本文用循环伏安、交流阻抗等电化学方法研究了Keggin型钴取代杂多阴离子PW₁₁O₃₉Co(II)(H₂O)^5-(PW₁₁Co)的电化学性质及其对H₂O₂和甲醇阳极氧化的电催化作用，提出了PW₁₁Co作为阳极媒质可能的电催化机理. 结果表明，PW₁₁Co除了2对可逆的W—O骨架峰之外，在1.367 V/1.266 V处还有1对准可逆的Co峰，对应于Co(II)/Co(III)电对的氧化还原响应. 该电极过程有质子参与，其交换电流密度i₀为5.7×10^-6 A·cm^-2. 在酸性条件下(pH 2.5)，PW₁₁Co对H₂O₂的阳极氧化具有明显的电催化活性，耦合甲醇的氧化可使甲醇的氧化速率显著提高.

The electrochemical properties of the Keggin-type Co(II)-substituted heteropolyanion PW₁₁O₃₉Co(II)(H₂O)^5- (PW₁₁Co), as well as the electrocatalytic properties of PW₁₁Co towards the anodic oxidations of H₂O₂ and CH₃OH were studied using the electrochemical methods such as cyclic voltammetry and AC impedance spectroscopy in this paper. An electrocatalytic mechanism of PW₁₁Co as an anodic medium was also proposed. It was found that PW₁₁Co showed a pair of pseudo-reversible redox peaks at the potentials of 1.367 V/1.266 V, corresponding to the redox responses of the Co(II)/Co(III) couple, apart from two pairs of reversible W—O skeleton redox peaks. A proton was involved in the electrode process of the Co(II)/Co(III) couple with an exchange current density (i₀) of 5.7×10^-6 A·cm^-2. In particular, the couple exhibited a high electrocatalytic activity towards the anodic oxidation of H₂O₂ in an acidic solution of pH 2.5, which can be coupled to catalyze the methanol oxidation.