Electrocatalysis Characteristics of a Polynuclear Cyanide Complex, Ruthenium Purple, for Dihydrogen Oxidation
Electrocatalysis Characteristics of a Polynuclear Cyanide Complex, Ruthenium Purple, for Dihydrogen Oxidation
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多核氰化物配合物钌紫对二氢氧化的电催化特性
DOI：
10.1023/b:joip.0000039365.88800.1b
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
A. Tajiri
中科院分区：
文献类型：
--
作者：
Toshiyuki Abe;T. Nagasaka;A. Tajiri
在钌紫（RP）表面涂覆铁（III）钌氰化物(即重复单元胞结构：FeIII4[RuII（CN)6]3或MFeIII[RuII(CN)6]和M =碱金属反离子）的电极上发现电催化二氢氧化发生。伏安法研究表明，在氧化氰金属酸盐中的fei2时，可诱导电催化二氢氧化反应。用伏安法研究了RP的电催化特性，特别是根据所使用的电解质类型（K+或Na+）， RP在K+中表现出比在Na+电解质体系中更有效的电催化作用。当feito fei3发生单电子电氧化时，阴离子RP（即还原RP）也会释放水合碱金属阳离子来补偿电荷。此外，在K+电解质体系中，阳离子更容易通过氰金属酸盐网络传输（例如，水合阳离子的尺寸：0.36 nm处Na+≈0.35 nm处RP的晶格通道> K+在0.24 nm处）。因此，目前的电催化很可能是由电氧化在动力学上主导的。
An electrocatalytic dihydrogen oxidation was found to take place on an electrode coated with iron(III) ruthenocyanide (i.e., repeating unit cell structure: FeIII4[RuII(CN)6]3or MFeIII[RuII(CN)6] and M = alkali metal counter ion) called ruthenium purple (RP). It was shown by voltammetric study that an electrocatalytic dihydrogen oxidation is induced on oxidizing the FeIIion in the cyanometallate. When the electrocatalysis characteristics of RP were investigated by voltammetry, especially in terms of the kinds of electrolyte used (K+or Na+), RP exhibited a more efficient electrocatalysis in the K+than in the Na+electrolyte system. While a one-electron electro-oxidation of FeIIto FeIIIoccurs, there is also a release of hydrated alkali metal cation(s) from the anionic RP (i.e., reduced RP) to compensate for charge. Moreover, cation transport through the cyanometallate network is more facile for the K+electrolyte system (cf., size of hydrated cation: Na+at 0.36 nm ≈ lattice channel of RP at 0.35 nm > K+at 0.24 nm). Therefore, it was most probable that the present electrocatalysis is kinetically dominated by the electro-oxidation.