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dc.contributor.authorAlwis, Kethsiri H.K.L.
dc.contributor.authorMucalo, Michael R.
dc.contributor.authorIngham, Bridget
dc.contributor.authorKappen, Peter
dc.date.accessioned2015-05-04T04:24:52Z
dc.date.available2015
dc.date.available2015-05-04T04:24:52Z
dc.date.issued2015
dc.identifier.citationAlwis, K. H. K. L., Mucalo, M. R., Ingham, B., & Kappen, P. (2015). A combined SNIFTIRS and XANES study of electrically polarised copper electrodes in DMSO and DMF solutions of cyanate (NCO⁻), thiocyanate (NCS⁻) and selenocyanate (NCSe⁻) ions. Journal of the Electrochemical Society, 162(7), H434–H448. http://doi.org/10.1149/2.0321507jesen
dc.identifier.issn0013-4651
dc.identifier.urihttps://hdl.handle.net/10289/9312
dc.description.abstractA SNIFTIRS (subtractively normalized interfacial Fourier transform infrared spectroscopy) and X-ray absorption spectroscopy (XAS) study of electrically polarized copper electrodes in six polar aprotic solvent-based systems is presented. In the systems investigated, i.e. dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) solutions containing pseudohalide species of cyanate (NCO⁻), thiocyanate (NCS⁻) and selenocyanate (NCSe⁻) codissolved with tetrabutylammonium perchlorate (TBAP), Cu was found to dissolve over a wide range of potentials to produce the corresponding Cu(I) pseudohalide and/or Cu(II) pseudohalide complex ion species. Insoluble deposited films were also observed at higher anodic applied potentials, thought to be CuSCN in the Cu/NCS⁻/DMSO or DMF systems, and solid K(SeCN)₃ in the Cu/NCSe⁻/DMSO or DMF systems respectively. The presence of the Cu(II) and/or Cu(I) oxidation states in complexes formed by polarization in Cu/pseudohalide ion systems in DMSO was clearly proven using XAS of cell solutions sampled after SNIFTIRS/electrical polarization experiments. In addition, Fourier transform infrared (FTIR) and X-ray absorption near edge spectroscopy (XANES) data obtained from model solutions prepared from mixing Cu(I) and/or Cu(II) salts with the respective pseudohalide ions in DMF and DMSO confirmed the speciation observed in the electrochemical experiments.
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.publisherElectrochemical Society
dc.rights© The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0321507jes] All rights reserved.
dc.titleA combined SNIFTIRS and XANES study of electrically polarised copper electrodes in DMSO and DMF solutions of cyanate (NCO⁻), thiocyanate (NCS⁻) and selenocyanate (NCSe⁻) ions
dc.typeJournal Article
dc.identifier.doi10.1149/2.0321507jes
dc.relation.isPartOfJournal of the Electrochemical Society
pubs.begin-pageH434
pubs.declined2015-05-04T16:15:19.155+1200
pubs.deleted2015-05-04T16:15:19.155+1200
pubs.elements-id119544
pubs.end-pageH448
pubs.issue7
pubs.publisher-urlhttp://jes.ecsdl.org/content/current
pubs.volume162


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