本文报道六氰亚铁酸钯膜修饰电极在ＨＣｌ，ＫＣｌ和ＮａＣｌ溶液中的现场反射ＦＴＩＲ光谱电化学研究，结果表明该修饰膜具有内外两层结构，分别为Ｐｄ２Ｆｅ（ＣＮ）６和Ｍ２ＰｄＦｅ（ＣＮ）６，其中Ｍ为支持电解质一价阳离子．在１ｍｏｌ／ＬＮａＣｌ中，内层的氧化电位Ｅｍ＝０．８７Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ），外层为０．７７Ｖ．在１ｍｏｌ／ＬＨＣｌ或ＫＣｌ中两层的氧化还原波重叠为一个大ＣＶ波峰而难以分辨，然而现场ＦＴＩＲ光谱电化学清晰地分辨出这两种结构在所有３种溶液中ＣＮ的不同振动频率，发现Ｈ＋离子是最佳的支持电解质，能使这两种结构同时发生氧化反应
The electrochemically deposited Palladium hexacyanoferrate thin film on Glassy Carbon electrode (PdHCF|GC) has been studied in HCl, KCl and NaCl solutions by in_situ external reflection FTIR spectroelectrochemical technique. It is found that the behavior of the electroactive PdHCF film can be understood in terms of two states: Pd2Fe(II)(CN)6 formed in the inner layer and (M+)2Fe(II)(CN)6 (M+: electrolyte cation) formed in the outer layer. The inner layer is oxidized at Em=0.87 V in 1 mol/L KCl, while for the outer layer Em=0.77 V(vs. Ag/AgCl). In 1 mol/L NaCl or HCl solutions, half_wave potentials of these two layers are not well resolved, however corresponding CN stretching frequencies for the two states have been well observed in all three solutions. H+ has been found as a good supporting electrolyte for redox reactions of these two layers.
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