Ionic Liquid-Glycol Mixtures for Direct Air Capture of CO2: Decreased Viscosity and Mitigation of Evaporation Via Encapsulation.

Herein we address the efficiency of the CO2 sorption of ionic liquids (IL) with hydrogen bond donors (e.g., glycols) added as viscosity modifiers and the impact of encapsulating them to limit sorbent evaporation under conditions for the direct air capture of CO2. Ethylene glycol, propylene glycol, 1,3-propanediol, and diethylene glycol were added to three different ILs: 1-ethyl-3-methylimidazolium 2-cyanopyrrolide ([EMIM][2-CNpyr]), 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]). Incorporation of the glycols decreased viscosity by an average of 51% compared to bulk IL. After encapsulation of the liquid mixtures using a soft template approach, thermogravimetric analysis revealed average reductions in volatility of 36 and 40% compared to the unencapsulated liquid mixtures, based on 1 h isothermal experiments at 25 and 55 °C, respectively. The encapsulated mixtures of [EMIM][2-CNpyr]/1,3-propanediol and [EMIM][2-CNpyr]/diethylene glycol exhibited the lowest volatility (0.0019 and 0.0002 mmol/h at 25 °C, respectively) and were further evaluated as CO2 absorption/desorption materials. Based on the capacity determined from breakthrough measurements, [EMIM][2-CNpyr]/1,3-propanediol had a lower transport limited absorption rate for CO2 sorption compared to [EMIM][2-CNpyr]/diethylene glycol with 0.08 and 0.03 mol CO2/kg sorbent, respectively; however, [EMIM][2-CNpyr]/diethylene glycol capsules exhibited higher absorptions capacity at ∼500 ppm of CO2 (0.66 compared to 0.47 mol of CO2/kg sorbent for [EMIM][2-CNpyr]/1,3-propanediol). These results show that glycols can be used to not only reduce IL viscosity while increasing physisorption sites for CO2 sorption, but also that encapsulation can be utilized to mitigate evaporation of volatile viscosity modifiers.

Tuning Surface, Phase, and Magnetization of Superparamagnetic Magnetite by Ionic Liquids: Single-Step Microwave-Assisted Synthesis.

Achieving colloidal and chemical stability in ferrofluids by surface modification requires multiple steps, including purification, ex situ modification steps, and operation at high temperatures. In this study, a single-step microwave-assisted methodology is developed for iron oxide nanoparticle (IONP) synthesis utilizing a series of imidazolium-based ionic liquids (ILs) with chloride, bis(trifluoromethylsulfonyl)imide, and pyrrolide anions as the reaction media, thus eliminating the use of volatile organics while enabling rapid synthesis at 80 °C as well as in situ surface functionalization. The characterized surface functionality, hydrodynamic particle size, magnetization, and colloidal stability of the IONPs demonstrate a strong dependence on the IL structure, ion coordination strength, reactivity, and hydrophilicity. The IONPs present primarily a magnetite (Fe3O4) phase with superparamagnetism with the highest saturation magnetization at 81 and 73 emu/g at 10 and 300 K, respectively. Depending on the IL coating, magnetization and exchange anisotropy decrease by 20 and 2-3 emu/g (at 35 wt % IL), respectively, but still represent the highest magnetization achieved for coated IONPs by a coprecipitation method. Further, the surface-functionalized superparamagnetic magnetite nanoparticles show good dispersibility and colloidal stability in water and dimethyl sulfoxide at 0.1 mg/mL concentration over the examined 3 month period. This study reports on the intermolecular and chemical interactions between the particle surface and the ILs under synthetic conditions as they relate to the magnetic and thermal properties of the resulting IONPs that are well suited for a variety of applications, including separation and catalysis.

Tailoring Electrochemical CO2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors.

Electrochemical CO2 reduction (CO2 RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO2 solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion-CO2 adducts and a hydrogen bond donor (HBD) upon CO2 absorption to modulate CO2 RR on Cu in a non-aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface-enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum-mechanical/molecular mechanics (IC-QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO2 availability, reduced overpotential, and suppressed HER where C4 products are obtained. This study deepens the understanding of electrolyte effects in CO2 RR and the role of IL ions towards electrocatalytic microenvironment design.

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.

Perspective and challenges in electrochemical approaches for reactive CO2 separations.

The desire toward decarbonization and renewable energy has sparked research interests in reactive CO2 separations, such as direct air capture that utilize electricity as opposed to conventional thermal and pressure swing processes, which are energy-intensive, cost-prohibitive, and fossil-fuel dependent. Although the electrochemical approaches in CO2 capture that support negative emissions technologies are promising in terms of modularity, smaller footprint, mild reaction conditions, and possibility to integrate into conversion processes, their practice depends on the wider availability of renewable electricity. This perspective discusses key advances made in electrolytes and electrodes with redox-active moieties that reversibly capture CO2 or facilitate its transport from a CO2-rich side to a CO2-lean side within the last decade. In support of the discovery of new heterogeneous electrode materials and electrolytes with redox carriers, the role of computational chemistry is also discussed.

Facilitated Transport Membranes With Ionic Liquids for CO2 Separations.

In recent years, significant development milestones have been reached in the areas of facilitated transport membranes and ionic liquids for CO2 separations, making the combination of these materials an incredibly promising technology platform for gas treatment processes, such as post-combustion and direct CO2 capture from air in buildings, submarines, and spacecraft. The developments in facilitated transport membranes involve consistently surpassing the Robeson upper bound for dense polymer membranes, demonstrating a high CO2 flux across the membrane while maintaining very high selectivity. This mini review focuses on the recent developments of facilitated transport membranes, in particular discussing the challenges and opportunities associated with the incorporation of ionic liquids as fixed and mobile carriers for separations of CO2 at low partial pressures (<1 atm).

Capsules of Reactive Ionic Liquids for Selective Capture of Carbon Dioxide at Low Concentrations.

The task-specific ionic liquid (IL), 1-ethyl-3-methylimidazolium 2-cyanopyrolide ([EMIM][2-CNpyr]), was encapsulated with polyurea (PU) and graphene oxide (GO) sheets via a one-pot Pickering emulsion, and these capsules were used to scrub CO2 (0-5000 ppm) from moist air. Up to 60 wt % of IL was achieved in the synthesized capsules, and we demonstrated comparable gravimetric CO2 capacities to zeolites and enhanced absorption rates compared to those of bulk IL due to the increased gas/liquid surface-to-volume area. The reactive IL capsules show recyclability upon mild temperature increase compared to zeolites that are the conventional absorber materials for CO2 scrubbing. The measured breakthrough curves in a fixed bed under 100% relative humidity establish the utility of reactive IL capsules as moisture-stable scrubber materials to separate CO2 from air, outperforming zeolites owing to their higher selectivity. It is shown that thermal stability, CO2 absorption capacity, and rate of uptake by IL capsules can be further modulated by incorporating low-viscosity and nonreactive ILs to the capsule core. This study demonstrates an alternative and facile approach for CO2 scrubbing, where separation from gas mixtures with extremely low partial pressures of CO2 is required.