Recent Progress on Biocatalysis and Biotransformations in Ionic Liquids

Ionic liquids have negligibly low vapor pressure, high stability and polarity. They are regarded as green solvents. Enzymes, especially lipases, as well as whole-cell of microbe, are catalytically active in ionic liquids or aqueous-ionic liquid biphasic systems. Up to date, there have been many reports on enzyme-exhibited features and enzyme-mediated reactions in ionic liquids. In many cases, remarkable results with respect to yield, catalytic activity, stability and (enantio-, regio-) selectivity were obtained in ionic liquids in comparison with those observed in conventional media. Accordingly, ionic liquids provide new possibilities for the application of new type of solvent in biocatalytic reactions.

Self-separation ionic liquid catalyst for the highly effective conversion of H_(2)S by α,β-unsaturated carboxylate esters under mild conditions

The deep-processing utility of pure hydrogen sulfide (H_(2)S) is a significant direction in natural gas chemical industry.Herein,a brand-new strategy of H_(2)S conversion by a,β-unsaturated carboxylate esters into thiols or thioethers using task-specific carboxylate ionic liquids (ILs) as catalyst has been developed,firstly accomplishing the phase separation of product and catalyst without introducing the third component.It can be considered as a cascade reaction in which the product selectivity can be controlled by adjusting the molar ratio of H_(2)S to a,β-unsaturated carboxylate esters.Also,the effects of ILs with different anions and cations,intermittent feeding operations,as well as pressure-time kinetic behaviors on cascade reaction were investigated.Furthermore,the proposed interaction mechanism of H_(2)S conversion using butyl acrylate catalyzed by[Emim][Ac]was revealed by DFT-based theoretical calculation.The approach enables the self-phase separation promotion of catalyst and product and achieves 99%quantitative conversion under mild conditions in the absence of solvent,making the entire process ecologically benign.High-efficiency reaction activity can still be maintained after ten cycles of the catalyst.Therefore,the good results,combined with its simplicity of operation and the high recyclability of the catalyst,make this green method environmentally friendly and cost-effective.It is anticipated that this self-separation method mediated by task-specific ILs will provide a feasible strategy for H_(2)S utilization,which will guide its application on an industrial scale.

Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO_(2)to Propylene Carbonate

Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.

Gas-phase dehydrochlorination of 1, 1, 2, 2-tetrachloroethane over the non-metal supported ionic liquid catalyst

Developing of non-metallic catalyst to replace metal catalyst is a meaningful and challenging direction.In this work,the non-metallic catalyst was synthetized successfully by loading ionic liquid onto the silica surface,which was applied for the gas-phase dehydrochlorination of 1,1,2,2-tetrachloroethane.The 12%TPPC/SiO2(wt%)showed the best results with the conversion of 1,1,2,2-tetrachloroethane reaching 100%.The selectivity of 1,1,2-trichloroethylene was 100%,and no deactivation was found during the evaluation period.The catalytic mechanism was investigated and possible reaction route was given,which was a reference for fabricating and design of solid base catalyst.

Amide Ionic Liquids(AILs)/L-Proline Synergistic Catalyzed Asymmetric Mannich Reactions

Amide ionic liquids （MLs）/L-proline synergistic catalyzed Mannich reactions of isovaleraldehyde, methyl ketones, and aromatic amines were carried out in moderate to high yields （ up to 96% ） and high stereo selectivities （ 〉99% e. e. ）. The products were easily isolated by extraction; and the catalyst system was readily recycled at least thrice without significant loss of efficiency. The scope of the substrates was studied and the interpretation of the manifest improvement of the reaction rates and enantio-selectivity of the novel catalyst system was speculated.

Olefin oligomerization via new and efficient Bronsted acidic ionic liquid catalyst systems

Olefin oligomerization reaction catalyzed by new catalyst systems（a Br？nsted‐acidic ionic liquid as the main catalyst and tricaprylylmethylammonium chloride as the co‐catalyst） has been investigat‐ed. The synthesized Br？nsted acidic ionic liquids were characterized by Fourier transform infrared spectroscopy（FT‐IR）, ultraviolet‐visible spectroscopy（UV）, ^1H nuclear magnetic resonance（NMR）, and ^13 C NMR to analyze their structures and acidities. The influence of different ionic liquids, ionic liquid loading, different co‐catalysts, catalyst ratios（mole ratio of ionic liquid to co‐catalyst）, reac‐tion time, pressure, temperature, solvent, source of reactants, and the recycling of catalyst systems was studied. Among the synthesized ionic liquids, 1‐（4‐sulfonic acid）butyl‐3‐hexylimidazolium hydrogen sulfate（[HIMBs]HSO4） exhibited the best catalytic activity under the tested reaction con‐ditions. The conversion of isobutene and selectivity of trimers were 83.21% and 35.80%, respec‐tively, at the optimum reaction conditions. Furthermore, the catalyst system can be easily separated and reused; a feasible reaction mechanism is proposed on the basis of the distribution of experi‐mental products.

