• Electrochemistry for Redox Polymer Film of N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium Ion
  • Cha SK
  • N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium이온의 산화-환원 고분자 피막에 대한 전기화학
  • 차성극
Abstract
The monomer N,N''-bis(3-pyrrol-1-yl-propyl)-4,4''-bipyridinium(PF6)2 was electrochemically polymerized on glassy carbon electrode surface. This polymer film electrode has electroactive sites on its bipyridinium ions distributed at the polymer strands. The formal potentials of the electrodes were -0.41V and -0.81V(vs. SSCE) for each step at phosphate buffer(pH=5.70). The diffusion coefficients of the dopants ions into the polymer matrix were 1.57*10-4 and 4.35*10-5 cm2s-1 for first and second redox couple, respectively. The rate constants of electron transfer at V2+/+ of the first step was a 57.53s-1, which was 22 times higher than V+/0 one having 2.63s-1 in the solution. The charge transfer resistance of the polymer film was influenced by the dopant ion of the electrolyte. Thus the resistances were 22.63, 16.81, 12.44 and 11.36 kΩ for LiClO4, NaClO4, KClO4, and phosphate buffer, respectively. The reaction order of the electropolymerization was first order and the rate constant of the polymerization was 1.31*10-1s-1 as determined by EQCM method. The G.C./p-BPB type electrode doped with phosphate ions showed a stability and reproducibility in CV procedure over 20 cycles.

단량체인 N,N''-bis(3-pyrrol-1-yl-propyl)-4,4''-bipyridinium(PF6-)2를 유리탄소전극 상에 전기화학적으로 중합하였다. 이 고분자 피막전극의 전기화학적 활성자리는 고분자 줄기에 분포된 bipyridinium이온이다. 이 전극은 인산염 완충용액(pH=5.7)에서 두 개의 산화-환원 쌍을 갖으며 그 형식전위는 각각 -0.41V와 -0.81V(vs. SSCE)였다. 이 고분자 피막 내에서 도판트 이온의 확산계수는 V2+/+와 V+/0단계에서 1.57*10-4과 4.35*10-5cm2s-1이였다. 환원과정보다 산화과정이 어려운 결과로 나타났다. 고분자 피막 내에서 전자전달 속도상수는 각 단계에서 각각 57.53과 2.63 s-1으로 첫째 단계가 22배나 큰 값을 보이고 있다. 이 피막의 전자전달 저항은 적용된 전해질의 양이온에 크게 영향을 받는다. 즉, LiClO4, NaClO4, KClO4 및 인산염 완충용액에서 도판트이온으로 작용하는 ClO4-와 PO43-이외에 이들의 대이온의 영향도 받아서 그 값이 각각 22.63, 16.81, 12.44 및 11.36 kΩ로 크게 차이가 났다. EQCM에 의한 전기화학적 중합반응의 속도상수 값은 일차 반응으로 초기에 1.31*10-1s-1였다. 이와 같이 PO43-이 도판트인 G.C./p-BPB형의 전극이 CV과정에서 안정하고 20회 이상 사용이 가능하며 재현성이 뛰어나다.

Keywords: N; N'-bis(3-pyrrol-1-yl-propyl)-4; 4'-bipyridine; electropolymerization; electrochemical quartz crystal microbalance(EQCM)

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This Article

  • 2001; 25(1): 6-14

    Published online Jan 25, 2001

  • Received on May 29, 2000