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

Ma, Chaoxiong; Xu, Wei; Wichert, William R. A.; Bohn, Paul W.

doi:10.1021/acsnano.6b00049

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

Journal Article · Tue Feb 23 23:00:00 EST 2016 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.6b00049· OSTI ID:1808196

Ma, Chaoxiong ^[1]; Xu, Wei ^[2]; Wichert, William R. A. ^[2]; Bohn, Paul W. ^[2]

Univ. of Notre Dame, IN (United States); University of Notre Dame
Univ. of Notre Dame, IN (United States)

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 (AF_ad) beyond simple redox cycling through both ion accumulation and ion migration effects. Here, separate contributions from ion accumulation and ion migration to the overall AF_ad were identified by studying NEAs with varying geometries, with larger AF_ad values being achieved in NEAs with smaller pores. In addition, larger AF_ad values were observed for Ru(NH₃)₆^3/2+ than for ferrocenium/ferrocene (Fc⁺/Fc) in aqueous solution, indicating that coupling efficiency in redox cycling can significantly affect AF_ad. 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 AF_ad up to 100× at low ionic strength. The pronounced AF_ad effects demonstrate the advantage of coupling redox cycling with ion accumulation and migration effects for ultrasensitive electrochemical measurements.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-07ER15851

OSTI ID:: 1808196

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 3 Vol. 10; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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

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