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dc.contributor.authorShiddiky, Muhammad JA
dc.contributor.authorO'Mullane, Anthony P
dc.contributor.authorZhang, Jie
dc.contributor.authorBurke, L Declan
dc.contributor.authorBond, Alan M
dc.date.accessioned2018-02-26T04:03:34Z
dc.date.available2018-02-26T04:03:34Z
dc.date.issued2011
dc.identifier.issn0743-7463
dc.identifier.doi10.1021/la2017819
dc.identifier.urihttp://hdl.handle.net/10072/172458
dc.description.abstractThe higher harmonic components available from large-amplitude Fourier-transformed alternating current (FT-ac) voltammetry enable the surface active state of a copper electrode in basic media to be probed in much more detail than possible with previously used dc methods. In particular, the absence of capacitance background current allows low-level Faradaic current contributions of fast electron-transfer processes to be detected; these are usually completely undetectable under conditions of dc cyclic voltammetry. Under high harmonic FT-ac voltammetric conditions, copper electrodes exhibit well-defined and reversible premonolayer oxidation responses at potentials within the double layer region in basic 1.0 M NaOH media. This process is attributed to oxidation of copper adatoms (Cu*) of low bulk metal lattice coordination numbers to surface-bonded, reactive hydrated oxide species. Of further interest is the observation that cathodic polarization in 1.0 M NaOH significantly enhances the current detected in each of the fundamental to sixth FT-ac harmonic components in the Cu*/Cu hydrous oxide electron-transfer process which enables the underlying electron transfer processes in the higher harmonics to be studied under conditions where the dc capacitance response is suppressed; the results support the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. The underlying quasi-reversible interfacial Cu*/Cu hydrous oxide process present under these conditions is shown to mediate the reduction of nitrate at a copper electrode, while the mediator for the hydrazine oxidation reaction appears to involve a different mediator or active state redox couple. Use of FT-ac voltammetry offers prospects for new insights into the nature of active sites and electrocatalysis at the electrode/solution interface of Group 11 metals in aqueous media.
dc.description.peerreviewedYes
dc.languageEnglish
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.relation.ispartofpagefrom10302
dc.relation.ispartofpageto10311
dc.relation.ispartofissue16
dc.relation.ispartofjournalLangmuir
dc.relation.ispartofvolume27
dc.subject.fieldofresearchAnalytical Chemistry not elsewhere classified
dc.subject.fieldofresearchcode030199
dc.titleLarge Amplitude Fourier Transformed AC Voltammetric Investigation of the Active State Electrochemistry of a Copper/Aqueous Base Interface and Implications for Electrocatalysis
dc.typeJournal article
dc.type.descriptionC1 - Articles
dc.type.codeC - Journal Articles
gro.hasfulltextNo Full Text
gro.griffith.authorShiddiky, Muhammad J.


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