기능성 전극의 전기촉매로의 응용-POly-MePMP+BF4-/Ferri-ferrocyanide/Ascorbic Acid계

장동훈; 오승모

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.1, 138-147, March, 1992

Chemically Modified Electrodes and Their Applications to Electrocatalysis-Poly-MePMP⁺BF₄^-/Ferri -ferrocyanide/Ascorbic Acid System

장동훈, 오승모

초록

기능성 전극(chemically modified electrodes)을 이용한 전기촉매반응을 조사하였다. 고분자 지지체로서 음이온 교환이 가능한 poly-[1-methyl-3-(pyrrol-1-ylmethyl) pyridinium]을 사용하였는데 이는 정전류 방법으로 직접 전극표면에 중합시켰다. 전극표면에 코팅되는 필름의 두께는 중합시 전체 전하량으로 조절하였으며, SEM을 이용하여 두께를 측정하였고, 필름의 두께와 전하량과의 직선관계를 조사하였다. 전기촉매반응에 활성을 갖는 ferro/ ferricyanide 이온은 빠른속도로 이온교환이 가능하였으며, 이온교환되는 양은 cyclic voltammetry 실험 결과 1.2∼1.3M이었다. 필름내에 존재하는 ferro/ferricyanide 이온이 ascorbic acid 산화반응의 매개체임을 cyclic votammetry 실험을 통하여 알 수 있었고, RDE 실험을 통하여 반응속도론적 파라미터를 규명하였는데 본 실험의 조건에서 Saveant 등의 모델 중 ER+S에 해당됨을 알 수 있었다. 이상적인 모델인 R+S가 되기 위하여 기능성 전극이 갖추어야 할 조건을 제시하였다.

Chemically-modified electrodes were fabricated and their electrocatalytic behaviors have been investigated. As a modifying layer, poly-[1-methyl-3-(pyrrol- 1-ylmethyl) pyridinium] was electropolymerized onto Pt electrodes under constant current. The thickness of the polymer film was controlled by means of total charge consumed during the electropolymerization. SEM was used to measure the thickness. There was a linear relationship between the passed charge and the film thickness. Ferro/ferricyanide, used as an electron mediator in this study, was rapidly ion-exchanged into the polymer layer with its concentration of 1.2∼ 1.3M. It was found that electrooxidation of ascorbic acid is catalyzed by incorporated ferri/ferrocyanide couple. Kinetic parameters for electrooxidation were determined by RDE experiments. The results indicate that the present system corresponds to ER+S case based on the Saveant theory. Improving methods have been proposed to be R+S case which is ideal for electrocatalysis.

[References]

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[1] Ohsaka T, Okajima T, Oyama N, J. Electroanal. Chem., 215, 191 (1986)

[2] Murray RW, Ewing AG, Durst RD, Anal. Chem., 59, 379A (1987)

[3] Feldman BJ, Burgmayer P, Murray RW, J. Am. Chem. Soc., 103, 1 (1981)

[4] Merz A, "Topics in Current Chemistry,", 152, 49 (1990)

[5] Heller A, Accounts Chem. Res., 23, 128 (1990)

[6] Bange K, Gambke T, Adv. Mater., 2, 10 (1990)

[7] Chidsey CED, Murray RW, Science, 231, 25 (1986)

[8] Wrington MS, Science, 231, 32 (1986)

[9] White HS, Kittlesen GP, Wrighton MS, J. Am. Chem. Soc., 106, 5375 (1984)

[10] Linford RG, "Electrochemical Science and Technology of Polymers-1," Elsevier, New York (1987)

[11] Faulkner LR, Electrochim. Acta, 34, 1699 (1989)

[12] Murray RW, Annu. Rev. Mater. Sci., 14, 145 (1954)

[13] Faulkner LR, Chem. Eng. News, 27, 28 (1984)

[14] Murray RW, Electroanalytical Chem., 13, 191 (1954)

[15] Andrieux CP, Dumas-Bouchiat JM, Saveant JM, J. Electroanal. Chem., 131, 1 (1982)

[16] Andrieux CP, Saveant JM, J. Electroanal. Chem., 134, 163 (1982)

[17] Andruiex CP, Dumas-Bouchiat JM, Saveant JM, J. Electroanal. Chem., 169, 9 (1984)

[18] Sawyer DT, "Experimental Electrochemistry for Chemists," John Wiley & Sons, New York (1974)

[19] Mao H, Pickup PG, J. Electroanal. Chem., 256, 127 (1989)

[20] Diaz AF, Castillo JI, Logan JA, Lee W, J. Electroanal. Chem., 205, 309 (1986)

[21] Diaz AF, Bargon J, Skotheim TA, "Handbook of Conducting Polymers Vol. I," Marcel Dekker, New York (1986)

[22] Zingler B, Miller LL, J. Am. Chem. Soc., 104, 4811 (1982)

[23] Daum P, Lenhard JR, Roleson D, Murray RW, J. Am. Chem. Soc., 102, 4649 (1980)

[24] Oh SM, Faulkner LR, J. Electroanal. Chem., 269, 77 (1989)

[25] Oh SM, Faulkner LR, J. Am. Chem. Soc., 111, 5613 (1989)