Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Electrochemical Mechanism of Ferrocene-Based Redox Molecules in Thin Film Membrane Electrodes
Show others and affiliations
2017 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 238, 357-367 p.Article in journal (Refereed) Published
Abstract [en]

Cyclic voltammetry (CV) in chloride-based aqueous electrolytes of ferrocene molecule doped thin membranes (similar to 200 nm in thickness) on glassy carbon (GC) substrate electrodes, both plasticized poly (vinyl chloride) (PVC) and unplasticized poly(methyl methacrylate)/poly(decyl methacrylate) (PMMA-PDMA) membranes, has shown that the electrochemical oxidation behavior is irreversible due most likely to degradation of ferrocene at the buried interface (GC vertical bar membrane). Furthermore, CV of the ferrocene molecules at GC electrodes in organic solvents employing chloride-based and chloride-free organic electrolytes has demonstrated that the chloride anion is inextricably linked to this irreversible ferrocene oxidation electrochemistry. Accordingly, we have explored the electrochemical oxidation mechanism of ferrocene-based redox molecules in thin film plasticized and unplasticized polymeric membrane electrodes by coupling synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) and near edge X-ray absorption fine structure (NEXAFS) with argon ion sputtering to depth profile the electrochemically oxidized thin membrane systems. With the PVC depth profiling studies, it was not possible to precisely study the influence of chloride on the ferrocene reactivity due to the high atomic ratio of chloride in the PVC membrane; however, the depth profiling results obtained with a chlorine-free polymer (PMMA-PDMA) provided irrefutable evidence for the formation of a chloride-based iron product at the GC| PMMA-PDMA interface. Finally, we have identified conditions that prevent the irreversible conversion of ferrocene by utilizing a high loading of redox active reagent and/or an ionic liquid (IL) membrane plasticizer with high ionicity that suppresses the mass transfer of chloride.

Place, publisher, year, edition, pages
Elsevier, 2017. Vol. 238, 357-367 p.
Keyword [en]
thin film, polymer membrane, ferrocene electrochemistry, synchrotron radiation X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-208789DOI: 10.1016/j.electacta.2017.04.047ISI: 000401113500040Scopus ID: 2-s2.0-85017547167OAI: oai:DiVA.org:kth-208789DiVA: diva2:1108837
Funder
EU, FP7, Seventh Framework Programme, 312284EU, European Research Council, 614002-SCHeMA
Note

QC 20170613

Available from: 2017-06-13 Created: 2017-06-13 Last updated: 2017-06-13Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Crespo, Gaston A.
In the same journal
Electrochimica Acta
Materials Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 37 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf