Competing Reactions of CO2 with Cations and Anions in Azolide Ionic Liquids

• Published in: ChemSusChem 2014-07, Vol.7 (7), p.1970-1975
• Main Authors: Gohndrone, Thomas R., Bum Lee, Tae, DeSilva, M. Aruni, Quiroz-Guzman, Mauricio, Schneider, William F., Brennecke, Joan F.
• Format: Article
• Language: English
• Subjects: Adsorption; Ammonium Compounds - chemistry; carbon capture; Carbon Dioxide - chemistry; Carbon Dioxide - isolation & purification; gas separations; ionic liquids; Ionic Liquids - chemistry; Ions; Liquids; Models, Molecular; Molecular Conformation; Organophosphorus Compounds - chemistry; phosphonium; Solvents; ylide
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201400009

We show that phosphonium azolide ionic liquids of interest for CO2 capture applications react with CO2 both through the normal anion channel and, at elevated temperatures, through a previously unrecognized cation channel. The reaction is caused by an interaction between the anion and cation that allows proton transfer, and involves a phosphonium ylide intermediate. The cation reaction can be mitigated by using ammonium rather than phosphonium cations. Thus, phosphonium and ammonium cations paired with aprotic heterocyclic anions (AHAs) react with CO2 through different mechanisms at elevated temperatures. This work shows that careful consideration of both physical properties and chemical reactivity of ILs based on AHA anions is needed when designing ionic liquids for CO2 separations. Two different paths: Phosphonium azolide ionic liquids of interest for CO2 capture applications react with CO2 both through the normal anion channel and, at elevated temperatures, through a previously unrecognized cation channel. The cation channel involves a phosphonium ylide intermediate that is formed due to cation/anion interactions. This channel is suppressed with less‐acidic ammonium cations.