Alwis, 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/10.1149/2.0321507jes
Permanent Research Commons link: http://hdl.handle.net/10289/9312
A 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.
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