Influence of experimental conditions on electrochemical behavior of Prussian blue type nickel hexacyanoferrate film
Influence of experimental conditions on electrochemical behavior of Prussian blue type nickel hexacyanoferrate film
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DOI：
10.1016/j.electacta.2003.08.001
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发表时间：
2003-12
影响因子：
6.6
通讯作者：
S. Zamponi;M. Berrettoni;P. Kulesza;K. Miecznikowski;M. Malik;Oktawian Makowski;R. Marassi
中科院分区：
文献类型：
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作者：
S. Zamponi;M. Berrettoni;P. Kulesza;K. Miecznikowski;M. Malik;Oktawian Makowski;R. Marassi
六氰高铁镍（II） （II， III）， NiHCNFe薄膜和微晶析出物的电化学性能与制备方法和实验条件密切相关。薄膜已在惰性金属（金）和母金属（镍）衬底上生成。利用原子吸收法和基于x射线能谱的表面检测获得的元素分析估计数据支持了电极上六氰高铁镍微观结构伏安响应的解释。电沉积膜和机械附着的六氰高铁酸镍沉淀物都构成了混合结构，其中K和Ni与Fe的相对比值反映了改性溶液的组成、沉积电位和时间的选择，以及系统在钾盐支撑电解质中伏安电位循环暴露的时间和电位极限。我们在这里证明，六氰高铁酸镍的正极峰组与含有相对较多钾和较少镍的形式的电活性有关。另一方面，系统的负峰组应归因于主要是钾的耗尽和相对于铁含有更多的镍的形式。在这种情况下，使用先前提出的近似公式，K2Ni[FeII(CN)6]和KNi1.5[FeII(CN)6]，对于主要的六氰高铁镍（还原）形式是合理的。
Electrochemical properties of thin films and microcrystalline precipitates of nickel(II) hexacyanoferrate(II, III), NiHCNFe, are strongly dependent on the method of their preparation and experimental conditions of their investigation. The films have been generated on both inert (gold) and parent metal (nickel) substrates. Interpretation of voltammetric responses of nickel hexacyanoferrate microstructures on electrodes is supported with the data of elemental analysis estimations obtained using atomic absorption and surface examination based on X-ray energy dispersive spectroscopy. Both electrodeposited films and mechanically-attached precipitates of nickel hexacyanoferrate constitute mixed structures in which the relative ratios of K and Ni to Fe reflect composition of a solution for modification, choice of the deposition potential and time, and the time and potential limits of exposure of the system to voltammetric potential cycling in potassium salt supporting electrolyte. We demonstrate here that the more positive set of peaks of nickel hexacyanoferrate is related to the electroactivity of the form containing relatively larger amount of potassium and smaller of nickel. On the other hand, the more negative set of the system’s peaks shall be attributed to the form that is largely potassium depleted and containing more nickel relative to iron. In this context, the use of the previously proposed approximate formulas, K2Ni[FeII(CN)6] and KNi1.5[FeII(CN)6], for the predominant nickel hexacyanoferrate (reduced) forms is justified.