Quantification of Ylide Formation in Phosphonium-Based Ionic Liquids Reacted with CO2.

Phosphonium-based ionic liquids (ILs) paired with aprotic heterocyclic anions (AHAs) are found to react with CO2 to form both a carbamate product and a carboxyl product. The carboxyl product is formed primarily at elevated temperatures through the formation of a phosphonium ylide intermediate. The formation of the carboxyl product leads to the formation of the neutral azole, which can lead to an irreversible process if the neutral azole is sufficiently volatile. To understand how the ILs would behave in a CO2 capture process operated at elevated temperatures, it was necessary to quantify the two reaction products. CO2 was reacted with seven different AHA ILs to determine the equilibrium amounts of carbamate and carboxyl, the equilibrium constants for both reactions, and the rate of CO2 absorption by each reaction path. The reactions were tracked and quantified in situ by using ATR-FTIR spectroscopy, while NMR spectroscopy was used after equilibrium was reached to determine the extent of each reaction at multiple temperatures and pressures. It was found that both the basicity and molecular size of the anion play key roles in the formation of the phosphonium ylide. In the extreme case of [P66614][4-Triaz] only half of the reacted product was the desired carbamate at 60 °C. Although there is a significant amount of the carboxyl product formed, the carbamate is kinetically favored.

CO2 Chemistry of Phenolate-Based Ionic Liquids.

We synthesized ionic liquids (ILs) comprising an alkylphosphonium cation paired with phenolate, 4-nitrophenolate, and 4-methoxyphenolate anions that span a wide range of predicted reaction enthalpies with CO2. Each phenolate-based IL was characterized by spectroscopic techniques, and their physical properties (viscosity, conductivity, and CO2 solubility) were determined. We use the computational quantum chemical approach paired with experimental results to reveal the reaction mechanism of CO2 with phenolate ILs. Model chemistry shows that the oxygen atom of phenolate associates strongly with phosphonium cations and is able to deprotonate the cation to form an ylide with an affordable activation barrier. The ATR-FTIR and (31)P NMR spectra indicate that the phosphonium ylide formation and its reaction with CO2 are predominantly responsible for the observed CO2 uptake rather than direct anion-CO2 interaction.

Competing reactions of CO2 with cations and anions in azolide ionic liquids.

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.

Reaction kinetics of CO2 absorption in to phosphonium based anion-functionalized ionic liquids.

The reaction kinetics between CO2 and trihexyl(tetradecyl)phosphonium ([P66614])-based ionic liquids (ILs) with prolinate ([Pro]), 2-cyanopyrrolide ([2-CNpyr]), and 3-(trifluoromethyl)pyrazolide ([3-CF3pyra]) anions are studied at temperatures from 22-60 °C. The absorption of CO2 is carried out in a stirred reactor under pseudo first order conditions. ILs are diluted to concentrations of 0.05, 0.1 and 0.15 M with tetraglyme--a nonreactive, low volatility solvent with much lower viscosity than the ILs. Physical solubility of CO2 in the mixtures is calculated using correlations developed from CO2 solubility measurements in tetraglyme and the N2O-analogy for ILs and dilute IL solutions. The diffusivity of CO2 is estimated from viscosity-dependent correlations chosen after a thorough literature review. The results indicate partial first order reaction kinetics with respect to IL with values ranging from 19,500 L mol(-1) s(-1) ([P66614][Pro]) to 3200 L mol(-1) s(-1) ([P66614][3-CF3pyra]) at 22 °C. The second order reaction rate constants follow Arrhenius behavior with the highest activation energy of 43 kJ mol(-1) measured for [P66614][Pro]. ILs with aprotic heterocylic anions (AHA), on the other hand, show small activation energies of 18 and 11 kJ mol(-1) for [P66614][3-CF3pyra] and [P66614][2-CNpyr], respectively. The ILs studied in this work exhibit reactivity comparable to or higher than common aqueous amines. High reaction rates and tunable capacity make ILs, and AHA ILs in particular, attractive solvents for CO2 separations.