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Decrease in the double layer capacitance by faradaic current

机译:通过法拉第电流减少双层电容

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摘要

This study describes the reverse of the well-known double layer effects on charge transfer kinetics in the relationship between a cause and an effect. The reversible redox reaction of a ferrocenyl derivative decreased the capacitive values of the double layer impedance up to negative values, corresponding to an inductive component. This observation was disclosed by the subtraction of the real admittance from the imaginary admittance, which can extract the net double layer capacitance from the Warburg impedance. The inductance-like behavior is caused due to two reasons: (i) the double layer capacitance in the polarized potential domain is determined by the low concentrations of the fieldoriented solvent dipoles that are considered as the conventionally employed redox concentrations and (ii) the double layer capacitance is caused by the orientation of the dipoles in the same direction as that of the electric field, whereas the redox reaction generates charge in the direction opposite to the field. The faradaic effect was demonstrated via the ac-impedance data obtained for the ferrocenyl compound in a KCl solution in the unpolarized potential domain between 1 Hz and 3 kHz frequency. The negative admittance was proportional to the frequency. The theory of negative capacitance was presented by combining the mirror-image surface charge with the Nernst equation.
机译:这项研究描述了成因与效应之间关系中众所周知的双层效应对电荷转移动力学的反作用。二茂铁基衍生物的可逆氧化还原反应将双层阻抗的电容值减小到负值,对应于电感性成分。通过从虚数导纳中减去实数导纳可以揭示此观察结果,这可以从Warburg阻抗中提取出净双层电容。类似于电感的行为是由于两个原因引起的:(i)极化电势域中的双层电容取决于被认为是常规使用的氧化还原浓度的低浓度的磁场定向溶剂偶极子,以及(ii)两倍层电容是由偶极子在与电场相同方向上的定向所引起的,而氧化还原反应则在与电场相反的方向上产生电荷。法拉第效应通过在1 Hz和3 kHz频率之间的非极化电势域中的KCl溶液中的二茂铁基化合物获得的交流阻抗数据得到证明。负导纳与频率成正比。通过将镜像表面电荷与能斯特方程相结合,提出了负电容理论。

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