Catalysis In Ionic Liquids Research Articles

Lignin Conversion Using Catalytic Ionic Liquids: Understanding the Role of Cations, Anions, and Hammett Acidity Functions

Because it is undisputable that lignin depolymerization is a must to make the biorefinery concept economically feasible, several efforts are put toward it; however, a lot of catalyst designing is required to achieve efficient depolymerization activities. In this work, we show a systematic approach in the synthesis and characterization of ionic liquids (ILs) with varying combinations of cations (imidazole, benzimidazole, phosphonium, and ammonium) and anions (HSO4, PTS (p-toluenesulfonate), Cl, H2PO4, SnCl3, FeCl4, and CuCl3) for the depolymerization of lignin into low-molecular weight aromatic fractions (<220 g/mol) under mild reaction conditions (120 °C, 1 h, ambient pressure). In a methodical approach, effects of various reaction parameters such as temperature (70–170 °C), time (15–360 min), pressure (N2, 0.5–3 MPa), solvents and substrate, and so forth were studied to achieve best activity. Among all the catalysts, IL with the imidazolium cation and HSO4 as the anion showed best activity (78% yield). Subsequent to depolymerization, three aromatic monomers (5 wt % pure vanillin) were isolated using flash column chromatography. These aromatic monomers were characterized using gas chromatography (GC), GC–mass spectrometry, and NMR techniques for their purity. Hammett acidity functions (H0) of ILs were measured using UV–vis photo-spectroscopy, and values are correlated with lignin depolymerization results. Lignin and tetrahydrofuran-soluble products were thoroughly characterized using assorted physicochemical techniques such as NMR (1H and 13C), gel permittivity chromatography, thermogravimetric analysis, and so forth. The catalyst was recycled up to six runs and showed similar results in consecutive reactions.

Highly efficient synthesis of 1-methoxy-2-propanol using ionic liquid catalysts in a micro-tubular circulating reactor

The catalysis of ionic liquids (ILs) in the traditional stirred reactor suffers from insufficient mass and heat transfer, which always needs a long reaction time and results in a low reaction rate. In this work, highly efficient synthesis of 1-methoxy-2-propanol via the alcoholysis reaction of propylene oxide (PO) with methanol was proposed and achieved by the combination of micro-tubular circulating reactor with the IL [N4444][Buty] catalyst. Compared with the stirred reactor, the rate of alcoholysis reaction in a micro-tubular circulating reactor was found to be significantly improved. The reaction time was remarkably shortened to 20 min from 180 min as well as the yield of 1-methoxy-2-propanol reached 92%. Moreover, the kinetic study further demonstrated that the main reaction rate to 1-methoxy-2-propanol (K1) was about 20 times larger than the side reaction rate to byproduct 2-methoxy-1-propanol (K2) in the temperature range of 363–383 K. Such combination of micro-tubular circulating reactor with IL catalysts is believed to be a class of effective process intensification technique for highly efficient synthesis of 1-methoxy-2-propanol.

Novel polymeric acidic ionic liquids as green catalysts for the preparation of polyoxymethylene dimethyl ethers from the acetalation of methylal with trioxane.

A series of micro–mesoporous polymeric acidic ionic liquids (PAILs) have been successfully synthesized and subsequently characterized using Fourier transform-infrared spectroscopy, N2 adsorption–desorption isotherms, scanning electron microscopy and thermogravimetry. Furthermore, the catalytic performance of the synthesized PAILs was investigated for the acetalation of methylal (DMM1) with 1,3,5-trioxane (TOX), micro–mesoporous PAILs copolymerized by divinylbenzene with cations and anions exhibited moderate to excellent catalytic activities for the acetalation. In particular, VIMBs–AMPs–DVB, with higher specific surface area (25.51 m2 g−1) and total pore volume (0.15 cm3 g−1) displayed an elevated conversion of formaldehyde (82.2%) and selectivity for polyoxymethylene dimethyl ethers (CH3O(CH2O)nCH3; PODEn or DMMn) n = 3–8 (52.6%) at 130 °C, 3.0 MPa for 8 h. Moreover, the influence of various reaction parameters was investigated by employing VIMBs–AMPs–DVB as the catalyst and it demonstrated high thermal stability and easy recovery.

In Situ Tracking of Organic Reactions at the Vapor/Liquid Interfaces of Ionic Liquids.

