Ionic Liquid Research Articles

Synthesis and Characterization of CL-PA Ionic Liquid

Caprolactam is most commonly used in the production of Nylon 6 in industry and is generally produced from cyclohexanone by the Beckmann rearrangement. Orthophosphoric acid is generally used in fertilizer production and is produced through two processes: wet and dry. In this study, detailed characterization of CL-PA was carried out by synthesizing CL-PA ionic liquid from orthophosphoric acid (PA) and caprolactam (CL). FTIR, Raman and UV-Vis spectroscopic analyses reveal that a bond is formed between CL and PA. The thermal behavior of CL-PA ionic liquid was inspected by TGA and DSC. It has been observed that the decomposition temperature of CL-PA ionic liquid is different from that of the starting materials (CL and PA). It was disclosed by DSC analysis that CL-PA ionic liquid only has a glass transition temperature. The room-temperature CL-PA ionic liquid synthesized from solid CL with melting point of 70.34 ℃ and 85 wt.% PA did not show any melting or freezing point and the glass transition temperature was found to be −27 ℃. It was revealed that CL-PA ionic liquid was more thermally stable than CL which alone almost completely evaporated at about 197 ℃. As a result of FTIR analysis of CL-PA ionic liquid and its constituents, it was demonstrated that –NH peaks of CL disappeared in the CL-PA spectrum and the peak of C=O group shifted to a lower frequency (i.e., 1604 cm⁻1). In the Raman analysis of CL-PA and its constituents, it was observed that the asymmetric C=O bending vibration and C=O stretching vibration of CL disappeared in the CL-PA spectrum. In the UV spectrum, it was observed that the maximum absorbance of CL-PA ionic liquid varied with respect to that of CL.

Mechanistic Study of the Electrochemical Reduction of CO2 in Aprotic Ionic Liquid in Air.

The capture and electrochemical conversion of dilute CO2 in air is a promising approach to mitigate global warming. Aiming to increase the efficiency of the electrochemical reduction of CO2, we fabricated electrodes and developed a custom-designed sealed electrochemical reaction system to study the mechanism of this conversion. The performance of three metal electrodes, Ag, Cu, and SUS 316L, was compared in an aprotic ionic liquid as the electrolyte to monitor the CO2 concentration and chemical reactions using a CO2 sensor and diffuse reflectance infrared Fourier transform spectroscopy and Raman spectroscopy in CO2/N2 (400 ppm CO2 and 99.96% N2) or synthetic air (400 ppm CO2, 21% O2, and 79% N2). The CO2 concentration decreased at negative potentials and was more drastic in synthetic air than in CO2/N2. At negative potential in synthetic air, IR revealed carbon monoxide, carbonate, or peroxydicarbonate on the Ag, Cu, or SUS 316L electrodes, respectively. Reaction intermediates were identified using Raman spectroscopy. Superoxide (O2•-), produced by the reduction of O2 on each electrode, promotes the electrochemical reduction of CO2 whose reduction potential is higher on the negative side than that of O2. This research deepens our understanding of the electrochemical capture/release and conversion of dilute CO2.

Constructing the high-efficiency “celluveyor conveyor” transport systems in membranes by IL@ZIF-8 for efficient CO2/CH4 separation

Inspired by the high-efficiency transport systems combined the “conveyor” transport pathways with the “celluveyor” transport pathways, the ionic liquid imide modified ZIF-8 (IL@ZIF-8) was prepared as a filler and incorporated into the self-polymerization-confined Pebax/polyethylene glycol methyl ether acrylate matrix (SPM) to prepare mixed matrix membranes (MMMs) for efficient CO2/CH4 separation. The incorporated IL@ZIF-8 can construct the high-efficiency “celluveyor conveyor” transport systems that consisted of the “celluveyor” transport pathways and the “conveyor” transport pathways, and it played important roles in MMMs. Therein, the “celluveyor” transport pathways can be constructed with the help of CO2 carriers (Zn2+) in oriented and ordered pore channels of IL@ZIF-8, contributing to promoting rapid CO2 transport in multiple direction. IL was uniformly distributed on ZIF-8, and it acted as “binder” between adjacent ZIF-8 in IL@ZIF-8. IL in IL@ZIF-8 can adsorb CO2 molecules as a consequence of its strong chemical affinity for CO2, and the “conveyor” transport pathways can be constructed with the help of CO2 carriers ([Tf2N]-) in IL for rapid CO2 transport between the adjacent ZIF-8, improving CO2 separation performance of MMMs. Consequently, it was possible to enhance the performance of CO2 separation by constructing the high-efficiency “celluveyor conveyor” transport systems in SPM/IL@ZIF-8 MMMs. Therefore, SPM/IL@ZIF-8 MMMs were endowed with the excellent CO2 separation performance. It showed an enhanced permeability for CO2, which increased by 96.9 %, and a better CO2/CH4 selectivity, which improved by 56.6 %, when compared to the performance of the pure SPM membrane. It implied that the constructed high-efficiency “celluveyor conveyor” transport systems in MMMs were a promising strategy for efficient CO2 separation.

