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Title: Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength

Abstract

Ion permselectivity can lead to accumulation in zero-dimensional nanopores, producing a significant increase in ion concentration, an effect which may be combined with unscreened ion migration to improve sensitivity in electrochemical measurements, as demonstrated by the enormous current amplification (~2000-fold) previously observed in nanopore electrode arrays (NEA) in the absence of supporting electrolyte. Ionic strength is a key experimental factor that governs the magnitude of the additional current amplification (AFad) beyond simple redox cycling through both ion accumulation and ion migration effects. Here, separate contributions from ion accumulation and ion migration to the overall AFad were identified by studying NEAs with varying geometries, with larger AFad values being achieved in NEAs with smaller pores. In addition, larger AFad values were observed for Ru(NH3)63/2+ than for ferrocenium/ferrocene (Fc+/Fc) in aqueous solution, indicating that coupling efficiency in redox cycling can significantly affect AFad. While charged species are required to observe migration effects or ion accumulation, poising the top electrode at an oxidizing potential converts neutral species to cations, which can then exhibit current amplification similar to starting with the cation. The electrical double layer effect was also demonstrated for Fc/Fc+ in acetonitrile and 1,2-dichloroethane, producing AFad up to 100× at low ionicmore » strength. The pronounced AFad effects demonstrate the advantage of coupling redox cycling with ion accumulation and migration effects for ultrasensitive electrochemical measurements.« less

Authors:
 [1];  [1];  [1];  [1]
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  1. Univ. of Notre Dame, IN (United States)
Publication Date:
Research Org.:
University of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1808196
Grant/Contract Number:  
FG02-07ER15851
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; redox cycling; nanopore electrode array; ion accumulation; ion migration; current amplification; electrical double layer effect; redox reactions; genetics; electrodes; ions; nanopores

Citation Formats

Ma, Chaoxiong, Xu, Wei, Wichert, William R. A., and Bohn, Paul W. Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength. United States: N. p., 2016. Web. doi:10.1021/acsnano.6b00049.
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Ma, Chaoxiong, Xu, Wei, Wichert, William R. A., & Bohn, Paul W. Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength. United States. https://doi.org/10.1021/acsnano.6b00049
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Ma, Chaoxiong, Xu, Wei, Wichert, William R. A., and Bohn, Paul W. Wed . "Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength". United States. https://doi.org/10.1021/acsnano.6b00049. https://www.osti.gov/servlets/purl/1808196.
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@article{osti_1808196,
title = {Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength},
author = {Ma, Chaoxiong and Xu, Wei and Wichert, William R. A. and Bohn, Paul W.},
abstractNote = {Ion permselectivity can lead to accumulation in zero-dimensional nanopores, producing a significant increase in ion concentration, an effect which may be combined with unscreened ion migration to improve sensitivity in electrochemical measurements, as demonstrated by the enormous current amplification (~2000-fold) previously observed in nanopore electrode arrays (NEA) in the absence of supporting electrolyte. Ionic strength is a key experimental factor that governs the magnitude of the additional current amplification (AFad) beyond simple redox cycling through both ion accumulation and ion migration effects. Here, separate contributions from ion accumulation and ion migration to the overall AFad were identified by studying NEAs with varying geometries, with larger AFad values being achieved in NEAs with smaller pores. In addition, larger AFad values were observed for Ru(NH3)63/2+ than for ferrocenium/ferrocene (Fc+/Fc) in aqueous solution, indicating that coupling efficiency in redox cycling can significantly affect AFad. While charged species are required to observe migration effects or ion accumulation, poising the top electrode at an oxidizing potential converts neutral species to cations, which can then exhibit current amplification similar to starting with the cation. The electrical double layer effect was also demonstrated for Fc/Fc+ in acetonitrile and 1,2-dichloroethane, producing AFad up to 100× at low ionic strength. The pronounced AFad effects demonstrate the advantage of coupling redox cycling with ion accumulation and migration effects for ultrasensitive electrochemical measurements.},
doi = {10.1021/acsnano.6b00049},
journal = {ACS Nano},
number = 3,
volume = 10,
place = {United States},
year = {Wed Feb 24 00:00:00 EST 2016},
month = {Wed Feb 24 00:00:00 EST 2016}
}
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https://doi.org/10.1021/acsnano.6b00049
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