CN107652186A - Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof - Google Patents

Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof Download PDF

Info

Publication number
CN107652186A
CN107652186A CN201710852368.4A CN201710852368A CN107652186A CN 107652186 A CN107652186 A CN 107652186A CN 201710852368 A CN201710852368 A CN 201710852368A CN 107652186 A CN107652186 A CN 107652186A
Authority
CN
China
Prior art keywords
room temperature
ionic liquid
heteropolyacid anions
liquid
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710852368.4A
Other languages
Chinese (zh)
Other versions
CN107652186B (en
Inventor
李春香
徐晟�
雷斌
袁青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201710852368.4A priority Critical patent/CN107652186B/en
Priority to CN201610224764.8A priority patent/CN105801449B/en
Publication of CN107652186A publication Critical patent/CN107652186A/en
Application granted granted Critical
Publication of CN107652186B publication Critical patent/CN107652186B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62Quaternary ammonium compounds
    • C07C211/63Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms

Abstract

Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof, it is related to a kind of ionic liquid at room temperature and preparation method thereof.The invention aims to solve the problems, such as that existing polyoxometalate ionic liquid species, quantity are few and it is non-liquid to be at room temperature.It is made up of victoria blue B cation, heteropolyacid anions and solvent;Method:First, prepare and contain [X2M18O62]4‑、[XM12O40]4‑Or [α SiMo12O40]4‑The mixed organic solvents of anion;2nd, victoria blue B solution is prepared;3rd, mix;4th, clean;Or it is made up of four n-octyl bromination ammonium cations, heteropolyacid anions and solvent;Method:The mixed organic solvents of anion are prepared using tungstate dihydrate acid sodium, acetonitrile and sulfuric acid solution as raw material, add four n-octyl ammonium bromide solution stirring reactions, then obtain through removal of impurities.Present invention is mainly used for prepare ionic liquid at room temperature.