Design of V-shaped ionic liquid crystals: atropisomerisation ability and formation of double-gyroid molecular assemblies.

We designed V-shaped ionic liquid crystals with two sterically congested ionic parts at the vertex. Depending on the degree of steric hindrance, atropisomerisation occurred in solution. All compounds formed bicontinuous cubic phases with double-gyroid structures in the bulk state, partially owing to the co-existence of atropisomers with opposite chirality.

Mechanistic understanding of enhancing bioactivity via bio-ionic liquid functionalization of biomaterials

The selection of biomaterials is a pivotal criterion for designing tissue engineering scaffolds, crucial for diverse biomedical applications. While natural biomaterials offer inherent bioactivity and biocompatibility, fine-tuning their properties for specific applications poses challenges. Conversely, synthetic biomaterials, while highly customizable, are often bio-inert. Functionalizing materials with bioactive molecules can improve cell-material interactions. Prevailing approaches utilizing RGD peptides or natural/synthetic composites have drawbacks including cost and immunogenicity. Bio-ionic liquids (BILs), a class of biocompatible ionic liquids derived from natural or synthetic biomolecules, offer a potential alternative. Herein, we present the biofunctionalization of a bio-inert polyethylene glycol diacrylate (PEGDA) with an acrylated choline-based BIL (“BioPEG”) as a method for enhancing the bioactivity of biomaterials. Cell studies using mouse myoblast C2C12 and human mesenchymal stem cells (hMSCs) revealed the excellence of BioPEG hydrogels in promoting cell attachment, growth, proliferation, and differentiation. Computational molecular dynamics (MD) simulations elucidated the mechanism by which BIL facilitates cell interaction with PEGDA. 3D printability of BioPEG hydrogel was showcased using a digital light processing (DLP) bioprinter, with printed scaffolds demonstrating excellent cytocompatibility. Collectively, these findings present BIL as a versatile bioactive agent for augmenting cell adhesion to materials, thus enriching the repertoire of biomaterials for advanced tissue engineering.

Flipping Water Orientation at the Surface of Water-in-Salt and Salt-in-Water Solutions.

Salt-in-water and water-in-salt mixtures are promising for battery applications and fine-tuning of room-temperature ionic liquid (RTIL) properties. Although critical processes take place at interfaces of these systems, including charge transfer and heterogeneous catalytic reactions, the microscopic interfacial structures remain unclear. Here, we apply heterodyne-detected sum-frequency generation spectroscopy to aqueous solutions of imidazolium-based RTILs to unveil the microscopic structure of the interfaces of these solutions with air. Our results show that, under salt-in-water conditions, the orientation of the OH group hydrogen-bonded to the other water molecules flips from the OH group pointing down into the liquid for pure water to up due to the accumulation of anions in the cation-rich interfacial region. However, under the water-in-salt condition, the interfacial water molecules are confined by RTIL, and their orientation is down. Details of the water organization depend critically on the alkyl chain length of the imidazolium cation. Our results demonstrate that the surface structure can be tuned by altering the molecular structure and concentration of the RTIL.

Atomistic simulations of polysaccharide materials for insights into their crystal structure, nanostructure, and dissolution mechanism

AbstractCrystalline polysaccharides are abundant in nature and can be transformed into highly functional materials. However, the molecular basis for the formation of higher-order structures remains unclear. Computer simulation is an advanced tool for modeling macromolecular structures, and the atomistic simulations provide valuable information on the crystalline polysaccharides. Fiber deformation, crystalline transition, and novel nanostructures of cellulose were characterized through molecular dynamics simulations and density functional theory calculations of models of molecular chain sheets extracted from the crystal structure of the cellulose polymorphs. Extended ensemble molecular dynamics simulations were applied to analyze the artificial crystal structure of non-natural amylose analog polysaccharides, revealing the hexagonal packing of double helices through the self-assembly of molecular chains dispersed in aqueous solution. Dissolution simulations of the cellulose and chitin crystalline fibers revealed that the anions of ionic liquids, with their solvation power, played a key role in the cleavage of intermolecular hydrogen bonds in the crystal structure, whereas the cations contributed to irreversible molecular chain dispersion. The good correlation between the actual solubility of polysaccharides and the predicted number of intermolecular hydrogen bonds prompted the development of a platform that combined simulations and machine learning for high-throughput screening of solvents for cellulose and chitin.

