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Stability and placement of Ag/AgCl quasi-reference counter electrodes in confined electrochemical cells
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Bentley, Cameron Luke, Perry, David and Unwin, Patrick R. (2018) Stability and placement of Ag/AgCl quasi-reference counter electrodes in confined electrochemical cells. Analytical Chemistry, 90 (12). pp. 7700-7707. doi:10.1021/acs.analchem.8b01588 ISSN 1520-6882.
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WRAP-Stability-quasi-counter-electrodes-electrochemical-cells-Bentley-2018.pdf - Accepted Version - Requires a PDF viewer. Download (1587Kb) | Preview |
Official URL: https://doi.org/10.1021/acs.analchem.8b01588
Abstract
Nanoelectrochemistry is an important and growing branch of electrochemistry that encompasses a number of key research areas, including (electro)catalysis, energy storage, biomedical/environmental sensing, and electrochemical imaging. Nanoscale electrochemical measurements are often performed in confined environments over prolonged experimental time scales with nonisolated quasi-reference counter electrodes (QRCEs) in a simplified two-electrode format. Herein, we consider the stability of commonly used Ag/AgCl QRCEs, comprising an AgCl-coated wire, in a nanopipet configuration, which simulates the confined electrochemical cell arrangement commonly encountered in nanoelectrochemical systems. Ag/AgCl QRCEs possess a very stable reference potential even when used immediately after preparation and, when deployed in Cl– free electrolyte media (e.g., 0.1 M HClO4) in the scanning ion conductance microscopy (SICM) format, drift by only ca. 1 mV h–1 on the several hours time scale. Furthermore, contrary to some previous reports, when employed in a scanning electrochemical cell microscopy (SECCM) format (meniscus contact with a working electrode surface), Ag/AgCl QRCEs do not cause fouling of the surface (i.e., with soluble redox byproducts, such as Ag+) on at least the 6 h time scale, as long as suitable precautions with respect to electrode handling and placement within the nanopipet are observed. These experimental observations are validated through finite element method (FEM) simulations, which consider Ag+ transport within a nanopipet probe in the SECCM and SICM configurations. These results confirm that Ag/AgCl is a stable and robust QRCE in confined electrochemical environments, such as in nanopipets used in SICM, for nanopore measurements, for printing and patterning, and in SECCM, justifying the widespread use of this electrode in the field of nanoelectrochemistry and beyond.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
SWORD Depositor: | Library Publications Router | ||||||||||||
Library of Congress Subject Headings (LCSH): | Nanochemistry, Electrochemistry -- Measurement, Silver | ||||||||||||
Journal or Publication Title: | Analytical Chemistry | ||||||||||||
Publisher: | American Chemical Society (ACS) | ||||||||||||
ISSN: | 1520-6882 | ||||||||||||
Official Date: | 19 June 2018 | ||||||||||||
Dates: |
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Volume: | 90 | ||||||||||||
Number: | 12 | ||||||||||||
Page Range: | pp. 7700-7707 | ||||||||||||
DOI: | 10.1021/acs.analchem.8b01588 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Reuse Statement (publisher, data, author rights): | “This document is the Accepted Manuscript version of a Published Work that appeared in final form in Analytical Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/page/policy/articlesonrequest/index.html.” | ||||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||||
Date of first compliant deposit: | 5 October 2018 | ||||||||||||
Date of first compliant Open Access: | 29 May 2019 | ||||||||||||
RIOXX Funder/Project Grant: |
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