Electrochemical correlation spectroscopy in nanofluidic cavities

Marcel A.G. Zevenbergen, Pradyumna S. Singh, Edgar D. Goluch, Bernhard L. Wolfrum, Serge G. Lemay

Research output: Contribution to journalArticlepeer-review

65 Scopus citations


We introduce both theoretically and experimentally a new electrochemical technique based on measuring the fluctuations of the faradaic current during redox cycling. By analogy with fluorescence correlation spectroscopy (FCS), we refer to this technique as electrochemical correlation spectroscopy (ECS). We first derive an analytical expression of the power spectral density for the fluctuations in a thin-layer-cell geometry. We then show agreement with measurements using ferrocenedimethanol, Fc(MeOH)2, in water and in acetonitrile in microfabricated thin-layer cells with a ∼70 nm electrode spacing. The fluctuation spectra provide detailed information about the adsorption dynamics of Fc(MeOH)2, which cause an apparent slowing of Brownian motion. We furthermore observe high-frequency fluctuations from which we estimate the rates of adsorption and desorption.

Original languageEnglish
Pages (from-to)8203-8212
Number of pages10
JournalAnalytical Chemistry
Issue number19
StatePublished - 1 Oct 2009
Externally publishedYes


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