An Efficient and Stable Ionic Liquid System for Synthesis of Ethylene Glycol via Hydrolysis of Ethylene Carbonate

An ionic liquid system of [Bmim]X/[Bmim]OH(X Cl,BF4,and PF6,) was developed for the hydroly-sis of ethylene carbonate to ethylene glycol. The important parameters,such as the variety of ionic liquids,molar ratio of [Bmim]X to [Bmim]OH,amount of ionic liquid,molar ratio of water to ethylene carbonate,reaction tem-perature,pressure and reaction time,were investigated systematically. Excellent yield(>93%) and high selectivity(99.5%) of ethylene glycol were achieved. Under the optimum reaction conditions,the ionic liquid system could be reused at least five times and the selectivity of ethylene glycol remained higher than 99.5%.

Protic vs aprotic ionic liquid for CO2 fixation:A simulation study

The cycloaddition of CO2 with epoxides catalyzed by ionic liquids(ILs)has been a widely ongoing studied hot topic over the years.Recent experimental research has shown that the protic ionic liquids(PILs)behave stronger hydrogen proton donating ability than aprotic ionic liquids(APILs),and can effectively catalyze the cycloaddition of CO2.Unfortunately,the mechanistic explanation remains primarily unraveled.Herein,a detailed simulation study on the cycloaddition reaction catalyzed by PIL([HDBU][Mim])in comparison with APIL([MeDBU][Mim])re-action catalysts was conducted,including the three-step route(ring-opening of PO(propylene oxide),insertion of CO2 and ring-closure of propylene carbonate(PC))and two-step route(simultaneously ring-opening of PO and addition of CO2,and then ring-closure of PC).Based on the activation energy barrier of the rate-determining step,PIL preferentially activates PO as the optimal route for the reaction with the energy barrier of 23.2 kcal mol-1,while that of APIL is 31.2 kcal mol-1.The role of[HDBU]+in the reaction was also explored and found that the direct formation of intermolecular hydrogen bond(H-bond)between[HDBU]+and the reactants(PO+CO2)was unfavorable for the reaction,while the cooperation with the anion[Mim]-to assist indirectly was more conducive.To fully consider the reaction microenvironment of ILs,ONIOM calculation was used to study the solvent effect.At last,the above conclusions were further verified by the analysis of intermediates with charge,non-covalent interaction(NCI),and atoms in molecules(AIM)methods.The computational findings show that ILs studied in this work have dual functions of catalyst and solvent,enabling a microscopic understanding of the ILs catalyst for CO2 utilization as well as providing guidance for the rational design of more efficient ILs-based catalysts.

FeCl_3·6H_2O Catalyzed Reaction of Aromatic Aldehydes with 5, 5-Dimethyl-1, 3-cyclohexandione in Ionic Liquids

The reaction of aromatic aldehydes 1 with 5, 5-dimethyl-1, 3-cyclohexandione 2 was investigated in this paper by using [bmim][BF4] as the reaction medium. It was found that when the reaction was carried out in the presence of catalytic amount of FeCl3·6H2O, xanthenediones 3 was obtained in high yields. On the other hand, when a combination of trimethylchlorosilane (TMSCl) and FeCl3·6H2O was employed as the catalyst, the reaction afforded ring-opening derivatives of xanthenediones 4 with high efficiency.

Efficient and sustainable V-catalyzed oxidative desulfurization of fuels assisted by ionic liquids

Fuel desulfurization is an appealing topic for the chemical industry since severe environmental regulations regarding SO_2 emissions have been legislated in many countries. In order to reduce the amount of sulfur-containing compounds in fuels,responsible for high SO_x emission levels,a green chemistry approach is compulsory. In this paper,vanadium salen and salophen complexes were used in the oxidation of a model aromatic sulfide,such as dibenzothiophene( DBT),in the presence of H_2O_2 as green oxidant. The oxidative process was successfully coupled with the extraction of the oxidized compounds by ionic liquids. The system resulted highly selective for sulfide oxidation,showing poor reactivity toward the oxidation of alkenes and allowing a significant reduction of S content in a model benzine. To note,the use of microwave in place of standard heating allowed to obtain 98% of DBT oxidation and almost complete sulfur extraction in the model fuel in 1000 s. For these reasons,this system was considered an easy,rapid and clean process to achieve fuel desulfurization.

