Fluctuation enhanced electrochemical reaction rates at the nanoscale

Vladimir Garcia-Morales; Katharina Krischer

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Fluctuation enhanced electrochemical reaction rates at the nanoscale

机译：波动提高了纳米级的电化学反应速率

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摘要

The electrode potential constitutes a dynamical variable whenever an electrode is resistively coupled to the electric circuit. We show that at the nanoscale, the discreteness and stochasticity of an electron transfer event causes fluctuations of the electrode potential that render all elementary electrochemical reactions to be faster on a nanoelectrode than predicted by the macroscopic (Butler-Volmer) electrochemical kinetics. This phenomenon is substantiated by means of a generalized (electro)chemical master equation.

机译：每当电极电阻耦合到电路时，电极电势就构成动态变量。我们表明，在纳米尺度上，电子转移事件的离散性和随机性会引起电极电位的波动，从而使所有基本的电化学反应在纳米电极上比由宏观（Butler-Volmer）电化学动力学预测的更快。这种现象通过广义的（电化学）化学主方程得以证实。

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来源
《Proceedings of the National Academy of Sciences of the United States of America》 |2010年第10期|p.4528-4532|共5页
作者
Vladimir Garcia-Morales; Katharina Krischer;
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作者单位

Physik-Department E19a, Technische Universitat Munchen, James-Franck-Strasse 1, D-85748 Garching, Germany;

Physik-Department E19a, Technische Universitat Munchen, James-Franck-Strasse 1, D-85748 Garching, Germany;

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收录信息美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
原文格式 PDF
正文语种 eng
中图分类
关键词
Butler-Volmer kinetics; chemical master equation; electrochemistry; electrode kinetics; nanoelectrodes;

机译：巴特勒-沃尔默动力学;化学主方程电化学电极动力学纳米电极;

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6. Fluctuation enhanced electrochemical reaction rates at the nanoscale [O] . Vladimir García-Morales, Katharina Krischer 2010

机译：波动提高了纳米级的电化学反应速率
7. Fluctuation enhanced electrochemical reaction rates at the nanoscale [O] . García-Morales, Vladimir, Krischer, Katharina 2010

机译：波动提高了纳米级的电化学反应速率
8. Probing Redox Reactions at the Nanoscale with Electrochemical Tip-Enhanced Raman Spectroscopy. [R] . Kurouski, D., Mattei, M., Van Duyne, R. P. 2015

机译：用电化学尖端增强拉曼光谱探测纳米尺度的氧化还原反应。

Fluctuation enhanced electrochemical reaction rates at the nanoscale

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