. F. van Baar;N. de Wit;C. J. Kroese;H. A. Colijn;Ber. Bunsenges
  20. Phys. Chem. v.85 J. A. R. van Veen;H. A. Colijn
  21. J. Catal. v.44 A. J. Appleby;J. Fleisch;M. Savy
  22. J. Am. Chem. Soc. v.102 J. P. Collman;P. Denisevich;Y. Konai;M. Marrocco;C. Koval;F. Anson
  23. J. Electroanal. Chem. v.132 K. Shigehara;F. Anson
  24. J. Electroanal. Chem. v.200 A. Elzing;A. van der Putten;W. Visscher;E. Barendrecht
  25. J. Electroanal. Chem. v.214 A. van der Putten;A. Elzing;W. Visscher;E. Barendrecht
  26. J. Electroanal. Chem. v.297 J. Ouyang;K. Shigehara;A. Yamada;Fred C. Anson
  27. Inorg. Chem. v.27 J. P. Collman;N. H. Hendricks;C. R. Leidner;E. Ngameni
  28. J. Am. Chem. Soc. v.105 R. R. Durand, Jr.;C. Susana Bencosme;J. P. Collman;F. C. Anson
  29. J. Phys. Chem. v.89 H. Y. Liu;I. Abdalmuhdi;C. K. Chang;F. C. Anson
  30. J. Am. Chem. Soc. v.106 C. K. Chang;H. Y. Liu;Abdalmuhdi
  31. J. Electroanal. Chem. v.306 S. Gupta;C. Fierro;E. Yeager
  32. J. Am. Chem. Soc. v.114 R. Karaman;A. Blasco;O. Almasson;R. Arasasingham;T. C. Bruice
  33. Electrochemical Methods A. J. Bard;L. R. Faulkner
  34. J. Phys. Chem. v.74 M. K. Tham;R. D. Walker;K. E. Gubbins
  35. J. Electrochem. Soc. v.112 K. E. Gubbins;R. D. Walker
  36. Electroanalysis v.3 A. Sucbeta;J. F. Resling
  37. Anal. Chem. v.57 A. S. Baranski;W. R. Fawcett;C. M. Gilbert