Probing the intrinsic catalytic activity of carbon nanotubes for the metal-free oxidation of aromatic thiophene compounds in ionic liquids

A metal-free catalytic system combining oxidized carbon nanotubes (oCNTs) and ionic liquids (ILs) is presented for the oxidation of aromatic thiophene compounds with H2O2 as an oxidant. The oCNTs exhibit impressively high activity and stability in the system, which show an even better performance than those of some reported metal catalysts. The ILs are proved to have indispensable influence on the enhanced catalytic performance of the oCNTs. Detailed characterization by TG-MS and XPS demonstrates that the carbonyl groups are the active sites for the oxidation process, which is further supported by the deactivation and the model catalysts experiments. The quantitative analysis of different oxygen groups in oCNTs could be achieved by an isothermal temperature programmed TG-MS method. The concentration of carbonyl groups is 1.46 mmol per 1 g oCNTs and the tuiriover frequency of oCNTs could also be obtained (10.7 h^-1 in the presence of OmimPF6). H2O2 decomposition experiments combined with the EPR results reveal that the presence of OmimPF6 can avoid the intermediate HO· to form O2 and then improve the catalytic performance of oCNTs for the oxidation of dibenzothiophene.

Efficient conversion of H_(2)S into mercaptan alcohol by tertiary-amine functionalized ionic liquids

The resource utilization of hydrogen sulfide(H_(2)S)is of great significance in natural gas chemical industry.Described herein have developed a novel method mediated in tertiary amine-functionalized ionic liquids(ILs)to convert H_(2)S into mercaptan alcohols with enols.The effect of ILs,substra te scope,and regeneration experiments have been investigated.It is found that the conversion of 3-methyl-2-buten-1-ol by H_(2)S can reach 52%with a 50%(mol)catalyst loading of bis(2-dimethylaminoethyl)ether methoxyacetate within 12 hat 90℃.The reaction mechanism was speculated based on theoretical calculation.Besides,a plausible reaction-separation-integrated strategy was further proposed.This work reveals an effective insight into the capture and catalytic conversion of H_(2)S to high valuable mercaptan alcohol,which makes the utilization method of H_(2)S resource universal and has the potentiality for industrial application.

Preparation of lactic acid from glucose in ionic liquid solvent system

A new reaction system was designed to economically convert glucose to lactic acid environment-friendly. Hydrophobic ionic liquids were chosen as solvent that can promote the decomposition reaction of glucose, and the catalytic performance of the solid bases was evaluated. Both the reaction temperature and time can affect the yield of lactic acid. A high yield （97%） of lactic acid was achieved under the optimal reaction condition. The IH NMR spectra and HPLC-MS were used to identify the formation of the lactic acid and variations of ionic liquid. It is found that ionic-liquids have a unique solvent effect for glucose and bases. Water can be used as solvent to extract calcium lactate. This shows a great potential of hydrophobic ionic liquids in the solid bases catalyzed reaction that is limited by the weak solubility of solid bases in organic and water solution.

Catalytic Oxidation of Cyclohexane over ZSM-5 Catalyst in N-alkyl-N-methylimidazolium Ionic Liquids

Heterogeneous oxidation of cyclohexane by tert-butyl hydroperoxide (TBHP) was carried out over ZSM-5 catalysts with different Si/Al ratios in ionic liquids and organic molecular solvents. Higher yield and selec-tivity of the desired products were found in ionic liquids than in molecular solvents. The conversion of cyclohexane exhibits a decrease from 15.8% to 10.8% with the increase of Si/Al ratio of the HZSM-5 catalyst, and all the cata-lysts exhibit good selectivity of monofunctional oxidation products at around 97%. The activity of catalyst is found strongly dependent on the alkyl chain length of ionic liquid.