The molecular structures of ionic liquids at interfaces play a crucial role in determining their chemical activities in applications. In situ X-ray photoelectron spectroscopy (XPS) was used to track the evolution of X-ray irradiation-induced chemical reactions in a series of ionic liquids ([Cn mim][AuCl4 ]; n=4, 6, 8, 10) on the Si (111) single-crystal surface. Analyses of microstructure and chemical bonding based on the XPS results indicated that reactions occurred at the vapor/liquid interfaces of the ionic liquids. The time-resolved XPS spectra revealed that with increasing irradiation time, the intensity of the peak corresponding to trivalent Au anion decreased for the four ionic liquids as Au was continually reduced to a lower chemical state and finally converted to gold nanoparticles. The rate and conversion of the reaction were associated with the length of the alkyl chain of the ionic liquids cation. Molecular dynamics simulations further revealed that the alkyl chain of the cation in the ionic liquids was oriented towards the vacuum environment at the vapor/liquid interface. Our results provide a real-time atomic-scale experimental evidence of organic reactions at the vapor/liquid interfaces of ionic liquids. The findings are important for understanding the roles of ionic liquids in catalysis, separation, electrochemistry, functional materials, and so on.

Conversion of Symphytum officinale and Panicum virgatum plant extracts to 5-hydroxymethylfurfural catalysed by metal chlorides in ionic liquids

The present work examined the potential for two plants grown on Canadian soil, Symphytum officinale L. (common comfrey) and Panicum virgatum L. (switchgrass), to produce 5-hydroxymethylfurfural using metal chloride catalysis in two ionic liquids, 1-butyl-3-methylimidazolium chloride or 1-ethyl-3-methylimidazolium chloride. Furthermore, two pre-treatments, namely the dilute sulfuric acid treatment and the methanol extraction, were studied as a way to improve sugar availability and increase 5-hydroxymethylfurfural yields compared with untreated biomass. The 0.5 mol/L H2SO4 hydrolysis under autoclave conditions produced sugar-rich extracts containing 230 ± 23 mg of sugars per gram of hydrolysed biomass for comfrey and 425 ± 13 mg of sugars per gram of hydrolysed biomass for switchgrass. The methanol extraction produced extracts high in simple sugars with concentration of 300 ± 60 mg of sugars per gram of dry extract for comfrey and 202 ± 16 mg of sugars per gram of dry extract for switchgrass. The yield of 5-hydroxymethylfurfural was improved from less than 1% using untreated biomass to 6.04% and 18.0% using dry methanol extracts of comfrey and switchgrass, respectively. These yields, although small, are important, as they show for the first time that a methanol extract could enhance the metal chloride catalysis in ionic liquids for 5-hydroxymethylfurfural production from biomass.

Volcano Plots Emerge from a Sea of Nonaqueous Solvents: The Law of Matching Water Affinities Extends to All Solvents.

The properties of all electrolyte solutions, whether the solvent is aqueous or nonaqueous, are strongly dependent on the nature of the ions in solution. The consequences of these specific-ion effects are significant and manifest from biochemistry to battery technology. The “law of matching water affinities” (LMWA) has proven to be a powerful concept for understanding and predicting specific-ion effects in a wide range of systems, including the stability of proteins and colloids, solubility, the behavior of lipids, surfactants, and polyelectrolytes, and catalysis in water and ionic liquids. It provides a framework for considering how the ions of an electrolyte interact in manifestations of ion specificity and therefore represents a considerable conceptual advance on the Hofmeister or lyotropic series in understanding specific-ion effects. Underpinning the development of the law of matching water affinities were efforts to interpret the so-called “volcano plots”. Volcano plots exhibit a stark inverted “V” shape trend for a range of electrolyte dependent solution properties when plotted against the difference in solvation energies of the ions that constitute the electrolyte. Here we test the hypothesis that volcano plots are also manifest in nonaqueous solvents in order to investigate whether the LMWA can be extended to nonaqueous solvents. First we examine the standard solvation energies of electrolytes in nonaqueous solvents for evidence of volcano trends and then extend this to include the solubility and the activity/osmotic coefficients of electrolytes, in order to explore real electrolyte concentrations. We find that with respect to the solvent volcano trends are universal, which brings into question the role of solvent affinity in the manifestation of specific-ion effects. We also show that the volcano trends are maintained when the ionic radii are used in place of the absolute solvation energies as the abscissa, thus showing that ion sizes, rather than the solvent affinities, fundamentally determine the manifestation of ion specificity. This leads us to propose that specific-ion effects across all solvents including water can be understood by considering the relative sizes of the anion and cation, provided the ions are spherical or tetrahedral. This is an extension of the LMWA to all solvents in which the “water affinity” is replaced with the relative size of the anion and cation.

