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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Frontiers of Ionic Liquids in Carbon Dioxide Separation and Valorization

Ionic liquids (ILs) have emerged as highly tunable sorbents and membranes for gas separation, especially in the purification of CO 2 -containing gas streams such as air, natural gas, biogas, and syngas. Their negligible volatility, high thermal stability, and chemical versatility position them as promising alternatives to conventional amine and alkaline metal derivative-based systems, effectively addressing key challenges such as volatility, stability, and high regeneration energy. Here, this Review explores IL-derived systems for CO 2 -related gas separation across dense, porous, and supported categories. At the dense liquid level, we discuss strategies for tailoring IL properties to optimize CO 2 sorption, focusing on the correlation between IL-CO 2 interaction strength, uptake capacity, and regeneration energy. Key advancements in carbon capture, including amino-functionalized (AILs) and superbase-derived ILs (SILs), are highlighted, along with strategies such as chemical structure engineering, multiple binding site integration, alternative driving force exploration, and stability enhancement. Then, the porous liquids (PLs) scale focuses on the emerging field integrating IL properties with permanent porosity engineering, spanning ultramicropores (<5 Å) to macropores (around 100 nm). These innovations improve gas uptake capacity, accelerate transport kinetics, introduce the gating effect, and enable the coexistence of active sites with antagonistic properties within a single IL medium. At the supported IL scale, the discussion shifts to IL- and ionic pair-modified sorbents and membranes, emphasizing the modulation of cations and anions, confinement effects from porous supports, and the IL–interface interaction to enhance CO 2 separation performance, particularly in diluted gas streams. Beyond separation, this Review highlights IL-based integrated processes for CO 2 capture and conversion into value-added chemicals via thermocatalytic, electrocatalytic, and photocatalytic pathways. At each scale, advanced computational and experimental tools for IL design are also discussed, providing insights into stability enhancement, sorption efficiency, and process integration. The Review concludes by addressing existing challenges and outlining future directions for IL-driven innovations in gas separation technologies.

Qiu, Liqi [Univ. of Tennessee, Knoxville, TN (Unit↗
DOE OSTI2025

Balancing solvation: stabilizing lithium metal batteries via optimized cosolvents for ionic-liquid electrolytes

In this study, we examined three cosolvents with distinct solvation capabilities for ionic-liquid electrolytes based on 1-methyl-1-propyl pyrrolidinium bis(fluorosulfonyl)imide (Py13FSI). We demonstrate that 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG) notably enhances the cycle life of Py13FSI-based electrolytes, outperforming 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropylether (TTE) and diglyme (DG). Electrochemical and surface analyses showed that this improvement could be attributed to the formation of a favorable cathode interphase, promoting efficient Li+ transport with reduced overpotential. Spectroscopic techniques (FTIR, Raman, and NMR spectroscopy) and molecular dynamics simulations revealed that cosolvents with varying solvation abilities can influence the solvation structures in Py13FSI-based electrolytes. The mild solvating strength and lithium stability of FDG are key contributors to its effectiveness. Conversely, DG, a strong solvating solvent, destabilized the Py13FSI-DG electrolyte at the lithium metal anode, while TTE, a non-solvating solvent, failed to enhance lithium transport or form a stable cathode interphase. Our findings highlight that balanced solvation exerted by the cosolvents is critical for forming a stable electrolyte–cathode interface, potentially through FSI decomposition. This study offers valuable insights into the development of durable ionic-liquid electrolytes, emphasizing the importance of selecting cosolvents with optimal solvation properties.

Li, Xinlin [Argonne National Laboratory (ANL), Arg↗
DOE OSTI2026

Direct Air Capture-Compatible Azolate and Amino Acid Ionic Liquids for Electrochemical CO 2 Reduction to CO on a Silver Cathode

