Electrochemistry of sulfur and polysulfides in ionic liquids

Ninie S A Manan; Leigh Aldous; Yatimah Alias; Paul Murray; Lesley J. Yellowlees; M. Cristina Lagunas; Christopher Hardacre

doi:10.1021/jp208159v

Electrochemistry of sulfur and polysulfides in ionic liquids

Ninie S A Manan, Leigh Aldous, Yatimah Alias, Paul Murray, Lesley J. Yellowlees, M. Cristina Lagunas, Christopher Hardacre

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Abstract

The electrochemistry of elemental sulfur (S₈) and the polysulfides Na₂S₄ and Na₂S₆ has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S₈ in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S₈ in [C₄mim][DCA] ([C ₄mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S₆^2- and S₄^2-, and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S₆^2- and S₄^2- appears to be slow in the ionic liquid, with only small amounts of the blue radical species S₃^•- formed in the solutions at r.t., in contrast with that observed in most molecular solvents.

Original language	English
Pages (from-to)	13873-13879
Number of pages	7
Journal	Journal of Physical Chemistry B
Volume	115
Issue number	47
DOIs	https://doi.org/10.1021/jp208159v
Publication status	Published - 1 Dec 2011

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@article{7018777067d547b39d0f25f03593d5a9,

title = "Electrochemistry of sulfur and polysulfides in ionic liquids",

abstract = "The electrochemistry of elemental sulfur (S8) and the polysulfides Na2S4 and Na2S6 has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S8 in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S8 in [C4mim][DCA] ([C 4mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S62- and S42-, and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S62- and S42- appears to be slow in the ionic liquid, with only small amounts of the blue radical species S3•- formed in the solutions at r.t., in contrast with that observed in most molecular solvents.",

author = "Manan, {Ninie S A} and Leigh Aldous and Yatimah Alias and Paul Murray and Yellowlees, {Lesley J.} and Lagunas, {M. Cristina} and Christopher Hardacre",

year = "2011",

month = dec,

day = "1",

doi = "10.1021/jp208159v",

language = "English",

volume = "115",

pages = "13873--13879",

journal = "Journal of Physical Chemistry B",

issn = "1520-6106",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Electrochemistry of sulfur and polysulfides in ionic liquids

AU - Manan, Ninie S A

AU - Aldous, Leigh

AU - Alias, Yatimah

AU - Murray, Paul

AU - Yellowlees, Lesley J.

AU - Lagunas, M. Cristina

AU - Hardacre, Christopher

PY - 2011/12/1

Y1 - 2011/12/1

N2 - The electrochemistry of elemental sulfur (S8) and the polysulfides Na2S4 and Na2S6 has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S8 in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S8 in [C4mim][DCA] ([C 4mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S62- and S42-, and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S62- and S42- appears to be slow in the ionic liquid, with only small amounts of the blue radical species S3•- formed in the solutions at r.t., in contrast with that observed in most molecular solvents.

AB - The electrochemistry of elemental sulfur (S8) and the polysulfides Na2S4 and Na2S6 has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S8 in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S8 in [C4mim][DCA] ([C 4mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S62- and S42-, and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S62- and S42- appears to be slow in the ionic liquid, with only small amounts of the blue radical species S3•- formed in the solutions at r.t., in contrast with that observed in most molecular solvents.

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U2 - 10.1021/jp208159v

DO - 10.1021/jp208159v

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SN - 1520-6106

VL - 115

SP - 13873

EP - 13879

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 47

ER -

Electrochemistry of sulfur and polysulfides in ionic liquids

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