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Electrochemistry on multi-walled carbon nanotubes in organic solutions

机译:有机溶液中多壁碳纳米管的电化学

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The oxidation of ferrocene (FeCp_2) to ferrocenium cation FeCp_2~+ (where Cp: cyclopentadienyl anion, C _5H_5~- was investigated by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) on either a glassy carbon (GC) electrode or a film consisted of multi-walled carbon nanotubes (MWCNT) in acetone (ACE), methanol (MeOH) and ACE/MeOH binary mixtures. The half-wave potentials (E_(1/2)), the diffusion coefficients (D) and the heterogeneous electron transfer rate constants (k_s) of the redox couple FeCp_2~(+/0) were determined. On both electrodes tested, the electron transfer process was found to be quasi-reversible and diffusion controlled in all investigated solvent mixtures. The E_(1/2) values were shifted toward less positive potentials with the enrichment of mixtures in MeOH, due probably to the larger Lewis basicity of the MeOH molecules. Furthermore, values of both D and k_s diminish with the increase of MeOH content following the progressive increase of viscosity of the solvent medium. Among the electrodes probed, GC provides faster electrochemical process since it affords less charge-transfer resistance (R_(ct)), and consequently, an insignificant barrier for interfacial electron transfer.
机译:通过循环伏安法(CV)和电化学阻抗谱(EIS)在玻璃碳(GC)电极上研究了二茂铁(FeCp_2)氧化为二茂铁阳离子FeCp_2〜+(其中Cp:环戊二烯阴离子,C _5H_5〜-)或由在丙酮(ACE),甲醇(MeOH)和ACE / MeOH二元混合物中的多壁碳纳米管(MWCNT)组成的薄膜半波电势(E_(1/2)),扩散系数(D)确定了氧化还原对FeCp_2〜(+ / 0)的异质电子传递速率常数(k_s),在两个测试电极上均发现电子传递过程是可逆的,并且在所有研究的溶剂混合物中均受扩散控制。随着MeOH混合物浓度的增加,E_(1/2)的值向正电位方向移动,这可能是由于MeOH分子的Lewis碱性较大,此外,D和k_s的值都随着MeOH含量的增加而减小。逐步增加溶剂介质的粘度。在所探测的电极中,GC提供了更快的电化学过程,因为它提供了较小的电荷转移电阻(R_(ct)),因此,对界面电子转移的影响很小。

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