Unexpected bell-shaped double layer capacitance promoted by nitrate anions at a-CNx / aqueous electrolyte interface and simulated with the lattice-gas model

Amorphous carbon nitride thin fims, a-CNx, are potentially low cost candidates for electrochemical nitrate treatment by comparison to boron doped diamond electrodes. In aqueous media, a-CNx electrodes are characterized by a large potential window and, in acidic pH solutions, no surface charge capacitive contribution. In perchloric acid at pH 1, nitrate reduction occurs at the negative limit of a potential domain without any significant redox reaction over almost 1 Volt. In this domain, in the presence of a nitrate salt, a bell-shaped behaviour was observed for the interfacial capacitance. Differences were evidenced according to the solvation state of the cations (Na+, K+, Li+, Cs+, (CH3)4N+, (C2H5)4N+), depending on the cation size. Experimental capacitance data were simulated by using the phenomenological theory developed by Kornyshev in the case of ionic liquids. A good agreement was obtained assuming a compact layer in series with the highly structured diffuse layer and taking into account the short-range ion-ion interactions. Thus, at the a-CNx/aqueous electrolyte interface, nitrate anions are engaged into strong anion-cation interactions (ion pairing) especially with small sized cations, leading to nitrate anion trapping in the multilayered interfacial region with a possible negative effect on the nitrate ions electroreduction.

Molecular insight into the dissolution-degradation process of cellulose bunch in ionic liquids

Ionic liquids (ILs) as green solvents have been utilized in dissolving cellulose and fabricating regenerated cellulose fibers. Imidazolium-based ILs with acetate or phosphate anions present advantage, due to the low viscosity and melting point, as well as its excellent ability to form hydrogen bonds (H-bonds) with the hydroxyl groups of cellulose chains. In this work, the microscopic dissolution processes of a cellulose bunch in four ILs were reproduced via molecular dynamics (MD) simulations. The cellulose bunch dissolution capabilities of these four ILs are [Emim][OAc] > [Emim][DMP] > [Emim][DEP] > [Bmim][DMP], as verified through in-situ polarized optical microscope. It is important to note that cellulose may degrade in some ILs during dissolution, affecting the performance of regenerated cellulose, while the underlying mechanism is unclear, and the strength of H-bonds formed between ILs and cellulose chains can reflect their degradation strength Combined with density functional theory (DFT) calculations, the H-bonds formed between different anions and cellulose hydroxyl groups were analyzed in depth and the order of H-bond strength is [OAc]− > [DEP]− > [DMP]−, which is different from the dissolution order of cellulose bunch in [Emim][DEP] and [Emim][DMP]. Further analysis revealed that the difference in diffusion coefficients leads to faster dissolution of cellulose in [Emim][DMP]. This study elucidates the dissolution and degradation processes of cellulose in ILs at the molecular level, offering theoretical insights crucial for the development of novel ILs that are efficient in the process of cellulose spinning.

Assessment of dissociation enthalpies of methane hydrates in the absence and presence of ionic liquids using the Clausius-Clapeyron approach

The Clausius-Clapeyron (CC) equation is generally preferred to obtain dissociation enthalpies (ΔH) of hydrate-forming systems due to its ease of use. The application of other direct and indirect methods becomes more problematic if complex additives such as ionic liquids (ILs) are also present in the system. In this work, around 400 equilibrium data points for methane hydrates in the presence of over 80 ILs were collected from the literature in the temperature and pressure ranges of (272.10 – 306.07) K and (2.48 – 100.34) MPa, respectively. The ΔH of methane hydrates in the absence and presence of ionic liquids (ILs) have been calculated using the CC equation. The compressibility factor (z), required to calculate ΔH at each phase equilibrium condition has been obtained from three different approaches viz., Peng-Robinson (PR) equation of state, Soave-Redlich-Kwong (SRK) equation of state and Pitzer (Pz) correlation. The results were compared to the experimentally reported dissociation enthalpy (54.5 ± 1.5 kJ.mol−1) of methane hydrates. The role of the compressibility factor along with the slope of the equilibrium data set and the temperature/pressure range in determining the outcome of the CC equation has been discussed. The effect of molar mass, molar volume, and hydrate suppression temperature of the ILs on the ΔH of methane hydrates has been explored. The tested ILs do not show a systematic and significant influence on enthalpies, rather they show a large scattering in the ΔH values, which might mask any existing subtle effect of the ILs on the dissociation enthalpies. Therefore, this approach should be dealt with care to obtain molecular-level insights.

