Journal of the Mineralogical Society of Korea (한국광물학회지)

The Mineralogical Society of Korea (한국광물학회)
권호 표지

The Electrocatalytic Reduction of Molecular Oxygen with Clay Modified Electrodes

점토광물을 이용한 산소환원의 전기화학적 촉매성에 관한 연구

  • Oh Sung-Hun (Department of Geology, Pusan National University) ;
  • Hwang Jin-Yeon (Department of Geology, Pusan National University) ;
  • Shim Yoon-Bo (Department of Chemistry, Pusan National University) ;
  • Lee Hyomin (Department of Geology, Pusan National University) ;
  • Yoon Jihae (Department of Geology, Pusan National University)
  • 오성훈 (부산대학교 자연과학대학 지질학과) ;
  • 황진연 (부산대학교 자연과학대학 지질학과) ;
  • 심윤보 (부산대학교 자연과학대학 화학과) ;
  • 이효민 (부산대학교 자연과학대학 지질학과) ;
  • 윤지해 (부산대학교 자연과학대학 지질학과)
  • Published : 2005.03.01
Download PDF
⟨ Previous Next ⟩

Abstract

The electrocatalytic reduction of O₂ was investigated with methyl viologen and methylene blue incorporated clay-modified electrodes. Clay suspensions were prepared with Na-montmorillonite, Ca-montmorillonite, and kaolinite. The methyl viologen-clay modified electrodes were made by coating clay suspensions adsorbing methyl viologen on a glassy carbon electrode. Cyclic voltammetry were performed in aqueous media to investigate the electrocatalytic property of the modified electrode in reducing O₂. A Na-montmorillonite modified electrode showed the greatest adsorption capacity for methyl viologen. The modified electrode made of Na-montmorillonite suspension of 0.87 g/10 mL and a 2.5 mM of methyl viologen solution showed the most effective electrocatalytic property, where the catalytic reduction potential was shifted by 242.6 mV toward the positive potential. The electrocatalytic ability was more significant in acidic (pH=3.7) and alkaline (pH=12.7) media than the neutral pH range (6.3∼8.3). The methyl viologen-Na-montmorillonite modified electrode had the good reproducibility and maintain the electrocatalytic property over 20 times reuse.

몇 가지 점토광물과 메틸바이올로젠 또는 메틸렌블루를 함유시킨 점토수식전극을 이용하여 산소환원에 대한 전기화학적 촉매성을 검토하였다. 점토광물로는 Na-몬모릴로나이트, Ca-몬모릴로나이트, 카오리나이트를 사용하였다. 점토수식전극은 유리탄소전극 표면에 점토 현탁액을 입히고 메틸바이올로젠을 흡착시킨 것을 사용하였으며, 전기화학적 산소환원의 정도는 순환 전압전류법(cyclic voltammetry)으로 측정하였다. 실험결과, 다른 점토시료에 비하여 Na-몬모릴로나이트가 메틸바이올로젠의 흡착효과가 가장 크게 나타났고, 메틸바이올로젠을 흡착시킨 점토수식전극이 산소환원에 대한 촉매성이 월등히 우수하였다. 즉 촉매산소환원 피크가 242.6 mV 만큼 +방향으로 이동하였다. 메틸바이올로젠을 흡착시킨 점토수식전극이 메틸렌블루를 흡착시킨 점토수식전극보다 산소환원에 대한 촉매성이 더 높게 나타났다. Ca-몬모릴로나이트의 경우는 변화가 없었으나 Na-몬모릴로나이트의 구조는 메틸바이올로젠의 흡착으로 변화되었다. 메틸바이올로젠- Na-몬모릴로나이트 점토수식전극은 현탁액의 점토 농도가 약 0.87 g/10 mL이고. 메틸바이올로젠의 수용액의 농도가 대략 2.5 mM일 때 산소환원 촉매 효과가 가장 탁월하였다. 지지전해질의 pH에 따른 점토수식 전극의 산소 환원 촉매성은 중성의 pH 범위(6.3과 8.3)에서보다 산성인 pH 3.7과 알칼리성인 pH 12.7에서 월등히 크게 나타났다.

Keywords

References

  1. Ahenach, J., Cool, P., and Vansant, E.F. (1998) Acidic/Base treatment of AI-PILC in KCl solution. Microporous and Mesoporous Material, 26, 185-192 https://doi.org/10.1016/S1387-1811(98)00232-7
  2. Boopathi, M., Won, M.S., Kim, Y.H., Shin, S,C., and Shim, Y.B. (2002) Electrocatalytic Reduction of Molecular Oxygen Using a Poly(terthiophene carboxylic acid) Appended by 1,5-Diaminonaphthalene Copper Complex. J. Electrochem. Soc., 149, No.7, pp. E265-E271
  3. Borek, Vol. and Morra, M.1. (1998) Cyclic Voltammetry of Aquocobalamin on Clay-Modified Electrodes. Environo. Sci. Technol., 32, 2149-2153 https://doi.org/10.1021/es970700c
  4. Carrado, K.A., Marshall C.L., Brenner, J.R., and Song, K. (1998) Materials derived from synthetic organo-clay complexes as novel hydrodesulfurization catalyst supports. Microporous & Mesoporous Material, 32, 17-26
  5. Ghantous, L., Lojou, E., and Bianco, P. (1998) Membrane electrodes for studying the interaction of humic acids with heavy metals: Cu(II), Pb (II), Cd (II), and U (VI), Electroanalysis. 10(18), 1249-1254 https://doi.org/10.1002/(SICI)1521-4109(199812)10:18<1249::AID-ELAN1249>3.0.CO;2-F
  6. Jeong, E.D., Won, M.S., and Shim, Y.B. (1998) The Electrocatalytic Reduction of Molecular Oxygen with a Co (II)-Glyoxal Bis (2-hydroxyanil) Complex Coated Electrode. Bull. Korean Chem. Soc., 19(4), 417-422.
  7. Ouyang, C.S. and Wang, C.M. (1998) Clay-enhanced electrochemiluminescence and its application in the detection of glucose. Journal of Electrochemical Society, 145(8), 2654-2659 https://doi.org/10.1149/1.1838695
  8. Ouyang, C.S. and Wang, C.M. (1999) Electrochemical characterization of the clay-enhanced luminol ecl reaction. Journal of Electroanalytical Chemistry, 474(1), 82-88 https://doi.org/10.1016/S0022-0728(99)00311-3
  9. Pecorari, M. and Bianco, P. (1998) lon-exchange Voltammetry of Cationic Species at Membrane Claymodified Electrode. Electroanalysis, 10(3), 181-186 https://doi.org/10.1002/(SICI)1521-4109(199803)10:3<181::AID-ELAN181>3.0.CO;2-#
  10. Shyu, S.C. and Wang, C.M. (1998) Characterization of Iron-Containing Clay Modified Electrodes and Their Application for Glucose Sensing. Journal of the Electrochemical Society, 145(1), 154-158 https://doi.org/10.1149/1.1838228
  11. Zen, J.M. and Chen, H.J. (1997) A Selective Voltammetric Method for Uric Acid and Dopamine Detection using Clay Modified Electrodes. Anal. Chem., 69(24)
  12. Zen, J.M., Jeng, S.H., and Chen, H.J. (1996) Determination of Paraquat by Square-Wave V oltammetry at a Perfluorosulfonated Ionomer/Clay Modified Electrodes. Anal. Chem., 68, 498-502 https://doi.org/10.1021/ac950590x