Fast Electron-Transfer Kinetics Probed in Nanofluidic Channels

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

doi:10.1021/ja902331u

Cited by 125 publications

(180 citation statements)

References 38 publications

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“…Transient space charge has also been analyzed in this way for large applied voltages, for both blocking electrodes [38,77] and FBV reactions [49]. A validation of the PNP-FBV theory was recently achieved by Soestbergen [78], who fitted the model to experimental data of Lemay and coworkers for planar nanocavities [79,80]. The FBV model has also been applied to nonlinear "induced-charge" electrokinetic phenomena [81], in the asymptotic limit of thin double layers.…”

Section: Historical Reviewmentioning

confidence: 99%

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Yan

Bazant

Biesheuvel³

et al. 2017

Phys. Rev. E

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Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. In this paper, we provide a comprehensive mathematical theory of voltammetry in electrochemical cells with unsupported electrolytes and for other situations where diffuse charge effects play a role, and present analytical and simulated solutions of the time-dependent PoissonNernst-Planck equations with generalized Frumkin-Butler-Volmer boundary conditions for a 1:1 electrolyte and a simple reaction. Using these solutions, we construct theoretical and simulated current-voltage curves for liquid and solid thin films, membranes with fixed background charge, and cells with blocking electrodes. The full range of dimensionless parameters is considered, including the dimensionless Debye screening length (scaled to the electrode separation), Damkohler number (ratio of characteristic diffusion and reaction times), and dimensionless sweep rate (scaled to the thermal voltage per diffusion time). The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, although capacitive charging of the electrical double layers is also studied, for early time transients at reactive electrodes and for nonreactive blocking electrodes. Our work highlights cases where diffuse charge effects are important in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.

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Section: Historical Reviewmentioning

confidence: 99%

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Yan

Bazant

Biesheuvel³

et al. 2017

Phys. Rev. E

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“…The basis of this OPEN ACCESS method is nanogap sensors [5], in which electrochemical active molecules undergo redox cycling between two closely spaced electrodes embedded in opposite walls of a nanochannel. The molecules travel back and forth by diffusion and are repeatedly oxidized and reduced at the electrodes, thereby shuttling electrons across the channel and generating an electrical current.…”

Section: Introductionmentioning

confidence: 99%

Pushing the Limits of Electrical Detection of Ultralow Flows in Nanofluidic Channels

Mathwig

Lemay

2013

Micromachines

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This paper presents improvements in flow detection by electrical cross-correlation spectroscopy. This new technique detects molecular number fluctuations of electrochemically active analyte molecules as they are transported by liquid flow through a nanochannel. The fluctuations are used as a marker of liquid flow as their time of flight in between two consecutive transducers is determined, thereby allowing for the measurement of liquid flow rates in the picoliter-per-minute regime. Here we show an enhanced record-low sensitivity below 1 pL/min by capitalizing on improved electrical instrumentation, an optimized sensor geometry and a smaller channel cross section. We further discuss the impact of sensor geometry on the cross-correlation functions.

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“…Their characteristics, such as fast mass-transport of reactants toward the electrode surface, sensitivity to extremely small currents and nanoscale dimensions have allowed the characterization of fast electron transfer reactions [1], single molecule detection [2] and individual enzyme immobilization [3]. In the field of electrocatalysis, ultrasmall amounts of platinum metal have been electrodeposited and studied as nanoelectrodes [4,5].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical characterization of nano-sized gold electrodes fabricated by nano-lithography

Kleijn

Yanson

Koper

2012

Journal of Electroanalytical Chemistry

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Fast Electron-Transfer Kinetics Probed in Nanofluidic Channels

Cited by 125 publications

References 38 publications

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Pushing the Limits of Electrical Detection of Ultralow Flows in Nanofluidic Channels

Electrochemical characterization of nano-sized gold electrodes fabricated by nano-lithography

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