Fluctuation enhanced electrochemical reaction rates at the nanoscale.
نویسندگان
چکیده
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.
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عنوان ژورنال:
- Proceedings of the National Academy of Sciences of the United States of America
دوره 107 10 شماره
صفحات -
تاریخ انتشار 2010