Functionalization of ionic liquids for heterogeneous catalysis in CO2 conversion: Cycloaddition of epoxides and hydrogenation

The mitigation of environmental impacts caused by greenhouse gas emissions has become increasingly urgent, and the use of CO2 as a primary carbon source is an alternative in chemical transformations, including the synthesis of organic carbonates, formic acid, or methanol. This work aims to synthesize ionic liquids from the imidazolium cation family to be used in the cycloaddition of CO2 with ILs anchored in SiO2-clay heterostructure, MCM-41 and KIT-6 mesoporous materials, as well as the hydrogenation of CO2 with ILs added to ruthenium complexes, i.e., two catalytic systems. The most satisfactory result for CO2 cycloaddition (TON PC = 226) was obtained using the IL (MeO)3Sipmim.Cl anchored in SiO2-clay heterostructure (0.16 mol%) as the catalyst and ZnBr2 (0.04 mol%) as the co-catalyst. The hydrogenation was conducted with the IL (edaO)3Sipmim.Cl and the ruthenium complex Ru-PNN were not successful, but with co-catalyst PEHA, formic acid/formamide was produced (TON Form = 552). The unique catalytic system that showed activity for forming methanol was the commercial Ru-MACHO, Ru-C29H30ClNOP2, (TON MeOH = 3.3). These results highlight the potential of ruthenium-based complexes and supported ionic liquids as active systems in CO2 conversion.

Ionic liquid catalysed synthesis of benzimidazolone from Ortho-Phenylenediamine in the presence of carbon dioxide as a carbonyl source under solvent free condition

In this study, we report synthesis of benzimidazolones from o-phenylene diamine by utilizing carbon dioxide as a carbonyl source under mild reaction conditions in the presence of ionic liquid as a catalyst. Six bifunctional protonic ionic liquids (PILs) were synthesised by reacting superbases 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) and 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) with proton donors such as Trifluoroethanol (TFE), Cyclopropane carboxylic acid (CPCA) and 2,2,2-Trifluoroacetic acid (TFA). Among them, [TBDH+][TFE−] was the most effective, achieving high conversion rates of o-phenylene diamine to 2-benzimidazolone at 1 bar CO2 pressure and 60° C. This PIL could be reused for up to six cycles. Our method offers a green and efficient approach for producing 2-benzimidazolone derivatives, with potential applications in pharmaceuticals and materials science.

Development of new sustainable pyridinium ionic liquids: From reactivity studies to mechanism-based activity predictions.

This study addresses the development of sustainable pyridinium ionic liquids (ILs) because of their potential applications in agriculture and pharmaceuticals. Pyridinium-based ILs are known for their low melting points, high thermal stability, and moderate solvation properties. We synthesized three novel pyridinium-based ILs: 1-(2-(isopentyloxy)-2-oxoethyl)pyridin-1-ium chloride, 1-(2-(hexyloxy)-2-oxoethyl)pyridin-1-ium chloride, and 1-(2-(benzyloxy)-2-oxoethyl)pyridin-1-ium chloride. The biological activities of these compounds were evaluated through plant growth promotion, herbicidal, and insecticidal assays. Our results show that the benzyloxy derivative significantly enhances wheat and cucumber growth, whereas the isopentyloxy compound has potent herbicidal effects. Computational methods, including DFT calculations and molecular docking, were applied to understand the structure‒activity relationships (SARs) and mechanisms of action. The computational techniques involved dispersion-corrected density functional theory (DFT) with the B3LYP functional and the 6-311G** basis set. Grimme's D3 corrections were included to account for dispersion interactions. The calculations were performed via GAMESS-US software. Quantum descriptors of reactivity, such as ionization potential, electron affinity, chemical potential, and electrophilicity index, were derived from the HOMO and LUMO energies. Molecular docking studies were conducted via the CB-Dock server via AutoDock Vina software to predict binding affinities to cancer-related proteins. Petra/Osiris/Molinspiration (POM) analysis was used to predict the drug likeness and other pharmaceutical properties of the synthesized ILs.