Direct air capture (DAC) compatible ionic liquids (ILs) are attractive for integrating CO 2 capture and conversion due to their high CO 2 solubility at low partial pressures, tunable chemisorption mechanisms, low volatility, and wide electrochemical windows. However, very few ILs have high CO 2 uptake at DAC conditions (420 ppm CO 2 ), and even fewer have been evaluated for chemical compatibility and mechanistic continuity for combined capture and electrochemical CO 2 reduction (eCO 2 RR). We demonstrate that two representative DAC-capable ILs, [P 4444 ][Val] (amino acid-based) and [P 66614 ][5-Me-Imd] (azolate-based), exhibit favorable electrochemical reduction behavior. CO and H 2 were the dominant gas-phase products by GC, while 1 H and 13 C NMR confirmed negligible liquid-phase HCOOH. Chronoamperometry at moderate applied potentials (−2.0 to −2.5 V vs Ag/AgCl) in a two-compartment H-cell with a Ag coated carbon paper as the working electrode yielded steady-state current densities of ∼10 mA cm −2 with CO FE of 96% for [P 4444 ][Val] and 95% for [P 66614 ][5-Me-Imd], highlighting the role of viscosity and chemically absorbed CO 2 -IL species to provide highly selective CO formation while suppressing H 2 evolution.

amino acid ionic liquid↗
DOE OSTI2025

A “Sweet” Biorefinery: Sugar-derived ionic liquids for the pretreatment of lignocellulosic biomass

Sugar-based ionic liquids (ILs) derived from biomass-based cations (choline, betaine) and sugar-derived anions were developed as sustainable pretreatment solvents to advance the concept of self-reliant biorefinery. Cholinium gluconate ([Ch][GlcA]) enabled streamlined one-pot sorghum pretreatment without the need for pH adjustment or washing, while betainium gluconate ([Bet][GlcA]) achieved higher sugar yields, improving overall process efficiency and economics. Both ILs produced hydrolysates fully compatible with microbial fermentation, demonstrating their potential for efficient, simplified biomass conversion. This work positions sugar-based ILs as powerful platforms that unite sustainable chemistry with integrated bioprocessing, marking a pivotal step toward realizing the self-reliant biorefinery.

Biomass-based ions↗
DOE OSTI2024

Computational Advances in Ionic Liquid Applications for Green Chemistry: A Critical Review of Lignin Processing and Machine Learning Approaches

The valorization and dissolution of lignin using ionic liquids (ILs) is critical for developing sustainable biorefineries and a circular bioeconomy. This review aims to critically assess the current state of computational and machine learning methods for understanding and optimizing IL-based lignin dissolution and valorization processes reported since 2022. The paper examines various computational approaches, from quantum chemistry to machine learning, highlighting their strengths, limitations, and recent advances in predicting and optimizing lignin-IL interactions. Key themes include the challenges in accurately modeling lignin’s complex structure, the development of efficient screening methodologies for ionic liquids to enhance lignin dissolution and valorization processes, and the integration of machine learning with quantum calculations. These computational advances will drive progress in IL-based lignin valorization by providing deeper molecular-level insights and facilitating the rapid screening of novel IL-lignin systems.

09 BIOMASS FUELS↗
DOE OSTI2026

Structuring, stochastic behavior, and charge storage capacity of redox-active microemulsions formulated with mixtures of toluene and ionic liquid as oil phase

Oil/water microemulsions (µEs) are promising electrolytes for redox flow batteries (RFBs) as they simultaneously improve charge capacity and ionic conductivity. Here, we report the successful formulation of bicontinuous µEs where the oil phase is a solution of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid in toluene with redox-active ferrocene. We examined the effect of supporting electrolyte anion (NO 3 – , Cl – , ClO 4 – ) on the structure, reactivity, transport, and electrolytic performance of redox-active µEs. Neutron scattering and nuclear magnetic resonance showed that the domain size increased as Cl – > NO 3 – > ClO 4 – while the ferrocene diffusion coefficient increased as NO 3 – > Cl – > ClO 4 – . Scanning electrochemical microscopy indicated anion-dependent current fluctuations during electrolysis, with ClO 4 – exhibiting the least high-frequency oscillations, which correlate to the highest charge and discharge capacity and reversibility. All ionic liquid containing systems improved the performance of toluene-based µEs, highlighting new design principles for these electrolytes.

diffusion↗
DOE OSTI2026

Molecular dynamics based study on the effects of cation size on the local structure and diffusion in polymerized ionic liquids

