Erratum: In Situ IR Study of the Anodic Polarization of Gold Electrodes in Polar Aprotic Solvents: DMSO and DMF Solutions of Cyanate, Thiocyanate and Selenocyanate Ions [J. Electrochem. Soc., 161, H738 (2014)]

Abstract

On page H739, right column, the caption for Figure 1 should be On page H745, Table II On page H747, right column, the caption for Figure 9 should be Electroanal. Chem., 92, 45 (1978).) unless CC License in place (see abstract

A fundamental in situ IR spectroelectrochemical study of the electrical polarization of nickel, copper and gold electrodes in the presence of the unstable tellurocyanate ion in DMSO and DMF solutions

“…In the Au/DMF/TeCN À SNIFTIRS spectrum, even though there is no characteristic peak due to [Au(CN) 2 ] À , but weak peaks due to solid KOCN (2156 cm À1 ) and CO 2 (2337 cm À1 ), 5,6 it is still obvious from the intensity-potential plots that TeCN À decomposes in this system. It is thus posited that Au is still dissolving in some form in this system to form Au + (which in turn is causing the decomposition of the TeCN À ion), even though the presence of Au + is not able to be veried in the SNIFTIRS spectra.…”

“…When present as an adatom on the surface, the Te was found not to catalyse CO oxidation because the adatom always existed in its reduced form on the electrode and hence could not transfer oxygen to effect the oxidation. [5][6][7] The successful preparation of the TeCN À ion, an inherently unstable ion, was reported in 1968 by Downs,8 who prepared it from the reaction of tetraethylammonium cyanide and elemental Te in DMF and isolated pale yellow crystals that were highly moisture and oxygen sensitive. 2,3 In other studies, technologically valuable lms, such as cadmium telluride thin lms, have been prepared by electrodeposition of Te on a Au electrode followed by reduction with metal ions present.…”

“…related pseudohalide ions of cyanate (NCO À ), thiocyanate (NCS À ) and selenocyanate (NCSe À ), have been subjected to previous IR spectroelectrochemical investigations in aqueous and polar aprotic solvents. [5][6][7] The successful preparation of the TeCN À ion, an inherently unstable ion, was reported in 1968 by Downs,8 who prepared it from the reaction of tetraethylammonium cyanide and elemental Te in DMF and isolated pale yellow crystals that were highly moisture and oxygen sensitive. A Raman spectrum of a solution of the ion showed a peak at 2080 cm À1 .…”

“…5,6 These studies indicated that complex ion species arose from the interaction of electrogenerated Ni(II) and Au(I) ions with the NCO À , NCS À and NCSe À ions in the electrolyte. For instance, Cauquis et al 14 reported a voltammetric study in 1975, in which the electrochemical oxidation of TeCN À in acetonitrile at a platinum microelectrode was discussed and compared with the electrochemistry of other structurally related pseudohalide ions, i.e.…”

“…Recently, we have applied in situ IR methods, such as subtractively normalised interfacial Fourier transform infrared spectroscopy (SNIFTIRS), to the study of Ni and Au electrodes anodically polarized in the presence of DMSO and DMF electrolytes containing the structurally related pseudohalide ions of NCO À , NCS À and NCSe À . 5,6 These studies indicated that complex ion species arose from the interaction of electrogenerated Ni(II) and Au(I) ions with the NCO À , NCS À and NCSe À ions in the electrolyte. As the TeCN À ion is fortuitously stable when prepared in dry DMSO and DMF solvents, it was decided to extend the previously reported work 8,9,11 and study by SNIF-TIRS Ni, Cu and Au electrodes electrically polarized in the presence of the TeCN À ion to (1) provide information in an area where there is a complete dearth of previous scientic investigation and also (2) to compare the electrochemistry of the TeCN À ion with that of its structurally related, more stable, analogue ions.…”