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首页> 外文期刊>Electroanalysis >Effect of the substituents on the ligand of iron phthalocyanines adsorbed on graphite electrodes on their activity for the electrooxidation of 2-mercaptoethanol
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Effect of the substituents on the ligand of iron phthalocyanines adsorbed on graphite electrodes on their activity for the electrooxidation of 2-mercaptoethanol

机译：取代基对吸附在石墨电极上的铁酞菁配体对其2-巯基乙醇电氧化活性的影响

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摘要

We have investigated the electrocatalytic activity of five iron phthalocyanines for the electrooxidation of 2-mercaptoethanol, with the complexes proadsorbed on a ordinary pyrolytic graphite electrode. The potential of Fe[II]/ Fe[I] and Fe[III]/Fe[II] redox processes on the adsorbed phthalocyanines are shifted to more positive potentials by the effect of electron withdrawing groups -CO2, -SO3 and -Cl and to more negative potentials by the electron-donating methoxy group compared to -H in unsubstituted FePc. The electrocatalytic activity, measured as current at constant potential, decreases as: Fe-octamethoxyphthalocyanine > Fe-phthalocyanine > Fe-tetracarboxyphthalocyanine > Fe-tetrasulfonatedphthalocyanine > Fe-perchlorinatedphthalocyanine, The most oxidant complex (Fe-perchlorinatedphthalocyanine) is the least active, which is contrary to what would be expected on thermodynamic grounds. This can be attributed to the fact that the reaction proceeds via an inner-sphere mechanism when the metal center is in state of oxidation II. [References: 51]
机译：我们已经研究了五种酞菁铁对2-巯基乙醇的电氧化的电催化活性，其配合物预先吸附在普通的热解石墨电极上。 Fe [II] / Fe [I]和Fe [III] / Fe [II]氧化还原过程在吸附的酞菁上的电势由于吸电子基团-CO2，-SO3和-Cl和与未取代的FePc中的-H相比，给电子的甲氧基可产生更大的负电势。在恒定电势下，以电流测量的电催化活性随以下条件而降低：Fe-八甲氧基酞菁> Fe-酞菁> Fe-四羧基酞菁> Fe-四磺化酞菁> Fe-全氯代酞菁，最具氧化剂的络合物（Fe-全氯代酞菁）活性最低。与热力学基础上的预期相反。这可以归因于以下事实：当金属中心处于氧化状态II时，反应通过内球机理进行。 [参考：51]

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