We have used coarse-grained molecular dynamics simulations to understand the effect of cation size on ion diffusion in polymerized ionic liquids at temperatures well above the glass transition temperature of the polymers. We investigated dependencies of the diffusion constant on the cation radius and static dielectric constant and interpreted these results in terms of underlying structural changes, and decoupling phenomenon. We have found non-monotonic effects of the cation radius on the diffusion constant, with a maximum at an intermediate radius resulting from two different size dependent effects. Changes in the radial distribution functions characterizing spatial distribution of cations with respect to anions result in a monotonic increase in the coordination number. This yields an increase in the effective interaction energy as a function of cation radius, which can explain the decrease in the diffusion constant. This increase is counteracted at small cation radii by a corresponding increase in decoupling of cation and anion dynamics. In addition, the diffusion constant is found to increase on increasing the static dielectric constant for all radii of the cations. These results highlight the significant role of decoupling in designing polymerized ionic liquids with an enhanced diffusion constant of cations.

Gillespie, Colin [ORNL] (ORCID:0000000320287080)↗
DOE OSTI2026

Molecular-Level Insights into the Influence of Ionic Liquids on the Structure and Dynamics of Neutral and Charged Polyimides

We use all-atom molecular dynamics simulations to investigate how increasing ionic functionalization influences polyimide (PI) behavior in ionic liquid (IL) solvation environments. Here, we examine three polymer systems with varying charge densities: a neutral polyimide [N−PI] containing imidazole rings and progressively introduce charge through quaternization to create singly [C−PI] + and doubly charged [C−2PI] 2+ variants across a wide range of IL concentration (0−90 wt %). Through comprehensive structural, mechanical, and electrostatic analyses, we reveal that polymer charge density plays a central role in shaping IL organization and interaction with the polymer matrix. At low IL content, charged systems exhibit strong electrostatic complexation, leading to chain compaction, localized ESP environments, and elevated dielectric constants. As IL concentration increases, the effect of the different polymer charge states becomes less significant. Notably, an intermediate composition regime at approximately 50 wt % IL is associated with changes in IL-rich domain connectivity and overall system behavior across all three PI systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Transformational Nano-confined Ionic Liquid Membrane for Greater than or Equal to 97 Percent Carbon Dioxide Capture from Natural Gas Combined Cycle Flue Gas

A transformational process based on nano-confined ionic liquid (NCIL) membranes was developed for capturing ≥97% CO 2 from natural gas combined cycle (NCCC) flue gas. The NCIL membranes were prepared by loading amino acid ionic liquid into a framework composed of single-walled carbon nanotube mesh filled with graphene oxide quantum dots. The membranes exhibited CO 2 permeance as high as 2,000 GPU with a CO 2 /N2 selectivity of 2,300 for a typical NGCC flue gas composition. When H 2 O vapor sweep was applied in the permeate side, 96.6% CO2 dry-basis purity and 97.6% CO 2 capture rate were achieved for a simulated NGCC flue gas with single stage. In the process design, a highly H 2 O-selective membrane would be needed to recover majority of the H 2 O vapor, and the recovered H 2 O vapor could be recycled to the permeate side of the NCIL membrane. Sulfonated poly(ether ether ketone) membranes were successfully developed for this purpose. These membranes exhibited H 2 O permeance great than 11,000 GPU and H 2 O/CO 2 selectivity greater than 1,000 at 70ºC for a feed mixture consisting of 14.5 vol% H2O and balanced CO 2 . A standalone membrane model using MATLAB platform was developed for process simulation. The model was validated with experimental data. Techno-economic analysis based on the testing data collected during the current program suggests this transformational membrane process can achieve 97% CO 2 capture efficiency with a cost of $47.8/tonne of CO 2 , which is a 21% reduction versus DOE’s reference case B31B.97.

