TY - JOUR
T1 - Electrochemical capture and release of carbon dioxide using a disulfide-thiocarbonate redox cycle
AU - Singh, Poonam
AU - Rheinhardt, Joseph H.
AU - Olson, Jarred Z.
AU - Pilarisetty, Tarakeshwar
AU - Mujica, Vladimiro
AU - Buttry, Daniel
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/1/25
Y1 - 2017/1/25
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.6b10806
DO - 10.1021/jacs.6b10806
M3 - Article
C2 - 28052189
AN - SCOPUS:85018520941
SN - 0002-7863
VL - 139
SP - 1033
EP - 1036
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -