Novel member of polymetalloporphines, namely manganese polymetalloporphine of type I (pMnP-I) obtained by ion exchange from magnesium polyporphine of type I (pMgP-I) is reported for the first time and compared to its cobalt analogue (pCoP-I). Both polymer films have been obtained via two-step procedure: demetalation of the pMgP-I electrode film via its exposure to trifluoroacetic acid solution, resulting in formation of the metal-free polyporphine of type I (pH2P-I) followed by electrochemically induced incorporation of Co or Mn ions from the acetonitrile solution of cobalt and manganese perchlorates. A further oxidative transformation of pCoP-I, pMnP-I polymer films has led to the corresponding polyporphines of type II, pCoP-II and pMnP-II, possessing such unique features as condensed polymer structure with a very high density of active sites and high electronic conductivity within a very broad potential range including the one corresponding to the neutral (uncharged) state of the polymer matrix. Both polymers of type II also exhibit interesting electrocatalytic activity toward oxygen electroreduction in aqueous neutral (pH 6.7) and alkaline (pH 13) media which was evaluated under cyclic voltammetric and steady-state conditions. The results demonstrate that the efficiency (regardless of the electrolyte) of both polymetalloporphines is comparable to bare platinum electrode. The effect of annealing of polymer-modified electrodes on their catalytic properties has also been considered.

中文翻译：

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锰钴聚卟啉薄膜对氧还原反应的电催化性能

首次报道了多金属卟吩的新成员，即 I 型锰多金属卟吩 (pMnP-I)，通过离子交换从 I 型镁聚卟啉 (pMgP-I) 获得，并与其钴类似物 (pCoP-I) 进行比较。两种聚合物薄膜都是通过两步程序获得的：pMgP-I 电极薄膜通过暴露于三氟乙酸溶液使其脱金属，导致形成 I 型无金属聚卟啉 (pH2P-I)，然后通过电化学诱导掺入从高氯酸钴和锰的乙腈溶液中提取 Co 或 Mn 离子。pCoP-I、pMnP-I 聚合物薄膜的进一步氧化转化导致相应的 II 型聚卟啉、pCoP-II 和 pMnP-II，具有这样的独特特征，例如具有非常高密度的活性位点和高电导率的缩合聚合物结构，在非常宽的电位范围内，包括对应于聚合物基质的中性（不带电）状态的电位范围。在循环伏安和稳态条件下评估的中性 (pH 6.7) 和碱性 (pH 13) 水溶液介质中，II 型两种聚合物还表现出对氧电还原的有趣电催化活性。结果表明，两种多金属卟吩的效率（无论电解质如何）与裸铂电极相当。还考虑了聚合物改性电极的退火对其催化性能的影响。