Wain Andrew J, Wildgoose Gregory G, Heald Charles G R, Jiang Li, Jones Timothy G J, Compton Richard G
Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ United Kingdom.
J Phys Chem B. 2005 Mar 10;109(9):3971-8. doi: 10.1021/jp040552u.
The influence of lithium ion pairing on the voltammetric reduction of anthraquinone in acetonitrile is reported. On gold electrodes, the single electron reduction generates a radical anion which forms a complex with lithium cations from the electrolyte. In situ ESR studies support this finding, and signal intensity measurements are used to estimate a value for the complexation equilibrium constant. Values calculated were of the of the order of 6000 mol(-1) dm3. Potential shift measurements and Digisim modeling are shown to be in support of a complexation mechanism in which a little of the complex precipitates on the electrode surface. The effect of lithium ion pairing is also demonstrated for the case in which 1-anthraquinonyl groups are covalently attached to multiwalled carbon nanotubes abrasively immobilized on a basal plane pyrolytic graphite electrode.
报道了锂离子配对对蒽醌在乙腈中伏安还原的影响。在金电极上,单电子还原产生一个自由基阴离子,它与电解质中的锂阳离子形成络合物。原位电子自旋共振(ESR)研究支持这一发现,并通过信号强度测量来估算络合平衡常数的值。计算得到的值约为6000 mol⁻¹ dm³。电位偏移测量和Digisim建模表明支持一种络合机制,即少量络合物沉淀在电极表面。对于1-蒽醌基共价连接到磨蚀固定在基面热解石墨电极上的多壁碳纳米管的情况,也证明了锂离子配对的影响。