03 NATURAL GAS↗
DOE OSTI2026

Rational Design of Weakly‐Solvating Molecules for Salt‐In‐Pre‐Ionic‐Liquid Electrolytes for Li Metal Batteries

Lithium metal batteries (LMBs) promise step‐changes in energy densities but suffer from poor cycle life due to unstable electrolyte‐lithium interfaces. Conventional carbonate electrolytes exhibit excessive lithium‐ion solvation and low oxidative stability, leading to rapid capacity loss. Herein, we report a rationally designed weakly‐solvating cyclic sulfonamide, 1‐trifluoromethanesulfonyl)amide pyrrolidine (TFMSPyr), which integrates an electron‐withdrawing trifluoromethanesulfonyl functional group at pyrrolidinic‐N. TFMSPyr acts as a pre‐ionic‐liquid solvent that forms intrinsically localized, anion‐dominated solvation, coupling molecular architecture, solvation topology, and transport dynamics. As a result, LiFSI based salt‐in‐pre‐ionic‐liquid (SIPIL) electrolytes exhibit high lithium‐ion transference number, oxidative stability > 5 V versus Li/Li + and anion‐derived solid electrolyte interphases (SEI). Li||Cu cells with SIPIL deliver a first cycle Coulombic efficiency (CE) of ≈ 99% with average CE of 99.2% for 100 cycles, and lithium half‐cells with lithium iron phosphate (LFP) cathode exhibit 82% capacity retention after 400 cycles with CE of 99.98%. In anode‐free full cells, 95% of initial capacity is retained after 63 cycles with an average CE of 99.5%. These results demonstrate that molecular engineering of solvents offers a powerful pathway to stabilize lithium metal interfaces and enable practical Anodeless LMBs.

25 ENERGY STORAGE↗
DOE OSTI2026

In situ molecular imaging of ion clusters reveals the acid gas capture capacity and mechanism of water-lean ionic liquids

Water-lean solvents are a promising technology for capturing acid gases like carbon dioxide (CO 2 ). In situ liquid time-of-flight secondary ionization mass spectroscopy (ToF-SIMS) is used to study a representative solvent N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (2-EEMPA) with different CO 2 loadings to reveal the complex solvent structure upon CO 2 capture. Characteristic peaks of 2-EEMPA, such as m/z – 215 C 11 H 23 N 2 O 2 – (deprotonated 2-EEMPA) and m/z + 217 C 11 H 25 N 2 O 2 + (protonated 2-EEMPA), are detected due to acid gas uptake. Also, solvent molecules and carboxylate ion pairs, such as m/z – 259 C 12 H 23 N 2 O 4 – [(deprotonated 2-EEMPA∙∙∙CO 2 )] and m/z + 261 C 12 H 25 N 2 O 4 + (protonated 2-EEMPA∙∙∙CO 2 ), are observed. Interestingly, more than one CO 2 molecule can be captured per each solvent molecule as evidenced in SIMS mass spectra, for example, m/z – 321 C 13 H 25 N 2 O 7 – [(deprotonated 2-EEMPA)∙∙∙2CO 2 ∙∙∙H 2 O], m/z + 305 C 13 H 25 N 2 O 4 + [(protonated 2-EEMPA)∙∙∙2CO 2 ], m/z – 389 C 17 H 29 N 2 O 8 – [(deprotonated 2-EEMPA)∙∙∙3CO 2 ∙∙∙3CH 2 ], and m/z + 373 C 16 H 25 N 2 O 8 + [(protonated 2-EEMPA)∙∙∙3CO 2 ∙∙∙2C]. However, the monomer of 2-EEMPA and CO 2 seems to be most prevalent. Furthermore, solvent clusters are detected in loaded solvents, for instance m/z + 433 C 22 H 49 N 4 O 4 + [(2-EEMPA)2∙∙∙H] and m/z + 646 [(2-EEMPA) 3 -2H], while capturing CO 2 at different amounts. Relative abundance of cluster ions provides a semi-qualitative venue to assess the free energies of gas capture energetics, indicating the relative stability trend within the same solvent system, previously impossible. These observed ion clusters are verified with molecular modeling, where dimer, trimer, and cluster ions are validated for their presence either due to weak molecular interactions or hydrogen bonds. In situ molecular imaging of ionic liquids and molecular modeling reveals that the acid gas capture mechanism by ionic liquids includes both physical adsorption and chemical bonding with multiple reaction pathways, engaging cluster formation and alteration of solvent structures.

