Variable temperature study of electro-reduction of 3-nitrophenolate via cyclic and square wave voltammetry: Molecular insights into electron transfer processes based on the asymmetric Marcus-Hush model

Research output: Contribution to journalArticlepeer-review

Authors

  • Eduardo Laborda
  • Danu Suwatchara
  • Martin C. Henstridge
  • Angela Molina
  • Richard G. Compton

Colleges, School and Institutes

External organisations

  • Universidad de Murcia
  • Department of Chemistry, Physical and Theoretical Chemistry Laboratory
  • University of Oxford
  • Departamento de Quimica Fisica
  • Facultad de Química
  • Campus Mare Nostrum

Abstract

In this study, variable temperature experiments have been used in conjunction with numerical fitting of cyclic and square wave voltammogram responses via the asymmetric version of Marcus theory to provide molecular insight into the electroreduction of the 3-nitrophenolate anion in DMSO on mercury hemispherical microelectrodes of 23 μm radius. As a result, the reorganization energy, differences between the inner-sphere force constants of the electroactive species, and the degree of adiabaticity have been evaluated. Furthermore, a comparison between the quality of fitting obtained through the Butler-Volmer and asymmetric Marcus-Hush models is also presented to examine the relative ability of the kinetic models in predicting voltammetric responses in a range of temperatures and scan rates.

Details

Original languageEnglish
Pages (from-to)772-779
Number of pages8
JournalElectrochimica Acta
Volume110
Early online date5 Jan 2013
Publication statusPublished - 1 Nov 2013
EventAnnual Meeting of the International Society of Electrochemistry, 63rd - Prague, Czech Republic
Duration: 19 Aug 201224 Aug 2012

Keywords

  • Adiabaticity, Asymmetric Marcus-Hush model, Reorganization energy, Variable temperature experiments