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Nanoscale visualization and multiscale electrochemical analysis of conductive polymer electrodes
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Daviddi, Enrico, Chen, Zhiting, Massani, Brooke Beam, Lee, Jaemin, Bentley, Cameron Luke, Unwin, Patrick R. and Ratcliff, Erin L. (2019) Nanoscale visualization and multiscale electrochemical analysis of conductive polymer electrodes. ACS Nano, 13 (11). pp. 13271-13284. doi:10.1021/acsnano.9b06302 ISSN 1936-0851.
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WRAP-nanoscale-visualization-multiscale-electrochemical-analysis-polymer-electrodes-Daviddi-2019.pdf - Accepted Version - Requires a PDF viewer. Download (2845Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/acsnano.9b06302
Abstract
Conductive polymers are exceptionally promising for modular electrochemical applications including chemical sensors, bioelectronics, redox-flow batteries, and photo-electrochemical systems due to considerable synthetic tunability and ease of processing. Despite well-established structural heterogeneity in these systems, conventional macroscopic electroanalytical methods – specifically cyclic voltammetry – are typically used as the primary tool for structure-property elucidation. This work presents an alternative correlative multi-microscopy strategy; data from laboratory and synchrotron-based micro-spectroscopies, including conducting-atomic force microscopy and synchrotron nanoscale infrared spectroscopy, is combined with potentiodynamic movies of electrochemical fluxes from scanning electrochemical cell microscopy (SECCM) to reveal the relationship between electrode structure and activity. A model conductive polymer electrode system of tailored heterogeneity is investigated, consisting of phase-segregated domains of poly(3-hexylthiophene) (P3HT) surrounded by contiguous regions of insulating poly(methyl methacrylate) (PMMA), representing an ultramicroelectrode array. Isolated domains of P3HT are shown to retain bulk-like chemical and electronic structure when blended with PMMA, and possess approximately equivalent electron-transfer rate constants compared to pure P3HT electrodes. The nanoscale electrochemical data are used to model and predict multiscale electrochemical behavior, revealing that macroscopic cyclic voltammograms should be much more kinetically facile than observed experimentally. This indicates that parasitic resistances rather than redox kinetics play a dominant role in macroscopic measurements in these conducting polymer systems. SECCM further demonstrates that the ambient degradation of the P3HT electroactivity within P3HT/PMMA blends is spatially heterogeneous. This work serves as a roadmap for benchmarking the quality of conductive polymer films as electrodes, emphasizing the importance of nanoscale electrochemical measurements in understanding macroscopic properties.
| Item Type: | Journal Article | |||||||||||||||||||||
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| Subjects: | Q Science > QD Chemistry Q Science > QH Natural history T Technology > TP Chemical technology |
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||||||||
| Library of Congress Subject Headings (LCSH): | Electrochemistry , Scanning electrochemical microscopy, Oxidation-reduction reaction, Poly(3-hexylthiophene), Polymers -- Deterioration | |||||||||||||||||||||
| Journal or Publication Title: | ACS Nano | |||||||||||||||||||||
| Publisher: | American Chemical Society | |||||||||||||||||||||
| ISSN: | 1936-0851 | |||||||||||||||||||||
| Official Date: | 26 November 2019 | |||||||||||||||||||||
| Dates: |
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| Volume: | 13 | |||||||||||||||||||||
| Number: | 11 | |||||||||||||||||||||
| Page Range: | pp. 13271-13284 | |||||||||||||||||||||
| DOI: | 10.1021/acsnano.9b06302 | |||||||||||||||||||||
| 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 ACS Nano, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to 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: | 6 November 2019 | |||||||||||||||||||||
| Date of first compliant Open Access: | 1 November 2020 | |||||||||||||||||||||
| RIOXX Funder/Project Grant: |
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