Acid gas capture↗
DOE OSTI2025

Influence of counterion substitution on the properties of imidazolium-based ionic liquid clusters

Due to their unique physiochemical properties that may be tailored for specific purposes, ionic liquids (ILs) have been investigated for various applications, including chemical separations, catalysis, energy storage, and space propulsion. The different cations and anions comprising ILs may be selected to optimize a range of desired properties, such as thermal stability, ionic conductivity, and volatility, leading to the designation of certain ILs as designer “green” solvents. The effect of counterions on the properties of ILs is of both fundamental scientific interest and technological importance. Herein, we report a systematic experimental and theoretical investigation of the size, charge, stability toward dissociation, and geometric/electronic structure of 1-ethyl-3-methyl imidazolium (EMIM)-based IL clusters containing two different atomic counterions (i.e., bromide [Br − ] and iodide [I − ]). This work extends our studies of EMIM + cations with atomic chloride (Cl − ) and molecular tetrafluoroborate (BF 4 − ) anions reported previously by Baxter et al. [Chem. Mater. 34, 2612 (2022)] and Zhang et al . [J. Phys. Chem. Lett. 11, 6844 (2020)], respectively. Distributions of anionic IL clusters were generated in the gas phase using electrospray ionization and characterized by high mass resolution mass spectrometry, energy-resolved collision-induced dissociation, and negative ion photoelectron spectroscopy experiments. The experimental results reveal anion-dependent trends in the size distribution, relative abundance, ionic charge state, stability toward dissociation, and electron binding energies of the IL clusters. Complementary global optimization theory provides molecular-level insights into the bonding and electronic structure of a selected subset of clusters, including their low energy structures and electrostatic potential maps, and how these fundamental characteristics are influenced by anion substitution. Collectively, our findings demonstrate how the fundamental properties of ILs, which determine their suitability for many applications, may be tuned by substituting counterions. These observations are critical in the sub-nanometer cluster size regime where phenomena do not scale predictably to the bulk phase, and each atom counts toward determining behavior.

cluster↗
DOE OSTI2025

Self‐Healable Poly(ionic liquid) Copolymers Driven by Polar and Dipolar Forces

Abstract Commodity aliphatic and aromatic acrylic‐based copolymers self‐heal due to ubiquitouskey‐and‐lock,ring‐and‐lock, andfluorophilic‐σ‐lockvan der Waals (vdW) interactions. However, the role of these interactions in the presence of covalently copolymerized ionic liquid (IL) is not known. This study is driven by the hypothesis that covalently incorporated cation–anion pairs to form poly(ionic liquid) copolymers (PILCs) can perturb inter‐ or intra‐chain vdW interactions reflected in mechanical and electrical responses. To test this hypothesis, we synthesized a series of PILCs comprising of pentafluorostyrene (PFS) and imidazolium‐based IL monomers with variable‐length aliphatic tails (methyl and butyl). Using a combination of 2D 1 H‐ 1 H and 19 F ‐ 19 F NOESY NMR and FTIR measurements supplemented by molecular dynamic (MD) simulations, these studies demonstrate that preferentially alternating/random PILCs topologies facilitate self‐healing. The introduction of cation–anion moieties modifies thefluorophilic‐σ‐lockinteractions and, along with longer aliphatic tails ─(CH 2 ) 3 CH 3 covalently attached to the imidazolium cation, enhances cation‐anion mobility, thus faster recovery from mechanical damage occurs. These findings underline how precise control over dipolar and ionic interactions through copolymer composition enables self‐healing in PILCs. These insights may open pathways for designing sustainable, mechanically resilient materials for applications in energy storage and energy harvesting.

Chemistry↗
DOE OSTI2026

Water-stable direct air capture of CO 2 with microcapsules of task-specific ionic liquid and their electrothermal regeneration

