dc.contributor.author | Shiddiky, Muhammad JA | |
dc.contributor.author | O'Mullane, Anthony P | |
dc.contributor.author | Zhang, Jie | |
dc.contributor.author | Burke, L Declan | |
dc.contributor.author | Bond, Alan M | |
dc.date.accessioned | 2018-02-26T04:03:34Z | |
dc.date.available | 2018-02-26T04:03:34Z | |
dc.date.issued | 2011 | |
dc.identifier.issn | 0743-7463 | |
dc.identifier.doi | 10.1021/la2017819 | |
dc.identifier.uri | http://hdl.handle.net/10072/172458 | |
dc.description.abstract | The 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.peerreviewed | Yes | |
dc.language | English | |
dc.language.iso | eng | |
dc.publisher | American Chemical Society | |
dc.relation.ispartofpagefrom | 10302 | |
dc.relation.ispartofpageto | 10311 | |
dc.relation.ispartofissue | 16 | |
dc.relation.ispartofjournal | Langmuir | |
dc.relation.ispartofvolume | 27 | |
dc.subject.fieldofresearch | Analytical chemistry not elsewhere classified | |
dc.subject.fieldofresearchcode | 340199 | |
dc.title | Large Amplitude Fourier Transformed AC Voltammetric Investigation of the Active State Electrochemistry of a Copper/Aqueous Base Interface and Implications for Electrocatalysis | |
dc.type | Journal article | |
dc.type.description | C1 - Articles | |
dc.type.code | C - Journal Articles | |
gro.hasfulltext | No Full Text | |
gro.griffith.author | Shiddiky, Muhammad J. | |