Biphasic Hydrogenation and Hydroformylation of Natural Olefins with a Binuclear Rhodium Complex in Ionic Liquid/Toluene

The complex [Rh（CO）（Pz）（TPPMS）]2, （TPPMS = m-sulfonatophenyl-diphenylphosphine, Pz = Pirazolate） was evaluated as a catalyst precursor in the hydroformylation of allylbenzenes （eugenol and estragol） and terpenes （limonene and myrcene） and in the hydrogenation of α,β-unsaturated aldehydes （crotonaldehyde, cinnamaldehyde and citral） in a biphasic medium toluene/ionic liquid. Under the reaction conditions studied （P = 600 psi, T= 95 ℃, S/C = 300：1）, the rhodium system showed a high activity and selectivity towards the desired aldehydes. The catalytic phase could be recycled up to five times without any evident loss of activity or selectivity.

Which is the determinant for cellulose degradation in cooperative ionic liquid pairs: dissolution or catalysis?

Catalytic conversion of sustainable cellulose to the value-added chemicals and high quality biofuel has been recognized as a perfect approach for the alleviation of the dependence on the non-renewable fossil resources. Previously, we successfully de- signed and explored novel and efficient cooperative ionic liquid pairs for this renewable material, which has advantages of high reactor efficiency than current technologies because of the dissolution and in situ catalytic decomposition mechanism. Here, the determinant of this process is further studied by the intensive investigation on the relationship between the cellulose conversion and the properties of ionic liquid catalyst and solvent. Scanning electron microscope （SEM）, thermogravimetric analysis （TG） and elemental analysis were used for the comparative characterization of raw cellulose and the residues. The re- suits demonstrate that this consecutive dissolution and in situ catalysis process is much more dependent on the dissolution ca- pability of ionic liquid solvent, while comparatively, the effect of in situ acid catalysis is relatively insignificant.

Heteropoly Ionic Liquid Functionalized MOF-Fe:Synthesis,Characterization,and Catalytic Application in Selective Acetalization of Glycerol to Solketal as a Fuel Additive at Room Temperature,Solvent-Free Conditions

In this work,we have reported the synthesis of a series of heterogeneous catalysts,viz.,[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe,[HMIm]_(3)[PMo_(12)O_(40)]@MOF-Fe,and[HMIm]_(4)[SiW_(12)O_(40)]@MOFFe,by a simple impregnation method.The catalysts were characterized by several techniques,such as FTIR,EDX,XRD,SEM,elemental mapping,and TGA.Among these materials,[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe had more acidic sites(confirmed by potentiometric titration)and high stability around 598℃(confirmed by TGA).The catalytic prospect of the materials was examined through selective acetalization of glycerol to solketal as a fuel additive under solvent-free and room-temperature conditions.[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe exhibited the highest catalytic activity among the three catalysts in terms of glycerol conversion(100%),solketal selectivity(100%),and solketal yield(100%).A recyclability study of[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe showed that the material could be reused for up to 7 cycles with insignificant loss in its catalytic performance.

Mesoporous poly(ionic liquid)s with dual active sites for highly efficient CO_(2)conversion

Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.

Bronsted acidic ionic liquid [C_3SO_3HDoim]HSO_4 catalyzed one-pot three-component Biginelli-type reaction: An efficient and solvent-free synthesis of pyrimidinone derivatives and its mechanistic study

A series of Bronsted acidic ionic liquids（ILs） were prepared and used for Biginelli-type condensation reaction among aromatic aldehydes, urea or thiourea and cyclopentanone. Through this reaction, the synthesis of various pyrimidinones could be achieved. Of interest, it was found that the reaction was efficiently catalyzed by a novel, eco-friendly functionalized IL [C3SO3HDoim]HSO4, which could be reused for at least 7 times without significantly loss of catalytic activity. The reaction proceeded efficiently at 80℃ to afford the desired products in good yield（up to 96%）. In addition, a possible mechanism that accounted for the IL [C3SO3HDoim]HSO4-catalyzed reaction was proposed.

Recent advances in ionic liquids-based hybrid processes for CO_(2) capture and utilization

CO_(2) capture and utilization(CCU)is an effective strategy to mitigate global warming.Absorption,adsorption and membranes are methods used for CO_(2) separation and capture,and various catalytic pathways have also been developed for CO_(2) utilization.Although widely researched and used in industry,these processes are energy-intensive and this challenge needs to be overcome.To realize further optimization,novel materials and processes are continuously being developed.New generation materials such as ionic liquids(ILs)have shown promising potential for cost-effective CO_(2) capture and utilization.This study reviews the current status of ILs-based solvents,adsorbents,membranes,catalysts and their hybrid processes for CO_(2) capture and utilization.The special properties of ILs are integrated into new materials through hybridization,which significantly improves the performance in the process of CCU.