Sustainable Catalysis in Ionic Liquids

Sustainable Catalysis in Ionic Liquids

Ionic Liquids in Asymmetric Synthesis: An Overall View from Reaction Media to Supported Ionic Liquid Catalysis

AbstractIonic liquids, as a special class of organic compounds, have attracted ever‐growing interest in recent years. They have been employed in many organic transformations as a green alternative to volatile organic solvents and as a catalyst to modify catalytic activity and recyclability. Recent developments have demonstrated that ionic liquids might also have many benefits in asymmetric reactions. In this review, we survey the use of ionic liquids in asymmetric transformations, including the use of ionic liquids as reaction media in asymmetric reactions, ionic‐liquid‐tagged chiral catalysts for use in asymmetric synthesis, and supported ionic liquid catalysts in asymmetric transformations.

Waste Recycling: Ionic Liquid-Catalyzed 4-Electron Reduction of CO2 with Amines and Polymethylhydrosiloxane Combining Experimental and Theoretical Study

The acetate-based ionic liquids (ILs), e.g., [nBu4N]OAc, have been developed for challenging 4-electron reduction of CO2 with amines and hydrosilane to afford aminals. Notably, polymethylhydrosiloxane, a cheap byproduct of the silicone industry, also works well as a reductant. Furthermore, an alternative pathway is rationally proposed via thorough density functional theory (DFT) study. In addition, the ILs play a surprisingly significant role through decreasing activation free energy. More importantly, the essence of being kinetically favorable with 4-electron reduction and thermodynamically favorable with 6-electron reduction is unveiled by DFT study, which guides us to successfully get 6-electron reductive products of CO2, i.e., methylamine. This work represents upgrading usage of both carbon and silicon wastes to valuable chemicals via IL catalysis.

Selective conversion of chitosan to levulinic acid catalysed by acidic ionic liquid: Intriguing NH2 effect in comparison with cellulose

A highly selective route to produce levulinic acid (LA), one of the top twelve platform chemicals, from chitosan has been provided by catalysis of acidic ionic liquids (ILs). The effect of NH2 group on the conversion efficiency, IL recyclability and catalytic mechanism has been elucidated thoroughly in comparison with cellulose. Dilution effect was displayed significantly at lower chitosan intake, whereby the yield of LA was dramatically improved up to 64%. The relationship between IL structure and LA yield was established, disclosing that acidity of IL dictates the conversion efficiency of chitosan to LA predominantly. Moreover, methyl isobutyl ketone (MIBK) proved to be efficient extractant for the separation of LA product, and IL can be recycled without loss of activity by supplementing sulfuric acid. In addition, the chemical structures and morphologies of the solid residues were investigated by SEM and IR, indicating two-stage mechanism that chitosan first quaternizes and depolymerizes to glucosammonium salt, followed by transformation into LA through NH3 elimination.

Glucose isomerization catalyzed by bone char and the selective production of 5-hydroxymethylfurfural in aqueous media

Glucose isomerization and selective production of 5-hydroxymethylfurfural in aqueous media, using combined catalysis of bone char and acidic ionic liquid.

Theoretical study on the effective dehydrochlorination of 1,2-dichloroethane catalyzed by tetraalkylphosphonium chlorides: electrostatically controlled reactivity

Herein, we report a DFT study on how and why tetraalkylphosphonium chlorides efficiently catalyze the dehydrochlorination of 1,2-dichloroethane.

A facile and efficient procedure for one-pot four-component synthesis of polysubstituted spiro pyrano[2,3-c]pyrazole and spiro 1,4-dihydropyridine catalyzed by a Dabco-based ionic liquid under mild conditions

Spiro pyrano[2,3-c]pyrazoles and spiro 1,4-dihydropyridines were obtained in high yields from different amine components under Dabco-based ionic liquid catalysis.

Lignocellulosic biomass delignification using aqueous alcohol solutions with the catalysis of acidic ionic liquids: A comparison study of solvents

The exploration of effective deconstruction of biomass complex structures and mild fractionation into individual components is a profound challenge for the development of biorefinery. Herein, a biomass fractionation process, via treating biomass in various aqueous alcohol solutions with the catalysis of acidic ionic liquids 1-butyl-3-methylimidazolium hydrogen sulfate, was demonstrated to fractionate coir and poplar into cellulose materials with a lignin content as low as 0.95% and lignin with a delignification rate of up to 98%. The participation of acidic ionic liquids into the solvent system greatly multiplied the biomass fractionation efficiency. The analysis on effects of the chemical structure and solubility parameter of alcohols on the delignification efficiency provided a rational and meaningful way to predict and screen solvent for the biomass fractionation process. Lignin in the present study exhibited similar structure with milled wood lignin, and comparable molecular and thermal properties with the conventional organosolv lignin.

