The stabilisation and characterisation by infrared spectroscopy of the different bonding modes of copper(I) thiocyanate adsorbed on high surface area solids

Clark, James H.; Jones, Christopher A.

doi:10.1016/s0020-1693(00)85370-0

Cited by 7 publications

(5 citation statements)

References 11 publications

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“…Support for this model accrues from a previously reported 2111 cm-1 IR feature for CuSCN aggregate formation on alumina (28).…”

Section: Applications Of Photoelectrochemistry and Spectroelectrochem...mentioning

confidence: 70%

Light in an Electrochemical Tunnel

Lezna¹

1992

Anal. Chem.

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“…Support for this model accrues from a previously reported 2111 cm-1 IR feature for CuSCN aggregate formation on alumina (28).…”

Section: Applications Of Photoelectrochemistry and Spectroelectrochem...mentioning

confidence: 70%

Light in an Electrochemical Tunnel

Lezna¹

1992

Anal. Chem.

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“…This trend makes it possible for us to assign this band to the formation of aggregates (CuSCN)x xCuSCN -* (CuSCN)x (2a) («)a-CuSCN + >e'-> yCu°+ (CuSCN)x + ySCN* (2b) where x + y = n. Thus electroreduction and bond-breaking in a-CuSCN facilitate aggregation via reaction 2b. Support for this model accrues from a previously reported 2111 cm"1 IR feature for CuSCN aggregate formation on alumina (28).…”

Section: Applications Of Photoelectrochemistry and Spectroelectrochem...mentioning

confidence: 71%

Light in an electrochemical tunnel? Solving analytical problems in electrochemistry via spectroscopy

Rajeshwar¹,

Lezna²,

Tacconi³

1992

Anal. Chem.

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“…This assignment is supported by work reported by Kilmartin et al 8 who studied the formation mechanism of electrochemically deposited copper thiocyanate films on a copper anode, in which he assigned a Raman peak observed at 2175 cm −1 to an underlying CuSCN barrier film. Other workers reporting spectroscopic data for CuSCN 10,40,42 have also reported peaks at 2173 cm −1 . These studies have suggested what the nature of the solid CuSCN film on the Cu electrode in the present study could be.…”

Section: H442mentioning

confidence: 84%

“…Other workers reporting spectroscopic data for CuSCN 10,40,42 have also reported peaks at 2173 cm −1 . These studies have suggested what the nature of the solid CuSCN film on the Cu electrode in the present study could be.…”

Section: H438mentioning

confidence: 84%

“…These studies have suggested what the nature of the solid CuSCN film on the Cu electrode in the present study could be. Clark et al 42 reported the IR spectrum of solid CuSCN to have a strong ν(CN) stretching peak at 2165 cm −1 which was assigned to S-bonded CuSCN. However, he also attributed a weak shoulder at 2173 cm −1 in the same spectrum to a bridge-bound Cu(I) species with thiocyanate.…”

Section: H442mentioning

confidence: 99%

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A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO⁻), Thiocyanate (NCS⁻) and Selenocyanate (NCSe⁻) Ions

Alwis

Mucalo

Ingham

et al. 2015

J. Electrochem. Soc.

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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. A wide variety of organic solvents are used in technological processes, 1 for example, electrodepositing of copper from nonaqueous solutions.2 In battery applications, the use of organic solvents like acetonitrile, for instance, allows use of the battery at low ambient temperatures.3 However, extensive electrochemical characterization of metal electrode action (e.g. dissolution and electrodeposition) in non-aqueous (organic) media has been lacking. For instance, even though copper in DMF is widely used in industry, few electrochemical studies of copper dissolution/reduction in DMF have been reported. [4][5][6][7] The same may be said for electrodissolution studies in DMSO. Thiocyanate ion has often been used in copper electrochemistry, as it can mimic the behavior of halide ions like chloride, 8 which disrupt the passivation layer of oxide coatings formed on copper, and consequently increase the corrosion rate. The electrochemistry of metal electrode/pseudohalide systems has previously been studied by Bowmaker et al.9,10 and Kilmartin et al., 8,11 who looked at thiocyanate interaction with copper anodes and platinum electrodes. In addition, Bron and Holze have also reported in situ IR work for thiocyanate and cyanate interactions with gold and copper electrodes in aqueous electrolytes.12 In situ IR spectroelectrochemistry can provide detailed information on electrochemical processes. [13][14][15][16][17][18][19][20][21][22] It is also valuable for characterizing the molecular species generated, especially in conjunction with conventional electrochemical techniques such as cyclic voltammetry, which is unable to identify discrete molecula...

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The stabilisation and characterisation by infrared spectroscopy of the different bonding modes of copper(I) thiocyanate adsorbed on high surface area solids

Cited by 7 publications

References 11 publications

Light in an Electrochemical Tunnel

Light in an Electrochemical Tunnel

Light in an electrochemical tunnel? Solving analytical problems in electrochemistry via spectroscopy

A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO⁻), Thiocyanate (NCS⁻) and Selenocyanate (NCSe⁻) Ions

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The stabilisation and characterisation by infrared spectroscopy of the different bonding modes of copper(I) thiocyanate adsorbed on high surface area solids

Cited by 7 publications

References 11 publications

Light in an Electrochemical Tunnel

Light in an Electrochemical Tunnel

Light in an electrochemical tunnel? Solving analytical problems in electrochemistry via spectroscopy

A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO−), Thiocyanate (NCS−) and Selenocyanate (NCSe−) Ions

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A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO⁻), Thiocyanate (NCS⁻) and Selenocyanate (NCSe⁻) Ions