Efficient separation of diisopropyl ether and ethanol using green solvents: Thermodynamic analysis and process simulation

Ionic liquids (ILs) and deep eutectic solvents (DESs) were first proposed as green solvents to study and compare their azeotropic separation effects in diisopropyl ether (DIPE) and ethanol (EA). The COSMO-RS model was used to screen ILs/DESs, and the feasibility of the extractants were comprehensively analyzed in terms of viscosity, thermal stability, and toxicity. Experiments were carried out on selected ILs and DESs, and the results showed that the separation effect of ILs was significantly stronger than that of DESs. Quantum chemical calculations and molecular dynamics simulations were combined to comprehensively analyze and compare the microscopic mechanisms of extraction separation. Based on the experimental data, a DIPE-EA extraction-coupled separation process was designed. For the first time, life cycle analysis was used to comprehensively evaluate the impact of this process on human health and the environment from multiple perspectives, providing theoretical guidance for the separation of alcohol ethers in the industry.

Highly Specific Non-Enzymatic Electrochemical Sensor for the Detection of Uric Acid Using Carboxylated Multiwalled Carbon Nanotubes Intertwined with GdS-Gd2O3 Nanoplates in Human Urine and Serum.

Herein, the electrochemical sensing efficacy of carboxylic acid functionalized multiwalled carbon nanotubes (C-MWCNT) intertwined with coexisting phases of gadolinium monosulfide (GdS) and gadolinium oxide (Gd2O3) nanosheets is explored for the first time. The nanocomposite demonstrated splendid specificity for nonenzymatic electrochemical detection of uric acid (UA) in biological samples. It was synthesized using the coprecipitation method and thoroughly characterized. The presence of functional groups and disorder in the as-synthesized nanocomposite are confirmed using Fourier transform infrared spectroscopy and Raman spectroscopy. Furthermore, field emission scanning electron microscopy, high-resolution transmission electron microscope, X-ray powder diffraction, and X-ray photoelectron spectroscopy provides a clear understanding of the morphology, coexisting phases, and elemental composition of the as-synthesized nanocomposites. The differential pulse voltammetry technique was utilized to elaborate the electrochemical sensing of UA using a GdS-Gd2O3/C-MWCNT modified glassy carbon electrode (GCE), The sensor showed an enhanced current response by more than 2-fold compared to bare GCE. Also, the sensor's performance was further improved by dispersing the nanocomposite in an ionic liquid with the exceptional reproducibility (SD = 0.0025, n = 3). The fabricated UA sensor GdS-Gd2O3/C-MWCNT/IL/GCE demonstrated a wide linear detection range from 0.5-30 μM and 30-2000 μM, effectively covering the entire physiological range of UA in biological fluids with a limit of detection (LOD) of 0.380 μM (+3SD of blank) and a sensitivity of 356.125 μA mM-1 cm-2. Moreover, the electrodes exhibited storage stability for 2 weeks with decrease in zero-day current by only 4.5%. The sensor was validated by quantifying UA in 12 unprocessed clinical human urine and serum samples, and its comparison with the gold standard test yielded remarkable results (p < 0.05). Hence, the proposed nonenzymatic electrochemical UA sensor is selective, sensitive, reproducible, and stable, making it reliable for point-of-care diagnostics.

Investigating the Influence of Protic Ionic Liquid on the Triboelectrical Properties of Trimethylolpropane Trioleate (TMPO)

Under triboelectric conditions, where tribocharging accelerates lubrication failure, lubricants with enhanced electrical properties are essential. Trimethylolpropane Trioleate (TMPO) oil, derived from esters that possess good lubricating properties and wear performance but is lacking in terms of electrical properties which can be further improved when blended with Ionic Liquid. This study blends 1 – 5 wt% of Protic Ionic Liquid (PIL) into TMPO and evaluate the frictional and wear performances of the blends under 1 – 2 A current conditions to understand the behaviour towards the tribological properties of different blends of material. Electric currents ranging around 1 – 2 A are implemented to the custom-designed ball-on-disc tribometer, with a constant 4.5 V voltage supply and the static resistance are measured. Mechanical wear properties are observed after the tribological test with different samples. The frictional properties of all concentrations of PIL in TMPO showed significant frictional improvements with 1%wt PIL showed 53% better results indicating improvements in frictional properties and wear performance under 2A current conditions, owing to its lowest film resistivity of 0.14 mΩ.

