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表面等离子体共振伏安法中的电荷转移动力学。

Charge transfer kinetics from surface plasmon resonance voltammetry.

作者信息

Lu Jin, Li Jinghong

机构信息

Department of Chemistry, Beijing Key Laboratory for Microanalytical Methods and Instrumentation, Tsinghua University , Beijing 100084, China.

出版信息

Anal Chem. 2014 Apr 15;86(8):3882-6. doi: 10.1021/ac404101w. Epub 2014 Apr 1.

Abstract

On the basis of a quantitative relationship between surface plasmon resonance signal and electrochemical current in the electrochemical surface plasmon resonance (EC-SPR), EC-SPR signal measures the semi-integral of faradaic current. We theoretically discussed the electrode potential and charge transfer kinetics to be determined from surface plasmon resonance voltammetry (or potential sweep EC-SPR) signals for the fully reversible, quasi-reversible, and irreversible redox reactions. The results indicated that the electroanalysis of EC-SPR signal is more straightforward than conventional electrochemical current. Then, we studied two model redox reactions of hexaammineruthenium chloride and 4-nitrotoluene, to obtain half wave potential of quasi-reversible redox reaction, transfer coefficient, and standard rate constant of irreversible redox reaction from EC-SPR signals.

摘要

基于电化学表面等离子体共振(EC-SPR)中表面等离子体共振信号与电化学电流之间的定量关系,EC-SPR信号测量法拉第电流的半积分。我们从理论上讨论了通过表面等离子体共振伏安法(或电位扫描EC-SPR)信号确定完全可逆、准可逆和不可逆氧化还原反应的电极电位和电荷转移动力学。结果表明,EC-SPR信号的电分析比传统电化学电流更直接。然后,我们研究了氯化六氨合钌和4-硝基甲苯的两个模型氧化还原反应,以从EC-SPR信号中获得准可逆氧化还原反应的半波电位、转移系数和不可逆氧化还原反应的标准速率常数。

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