Electrochemical capture and release of carbon dioxide using a disulfide-thiocarbonate redox cycle

Poonam Singh, Joseph H. Rheinhardt, Jarred Z. Olson, Pilarisetty Tarakeshwar, Vladimiro Mujica, Daniel A. Buttry

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We describe a new electrochemical cycle that enables capture and release of carbon dioxide. The capture agent is benzylthiolate (RS"), generated electrochemically by reduction of benzyldisulfide (RSSR). Reaction of RS- with CO2 produces a terminal, sulfurbound monothiocarbonate, RSCO2 -, which acts as the CO2 carrier species, much the same as a carbamate serves as the CO2 carrier for amine-based capture strategies. Oxidation of the thiocarbonate releases CO2 and regenerates RSSR The newly reported S-benzylthiocarbonate (IUPAC name benzylsulfanylformate) is characterized by 1H and 13C NMR, FTIR, and electrochemical analysis. The capture-release cycle is studied in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP TFSI) and dimethylformamide. Quantum chemical calculations give a binding energy of CO2 to benzyl thiolate of -66.3 kJ mol-1, consistent with the experimental observation of formation of a stable CO2 adduct. The data described here represent the first report of electrochemical behavior of a sulfur-bound terminal thiocarbonate.

Original languageEnglish
Pages (from-to)1033-1036
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number3
DOIs
Publication statusPublished - Jan 25 2017

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Ionic Liquids
Dimethylformamide
Carbamates
Fourier Transform Infrared Spectroscopy
Binding energy
Ionic liquids
Sulfur
Carbon Dioxide
Disulfides
Oxidation-Reduction
Names
Amines
Carbon dioxide
Nuclear magnetic resonance
Observation
Oxidation
Proton Magnetic Resonance Spectroscopy
Carbon-13 Magnetic Resonance Spectroscopy
1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Electrochemical capture and release of carbon dioxide using a disulfide-thiocarbonate redox cycle. / Singh, Poonam; Rheinhardt, Joseph H.; Olson, Jarred Z.; Tarakeshwar, Pilarisetty; Mujica, Vladimiro; Buttry, Daniel A.

In: Journal of the American Chemical Society, Vol. 139, No. 3, 25.01.2017, p. 1033-1036.

Research output: Contribution to journalArticle

Singh, Poonam ; Rheinhardt, Joseph H. ; Olson, Jarred Z. ; Tarakeshwar, Pilarisetty ; Mujica, Vladimiro ; Buttry, Daniel A. / Electrochemical capture and release of carbon dioxide using a disulfide-thiocarbonate redox cycle. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 3. pp. 1033-1036.
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