多钒取代聚氧乙烯酸盐在玻碳电极上低电位氧化l-半胱氨酸的高效电催化剂
Multi-vanadium substituted polyoxometalates as efficient electrocatalysts for the oxidation of l-cysteine at low potential on glassy carbon electrodes
摘要：
研究了Dawson型钒配合物[As_2 W_（18）（VO）_3 O_（66）]_（11-）在pH = 7介质中的电化学行为，并与[P_2V_2W_（16）O_（62）]_（8-）（P_2V_2W_（16）），[P_2MoV_2W_（15）O_（62）]_（8-）（P_2MoV_2W_（15））和[P_2V_3W_（15）O_（62）]_（9-）（P_2V_3W_（15））的电化学行为进行了比较。电化学研究表明，该POM含有2个VIV中心和1个VV中心，其化学式为As_2V_2IVVW_（18），与滴定、元素分析和磁性测量结果一致。所有的多金属氧酸盐都能有效地氧化L-半胱氨酸。与单钒取代的POM的结果的比较表明，钒原子在POM骨架中的积累是有益的电催化过程。此外，本工作强调了POM结构在L-半胱氨酸电催化氧化中的重要影响。这项工作的显着成果是，L-半胱氨酸的氧化在选定的POM的存在下的潜力已基本上驱动在负方向相比，单独的玻璃碳的情况下，这是与更快的动力学的特征。还必须指出系统的稳定性。
英文摘要：
The electrochemical behaviours of the sandwich-type complex [As2W18(VO)3O66]11- were studied in a pH 7 medium and compared with those of the three following Dawson-type vanadium-substituted complexes: [P2V2W16O62]8- (P2V2W16), [P2MoV2W15O62]8- (P2MoV2W15) and [P2V3W15O62]9- (P2V3W15). Electrochemistry shows that the sandwich-type POM contains 2 VIV centers and one VV center and must be formulated As2V2IVVW18, in agreement with titration, elemental analysis and magnetic measurements on this element.. All the POMs of this work proved efficient for the oxidation of L-cysteine. Comparison of the present results with those of mono-Vanadium substituted POMs indicates that accumulation of vanadium atoms in the POM framework is beneficial in the electrocatalytic process. In addition, the present work highlights the important influence of the POM structure in the electrocatalytic oxidation of L-cysteine. The remarkable outcome of this work is that the potential for the oxidation of L-cysteine in the presence of the selected POMs has been substantially driven in the negative direction compared to the case of glassy carbon alone, a feature which is associated with faster kinetics. The stability of the systems must also be pointed out.
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