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dc.contributor.authorAlwis, Kethsiri H.K.L.
dc.contributor.authorIngham, Bridget
dc.contributor.authorMucalo, Michael R.
dc.contributor.authorKappen, Peter
dc.contributor.authorGlover, Chris
dc.date.accessioned2015-04-21T00:16:48Z
dc.date.available2015
dc.date.available2015-04-21T00:16:48Z
dc.date.issued2015
dc.identifier.citationAlwis, K. H. K. L., Ingham, B., Mucalo, M. R., Kappen, P., & Glover, C. (2015). An X-ray absorption spectroscopy investigation of the coordination environment of electrogenerated Ni(ii)-pseudohalide complexes arising from the anodic polarization of Ni electrodes in DMSO solutions of NCO⁻ , NCS⁻ and NCSe⁻ ions. RSC Advances, 5(20), 15709–15718. http://doi.org/10.1039/C4RA14940Hen
dc.identifier.urihttps://hdl.handle.net/10289/9279
dc.description.abstractX-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) were used to provide direct information in solution on the coordination state of electrogenerated products from anodically polarized nickel electrodes in pseudohalide-ion-containing dimethyl sulfoxide (DMSO) solvent (i.e. NCX⁻, X = O, S, Se) in the presence of a supporting electrolyte of tetrabutylammonium perchlorate (TBAP). Electrogenerated solutions and model solutions representative of the chemical speciation in electrolyzed systems (prepared by mixing Ni(II) and pseudohalide ion solutions in DMSO), were also examined. In general for Ni(II) interacting with NCS⁻ and NCSe⁻, the complex ion generated appears to be 6-coordinate [Ni(NCX)(DMSO)5]⁺, while EXAFS/XANES data of the Ni/cyanate system suggest an average coordination number of 5, which in reality is due to the electrogenerated solution containing a mixture of 4 coordinate (tetrahedral) [Ni(NCO)4]²⁻ and octahedral [Ni(DMSO)6]²⁺ species. These observations of the octahedral geometry for the Ni(II)/thiocyanate and Ni(II)/selenocyanate systems and 5-coordinate geometry in the Ni(II)/cyanate systems (being electrogenerated products of anodic polarisation of Ni in the DMSO-supported pseudohalide ion electrolytes) agree with the differences in colour observed between samples. EXAFS/XANES measurements combined with IR spectroelectrochemical analyses of solutions provide a versatile way of analyzing these electrochemical systems without the need for isolating compounds from the electrolyte.
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.relation.urihttp://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C4RA14940H#!divAbstract
dc.rightsThis is an author’s accepted version of an article published in the journal: RCS Advances. © 2015 The Royal Society of Chemistry.
dc.subjectEXAFS/XANES
dc.subjectIR spectroelectrochemistry
dc.subjectNickel
dc.subjectanodic polarization
dc.subjectcyanate
dc.subjectthiocyanate
dc.subjectselenocyanate
dc.subjectnicke1(II)-pseudohalide complexes
dc.titleAn X-ray absorption spectroscopy investigation of the coordination environment of electrogenerated Ni(ii)-pseudohalide complexes arising from the anodic polarization of Ni electrodes in DMSO solutions of NCO⁻ , NCS⁻ and NCSe⁻ ions
dc.typeJournal Article
dc.identifier.doi10.1039/C4RA14940H
dc.relation.isPartOfRSC Advances
pubs.begin-page15709
pubs.elements-id119327
pubs.end-page15718
pubs.issue20
pubs.notesEvidence of peer review: http://www.rsc.org/publishing/journals/ra/About.asp
pubs.organisational-group/Waikato
pubs.organisational-group/Waikato/FSEN
pubs.organisational-group/Waikato/FSEN/School of Science
pubs.volume5
dc.identifier.eissn2046-2069


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