Microcapsules of the task specific ionic liquid (TSIL) 1-ethyl-3-methylimidazolium 2-cyanopyrrolide [EMIM][2CNpyr] with composite polydimethylsiloxane (PDMS) shells were fabricated for use in CO 2 direct air capture (DAC) conditions. The TSIL was encapsulated using an oil-in-oil emulsion as a templating procedure through two different approaches. In the first approach, a PDMS-polyurea (PU) shell was constructed by interfacial polymerization, while in the second approach, a graphene oxide (GO)-PDMS shell was constructed by cross-linking GO sheets. The composition and structure of both capsule types were fully characterized, and their CO 2 DAC performance was evaluated by gravimetric and breakthrough analysis. Both capsules exhibited competitive capacities, with the PDMS-PU capsules and the GO-PDMS capsules reaching 0.75 mol kg −1 and 0.66 mol kg −1 , respectively. We further demonstrate that both capsule systems can be regenerated with complementary electrothermal methods. Microwave (MW) regeneration was used for the PDMS-PU capsules, effectively releasing absorbed CO 2 in less than an hour. Owing to the electrical conductivity of GO, GO-PDMS capsules were regenerated via radio frequency heating (RF). This work highlights the importance and opportunity of tuning solid–liquid composite performance for advanced applications, including direct air capture of carbon dioxide.

Al-Mahbobi, Luma [Texas A&M University, College St↗
DOE OSTI2026

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ionic Liquid Aided [ 11 C]CO Fixation for Synthesis of 11 C‐carbonyls

Tributyl(ethyl)phosphonium oxopentenolate ([P 4442 ][Pen]) is an ionic liquid developed to capture CO and has shown ability to catalyze carbonylation reactions in organic chemistry. Carbon-11 ( 11 C, t 1/2 =20.4 min) labeled CO is a highly versatile building block for the synthesis of positron emission tomography (PET) radiotracers that are applied for medical imaging. The use of [ 11 C]CO is limited by its low solubility in organic solvents. Herein, we report a proof-of-concept study evaluating a new method to prepare 11 C-labeled amides, ureas and carbamates via reaction of [ 11 C]CO in [P 4442 ][Pen] and applied for fully automated radiosyntheses of Bruton's tyrosine kinase inhibitors, [ 11 C]evobrutinib and [ 11 C]ibrutinib.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Temperature-dependent changes in gas chromatographic separation metrics for trihexyl(tetradecyl)phosphonium-based ionic liquid stationary phases and comparison to conventional polysiloxane stationary phases

Here, to assess whether the trihexyl(tetradecyl)phosphonium chloride ([P 66614 + ][Cl - ]) ionic liquid (IL), employed as a gas chromatographic stationary phase, exhibits temperature-dependent phase transitions or structural heterogeneity, retention thermodynamics for probe molecules of varied chemical structure were investigated by gas chromatography (GC) over the temperature range of 25 to 64 °C using van’t Hoff analysis. All van’t Hoff plots for n-alkanes (C8–C12) and other probe analytes were linear, indicating the absence of detectable phase-transition behavior. The [P 66614 + ][Cl - ] IL was further compared with the [P 66614 + ] bis[(trifluoromethyl)sulfonyl]imide ([P 66614 + ][NTf 2 - ]) IL and commercial polysiloxane stationary phases in terms of temperature-dependent resolution behavior and chromatographic selectivity over the temperature range of 28–52 °C. The resolution factors of analytes in mixtures obtained using gas chromatography–mass spectrometry (GC–MS) and the summation of resolution values decreased smoothly with temperature on both IL stationary phases and on the dimethylphenylcyano-substituted polymeric stationary phase (OV-1701), whereas the poly(50% diphenyl/50% dimethyl siloxane) stationary phase (SPB-50) exhibited irregularities in its temperature-dependent summation of resolution profile, showing a distinct maximum in the temperature range of 34–40 °C. Selectivity values for the IL stationary phases were largely determined by the anion, with the [P 66614 + ][Cl - ] IL providing enhanced separation between polar and aromatic analytes, while the [P 66614 + ][NTf 2 - ] IL favored dispersive and π-π interactions that resulted in a reversal of elution order for some aliphatic–aromatic and alkyne-containing analyte pairs. Capillary columns prepared using different surface activation methods and coated with identical [P 66614 + ][Cl - ] IL stationary phase showed indistinguishable temperature-dependent trends in summation of resolution value and selectivity. An evaluation of analyte-specific selectivity provides insight into the characteristic separation behavior of the stationary phases and enables identification of analyte classes that are more efficiently separated on the [P 66614 + ]-based IL stationary phases compared to conventional stationary phase materials.

Chromatographic selectivity↗