Catalytic Ionic-Liquid Membranes: The Convergence of Ionic-Liquid Catalysis and Ionic-Liquid Membrane Separation Technologies.

Membrane technologies enable the facile separation of complex mixtures of gases, vapours, liquids and/or solids under mild conditions. Simultaneous chemical transformations can also be achieved in membranes by using catalytically active membrane materials or embedded catalysts, in so-called membrane reactors. A particular class of membranes containing or composed of ionic liquids (ILs) or polymeric ionic liquids (pILs) have recently emerged. These membranes often exhibit superior transport and separation properties to those of classical polymeric membranes. ILs and pILs have also been extensively studied as separation solvents, catalysts and co-catalysts in similar applications for which membranes are employed. In this review, after introducing ILs and their applications in catalysis, catalytic membranes and recent advances in membrane separation processes based on ILs are described. Finally, the nascent concept of catalytic IL membranes is highlighted, in which catalytically active ILs/pILs are incorporated into membrane technologies to act as a catalytic separation layer.

Group IIIA Halometallate Ionic Liquids: Speciation and Applications in Catalysis

Group IIIA halometallate ionic liquids (ILs) present fascinating properties for the field of catalysis, particularly through the ability to tune their Lewis acidity solely by changing the metal complex speciation. In this Review, we present a critical perspective on the use of Group IIIA halide-derived ILs in catalysis, focusing on the effect of speciation of the metal-containing ions on various acid-catalyzed reactions, some of which are applied industrially. We summarize all applications of Group IIIA halometallates in catalysis (where they are notably well-represented in reactions of importance in petroleum refining and processing), compare the authors’ investigations or assumptions with regard to chemical speciation, and present examples of how the tunability of these materials is used to overcome their initially perceived drawbacks. Further, advances in the field of halometallate ILs such as the role of the cations in the IL, IL analogues, and heterogenization strategies are discussed. High selectivi...

The Beneficial Sinergy of MW Irradiation and Ionic Liquids in Catalysis of Organic Reactions

The quest for sustainable processes is becoming more and more important, with catalysis playing a major role in improving atom economy and reducing waste. Organic syntheses with less need of protecting/de-protecting steps are highly desirable. The combination of microwave irradiation, as energy source, with ionic liquids, as both solvents and catalysts, offered interesting solutions in recent years. The literature data of the last 15 years concerning selected reactions are presented, highlighting the importance of microwave (MW) technology coupled with ionic liquids.

Functional Ionic Liquids Promoted Double Michael Reaction of Benzofuran‐3‐one or 1‐Indone and Symmetric Dienones: Construction of Spiro[benzofuran‐2,1’‐cyclohexane]‐3‐one or Spiro[cyclohexane‐1,2’‐indene]‐1’,4(3’H)‐dione Derivatives

The double Michael reactions between benzofuran‐3‐one or 1‐indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran‐2,1’‐cyclohexane]‐3‐one or spiro[cyclohexane‐1,2’‐indene]‐1’,4(3’H)‐dione derivatives containing a spiro quaternary stereogenic center, which widely exist in biologically active products and building blocks in organic synthesis, were obtained in excellent yields (up to 99%). This catalytic system was also extended to the double Michael reaction of less reactive 1‐indone and the desired products were also obtained in 31%‐62% yields. The catalytic system was highly active and efficient for a broad of substrates under mild conditions.

Solvent-free Knoevenagel reaction catalysed by reusable pyrrolidinium base protic ionic liquids (PyrrILs): synthesis of long-chain alkylidenes

In this work, an efficient and reusable pyrrolidinium ionic liquid (PyrrIL) catalysis system was developed and used in a Knoevenagel condensation reaction of long-chain aldehydes with several 1,3-dicarbonyl compounds.

Surface-active ionic liquids in catalysis: Impact of structure and concentration on the aerobic oxidation of octanol in water

We present design and synthesis of surface-active ionic liquids for the application in micellar catalysis. A series of 1-methyl-3-dodecylimidazolium based ionic liquids with variable core structures including dicationic and zwitterionic ones was synthesized and characterized. These surface-active ionic liquids where applied in the aerobic oxidation of aliphatic alcohols to carbonyl compounds. A strong dependence on the ionic liquid concentration and structure was identified, which is in accordance with the concepts of micellar catalysis. Optimum conditions for the oxidation of 1-octanol could be identified, and the use of surface-active ionic liquids strongly improved the reaction performance compared to pure water. Under optimized conditions, it was possible to isolate up to 75% of octanoic acid using only small amounts of surface-active ionic liquid in a 0.05mM solution in water without further ligands.