Reactive capture and electrochemical conversion of CO2 with ionic liquids and deep eutectic solvents.

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO2 due to their wide electrochemical stability window, low volatility, and high CO2 solubility. There is environmental and economic interest in the direct utilization of the captured CO2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO2, eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO2 with aqueous electrolytes presents limited CO2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO2, often diluting them with aqueous or non-aqueous solvents. The resulting electrode-electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation.

Formation of choline salts and dipolar ions for CO2 reactive eutectic solvents.

Choline-based sorbents derived from imidazole (ImH), phenol (PhOH), pyrrole-2-carbonitrile (CNpyrH), and 1,2,4-triazole (TrzH) are developed for CO2 capture to enable alternative regeneration approaches over aqueous amines. During synthesis, the equilibrium between [Ch]+[OH]- and Ch± dipolar in water shifts to support the formation of Ch±ImH and Ch±PhOH in the presence of ImH and PhOH upon drying. In contrast, salts of [Ch]+[CNpyr]- and [Ch]+[Trz]- were obtained with CNpyrH and TrzH, as confirmed by NMR and FTIR spectroscopy. Density functional theory (DFT) calculations support a spontaneous proton transfer from CNpyrH and TrzH to Ch±, while they show an energy barrier in the case of ImH. These sorbents formed eutectic solvents upon mixing with ethylene glycol (EG) where deprotonation of EG and subsequent binding of CO2 contributed to capacities up to 3.56 mol CO2 kg-1 at 25 °C and 1 bar of CO2. The regenerability of the eutectic solvents was demonstrated by dielectric heating via microwaves (MWs) in support of renewable energy utilization. This study shows the impact of proton sharing on the CO2 capacity and regenerability of eutectic sorbents as molecular design guidance.

Microwave Regeneration and Thermal and Oxidative Stability of Imidazolium Cyanopyrrolide Ionic Liquid for Direct Air Capture of Carbon Dioxide.

Understanding the oxidative and thermal degradation of CO2 sorbents is essential for assessing long-term sorbent stability in direct air capture (DAC). The potential degradation pathway of imidazolium cyanopyrrolide, an ionic liquid (IL) functionalized for superior CO2 capacity and selectivity, is evaluated under accelerated degradation conditions to elucidate the secondary reactions that can occur during repetitive absorption-desorption thermal-swing cycles. The combined analysis from various spectroscopic, chromatographic, and thermal gravimetric measurements indicated that radical and SN 2 mechanisms in degradation are encouraged by the nucleophilicity of the anion. Thickening of the liquid and gas evolution are accompanied by 50 % reduction in CO2 capacity after a 7-day exposure to O2 under 80 °C. To prevent long exposure to conventional thermal heating, microwave (MW) regeneration of the CO2 -reactive IL is used, where dielectric heating at 80 and 100 °C rapidly desorbs CO2 and regenerates the IL without any measurable degradation.

Facilitated transport membrane with functionalized ionic liquid carriers for CO2/N2, CO2/O2, and CO2/air separations.

CO2 separations from cabin air and the atmospheric air are challenged by the very low partial pressures of CO2. In this study, a facilitated transport membrane (FTM) is developed to separate CO2 from air using functionalized ionic liquid (IL) and poly(ionic liquid) (PIL) carriers. A highly permeable bicontinuous structured poly(ethersulfone)/poly(ethylene terephthalate) (bPES/PET) substrate is used to support the PIL-IL impregnated graphene oxide thin film. The CO2 separation performance was tested under a mixture feed of CO2/N2/O2/H2O. Under 410 ppm of CO2 at 1 atm feed gas, CO2 permanence of 3923 GPU, and CO2/N2 and CO2/O2 selectivities of 1200 and 300, respectively, are achieved with helium sweeping on the permeate side. For increased transmembrane pressure (>0 atm), a thicker PIL-IL/GO layer was shown to provide mechanical strength and prevent leaching of the mobile carrier. CO2 binding to the carriers, ion diffusivities, and the glass transition temperature of the PIL-IL gels were examined to determine the membrane composition and rationalize the superior separation performance obtained. This report represents the first FTM study with PIL-IL carriers for CO2 separation from air.