The thiophene‐modified iron porphyrin FeT3ThP and the respective iron Hangman porphyrin FeH3ThP, incorporating a carboxylic acid hanging group in the second coordination sphere of the iron center, were electropolymerized on glassy carbon electrodes using 3,4‐ethylenedioxythiophene (EDOT) as co‐monomer. Scanning electron microscopy images and Resonance Raman spectra demonstrated incorporation of the porphyrin monomers into a fibrous polymer network. Porphyrin/polyEDOT films catalyzed the reduction of molecular oxygen in a four‐electron reaction to water with onset potentials as high as +0.14 V vs. Ag/AgCl in an aqueous solution of pH 7. Further, FeT3ThP/polyEDOT films showed electrocatalytic activity towards reduction of hydrogen peroxide at highly positive potentials, which was significantly enhanced by introduction of the carboxylic acid hanging group in FeH3ThP. The second coordination sphere residue promotes formation of a highly oxidizing reaction intermediate, presumably via advantageous proton supply, as observed for peroxidases and catalases making FeH3ThP/polyEDOT films efficient mimics of heme enzymes.

中文翻译：

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Hangman效应增强噻吩基取代的卟啉铁聚合物的电催化活性

噻吩改性的铁卟啉FeT3ThP和相应的Hangman卟啉FeH3ThP铁在铁中心的第二个配位球中结合了一个羧酸悬挂基团，并使用3,4-乙烯二氧噻吩（EDOT）作为共聚单体在玻碳电极上进行电聚合。扫描电子显微镜图像和共振拉曼光谱证明了卟啉单体掺入到纤维状聚合物网络中。卟啉/ polyEDOT膜催化四电子反应中的分子氧还原成水，在pH 7的水溶液中，其起始电势相对于Ag / AgCl高达+0.14V。此外，FeT3ThP / polyEDOT膜显示出对在高正电位下还原过氧化氢，通过在FeH3ThP中引入羧酸悬挂基团，其显着增强。第二个配位球残基可能通过有利的质子供应来促进高氧化反应中间体的形成，如过氧化物酶和过氧化氢酶所观察到的，使FeH3ThP / polyEDOT膜有效地模仿了血红素酶。