Mild one-pot production of glycerol carbonate from CO2 with separation from ionic liquid catalyst

Carbon capture and utilization stands as way forward in the minimization of CO2 emissions. It complements the search for clean and effective energy, as it is challenging to achieve zero to negative CO2 net emissions. The glycerol carbonate product opens a new strategy based on a double-residue approach (glycerol and CO2) to contribute, together with ionic liquids (ILs), drafting a new one-pot concept (intensified three phase reactor) at mild conditions and using homogeneous catalysts. In this work, the catalytic activity of [P666,14][Br] in the cycloaddition of CO2 to glycidol has been demonstrated to be highly effective under mild conditions of 45 °C and 5 bar. In addition, liquid–liquid extraction approach is found to be an efficient separation strategy for carbonate product and IL catalyst. 1-Decanol (DOH) is selected as efficient extracting solvent, due to its almost complete immiscibility with glycerol carbonate, as well as the high distribution ratio of the IL catalyst in DOH rich phase. It implies an easy product separation and, simultaneously, an easy catalyst recovery. A preliminary kinetic validation of the three-phase reactor performance has been properly described, enabling the intensified concept. Finally, combining COSMO/Aspen simulation and life cycle assessment (LCA) methodologies, low energy consumption (avoiding heating) and low GWP scenarios for the CO2 conversion process have been concluded. This work enables a new concept together with concluding the path to developing this CCU technology in the search of zero to negative CO2 emissions to sustainably capture and convert CO2 into value-added products.

Synthesis, Characterization, Bioavailability and Antimicrobial Studies of Cefuroxime-Based Organic Salts and Ionic Liquids

Low oral bioavailability is a common feature in most drugs, including antibiotics, due to low solubility in physiological media and inadequate cell permeability, which may limit their efficacy or restrict their administration in a clinical setting. Cefuroxime is usually administered in its prodrug form, cefuroxime axetil. However, its preparation requires further reaction steps and additional metabolic pathways to be converted into its active form. The combination of Active Pharmaceutical Ingredients (APIs) with biocompatible organic molecules as salts is a viable and documented method to improve the solubility and permeability of a drug. Herein, the preparations of five organic salts of cefuroxime as an anion with enhanced physicochemical characteristics have been reported. These were prepared via buffer-assisted neutralization methodology with pyridinium and imidazolium cations in quantitative yields and presented as solids at room temperature. Cell viability studies on 3T3 cells showed that only the cefuroxime salts combined with longer alkyl chain cations possess higher cytotoxicity than the original drug, and while most salts lost in vitro antibacterial activity against E. coli, P. aeruginosa and B. subtilis, one compound, [PyC10Py][CFX]2, retained the activity. Cefuroxime organic salts have a water solubility 8-to-200-times greater than the original drug at 37 °C. The most soluble compounds have a very low octanol-water partition, similar to cefuroxime, while more lipophilic salts partition predominantly to the organic phase.

Intermolecular Proton Transfer Enabled Reactive CO2 Capture by the Malononitrile Anion.

Task-specific ionic liquids (ILs) employing carbanions represent a new class of ILs for carbon capture. The deprotonated malononitrile carbanion, [CH(CN)2]-, has shown close to equimolar capacity for reactive CO2 capture. Although the formation of the [C(CN)2COOH]- carboxylic acid was found to be the final product, how the hydrogen atom on the [CH(CN)2]- carbanion transfers to the carboxylate group as a proton has not been fully understood. In this work, we employ density functional theory calculations with an implicit solvation model to investigate the proton transfer mechanisms in forming carboxylic acid from the reaction of the [CH(CN)2]- carbanion with CO2. We find that the intramolecular proton-transfer pathway in [CH(CN)2COO]- to form [C(CN)2COOH]- is unlikely due to the high energy barrier of 152 kJ/mol. Instead, the intermolecular proton transfer pathway between two [CH(CN)2COO]- anions is more feasible to form two molecules of [C(CN)2COOH]-, with a significantly lower activation energy of 50 kJ/mol. Moreover, the [C(CN)2COOH]- dimer is further stabilized by the intermolecular hydrogen bonds of the two -COOH groups in the Z-configuration of the π-conjugated planar geometry. This insight of reactive CO2 capture enabled by intermolecular proton transfer will be useful in designing novel carbanions and ILs for carbon capture and conversion.

Feasibility Prediction of Thermally Rearranged Polyimide Membranes with Ionic Liquid Capping for Large‐Scale Industrial Biogas Purification Applications

Feasibility Prediction of Thermally Rearranged Polyimide Membranes with Ionic Liquid Capping for Large‐Scale Industrial Biogas Purification Applications