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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