Description

Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof
Technical field
The present invention relates to a kind of ionic liquid at room temperature and preparation method thereof, it is on April 12nd, 2016 applying date to be, application number For 201610224764.8《Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof》Divisional application.
Background technology
Ionic liquid refer at room temperature or<Under 100 DEG C of temperature conditionss present liquid, substantially by anions and canons institute group Into salt, also referred to as low temperature molten salt.Compared with traditional liquid material, ionic liquid has following prominent characteristics:(1) steam Force down, it is non-volatile, it is nonflammable, to human and environment low toxicity;(2) fusing point is low, and liquid condition temperature range is wide (to be below or near to room - 300 DEG C of temperature), chemical stability and heat endurance are good;(3) electrochemical stability is high, and electrochemical window is wider;(4) solvability By force, inorganic matter, organic matter and polymer can be dissolved;(5) two-phase or multiphase system can be formed with other solvents, is adapted to be reaction Jie Matter, catalyst and separation solvent etc.;(6) it is reusable.At present, ionic liquid is as a kind of new solvent and medium, quilt It is widely used in the processes such as organic reaction, materials synthesis and mixture separation.Especially as " green solvent " by as reaction Solvent replaces organic solvent to carry out the product of catalyst-solvent or extractive reaction mixture, greatly reduces heterogeneous catalytic reaction body The use of organic solvent in system, organic solvent can be reduced to harm caused by atmospheric environment and health.
Ionic liquid is made up of organic cation and inorganic or organic anion, common cation have quaternary ammonium salt from Son, quaternary phosphine salt ion, imidazolium ion etc., anion has halide ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc.. In the ionic liquid studied at present, cation is mainly based on glyoxaline cation, and anion is mainly with halide ion and other Based on inorganic acid ion.Ionic liquid can be divided into halogenation ionic liquid and the major class of new ionic liquid two by the difference of anion. Halogenation ionic liquid is by organic cation AlCl3Or AlBr3Form, specific preparation method is that SOLID ORGANIC is cationic halogenated Salt and AlCl3Or AlBr3It is obtained by mixing, its composition is not fixed.Such ionic liquid substantial amounts, but it is sensitive to water and air, it is main To be employed as reaction dissolvent.New ionic liquid is a kind of multifunctional ion liquid just to have grown up in the recent period, is had solid Fixed chemical composition, to water, air-stable, according to the difference of anion, such as C3F7COO-、SbF6 -、AsF6 -, heteropolyacid anions Deng assigning new ionic liquid more rich property by anion, such as catalysis, extract and separate metal ion, absorption and separation gas. At present, the application study of new ionic liquid is concentrated mainly on organic synthesis, catalytic reaction, isolation technics and utilizes ionic liquid Desulfurization etc..
Generally, the preparation method of organic ion liquid has one-step synthesis and two-step synthesis method.One-step synthesis is to pass through What acid-base neutralization reaction or quaterisation one-step synthesis obtained.One-step synthesis is simple to operate, and without accessory substance, product is very Easily purifying.The first step of two-step synthesis method be by imidazoles and alkyl halide reaction synthesis quaternary ammonium salt, second step be quaternary ammonium salt with Lewis acid is reacted or enters line replacement reaction with the alkali metal salt containing required anion or acid, obtains object ion liquid. Or proper ratio organic cation or inorganic anion are added directly into inorganic or organic salt, corresponding ionic liquid is made (direct method).It is particularly cloudy comprising heteropoly acid by one-step method or direct method, two-step synthesis method, the new ionic liquid of synthesis The ionic liquid of ion, because polyoxometallate ionic charge density is high, bonding action power is strong between anions and canons so that its Most of is at ambient temperature solid, is only existed>Liquid could be presented under 100 DEG C or 200 DEG C of temperature conditionss.Narrowly, It can not be referred to as ionic liquid under this kind of room temperature condition for the material of solid.Therefore, new ionic liquid is prepared, it is particularly more golden Belong to oxygen hydrochlorate ionic liquid, can not only enrich species, the quantity of ionic liquid, can also rely on heteropolyacid anions to assign ionic liquid The application of ionic liquid is extended to multiple subjects such as chemistry, biomedicine, Food Science by the new property of body, and it is special to have Significance.Meanwhile heteropolyacid anions ionic liquid, also by abundant, expansion polyoxometallate research, using model Farmland, assign its new application value.
The content of the invention
It is few and at room temperature to be non-the invention aims to solve existing polyoxometalate ionic liquid species, quantity The problem of liquid, and a kind of ionic liquid at room temperature based on polyoxometallic acid salt ion and preparation method thereof is provided.
It is a kind of based on the ionic liquid at room temperature of heteropolyacid anions by victoria blue B cation and heteropolyacid anions group Into, the mass fraction of victoria blue B cation is 50.9% in the ionic liquid at room temperature based on heteropolyacid anions, The mol ratio of victoria blue B cation and heteropolyacid anions in the described ionic liquid at room temperature based on heteropolyacid anions For 4:1;Described victoria blue B cationic chemical formula is [C33H32N3]+;Described heteropolyacid anions chemical formula for [α- SiMo12O40]4-
A kind of preparation method of above-mentioned ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps 's:
First, prepare and contain [α-SiMo12O40]4-The mixed organic solvents of anion:Sodium molybdate is dissolved in distilled water, It is 2.03mol/L sodium silicate aqueous solutions that concentrated nitric acid and concentration are added dropwise under stirring condition, after temperature is down to room temperature, adds acetonitrile, Then room temperature is cooled to after condensing reflux reaction 30min, stratification, collects upper solution, that is, contained [α-SiMo12O40]4- The mixed organic solvents of anion;The quality of the sodium molybdate and the volume ratio of distilled water are 5.5g:30mL;The distilled water with The volume ratio of concentrated nitric acid is 30:7.5;The distilled water is 30 with the volume ratio that concentration is 2.03mol/L sodium silicate aqueous solutions: 10;The volume ratio of the distilled water and acetonitrile is 30:100;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
The concentration of victoria blue B cation is 3.0mol/L in victoria blue B solution described in step 2, wherein Described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise in the case where temperature is 50 DEG C and stirring condition and contains [SiMo12O40]4- In the mixed organic solvents of anion, room temperature is cooled to after mixing, stratification, lower floor's solution is collected, that is, obtains room-temperature ion Liquid crude product;Victoria blue B cation is with containing [α-SiMo in victoria blue B solution described in step 312O40]4-It is cloudy [α-SiMo in the mixed organic solvents of ion12O40]4-Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 3 times, it is dried in vacuo 8 hours at being finally 75 DEG C in temperature, that is, obtains the ionic liquid at room temperature based on heteropolyacid anions; Victoria blue B cation mass content is in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 50.9%.
It is a kind of based on the ionic liquid at room temperature of heteropolyacid anions by victoria blue B cation and heteropolyacid anions group Into, in the ionic liquid at room temperature based on heteropolyacid anions the mass fraction of victoria blue B cation be 30%~ 60%, victoria blue B cation and heteropolyacid anions in the ionic liquid at room temperature based on heteropolyacid anions Mol ratio is 4:1;Described victoria blue B cationic chemical formula is [C33H32N3]+;Described heteropolyacid anions chemical formula For [X2M18O62]4-, [X2M18O62]4-Middle X is Si, S or P, and M is W or Mo.
A kind of preparation method of above-mentioned ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps 's:
First, prepare and contain [X2M18O62]4-The mixed organic solvents of anion:M acid sodium is dissolved in distilled water, stirred Under the conditions of be added dropwise the solution of chemicals containing X, after temperature is down to room temperature, add acetonitrile, then condensing reflux react 1h~2h after it is cold But to room temperature, stratification, upper solution is collected, that is, is contained [X2M18O62]4-The mixed organic solvents of anion;
M acid sodium described in step 1 is sodium molybdate or sodium tungstate;The solution of chemicals containing X described in step 1 is dense sulphur Acid, concentration are 2.03mmol/L sodium silicate aqueous solutions or concentrated phosphoric acid;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
In victoria blue B solution described in step 2 the concentration of victoria blue B cation be 0.5mol/L~ 2.5mol/L, wherein described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise under agitation and contains [X2M18O62]4-Anion is mixed with In machine solution, stratification after mixing, lower floor's solution is collected, that is, obtains ionic liquid at room temperature crude product;Tieed up described in step 3 Victoria blue B cation is with containing [X in more Leah indigo plant B solutions2M18O62]4-[X in the mixed organic solvents of anion2M18O62]4- Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 2~4 times, it is dried in vacuo 8 hours at being finally 50 DEG C~80 DEG C in temperature, that is, obtains the room temperature based on heteropolyacid anions Ionic liquid;The matter of victoria blue B cation in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 It is 30%~60% to measure fraction.
It is a kind of based on the ionic liquid at room temperature of heteropolyacid anions by victoria blue B cation and heteropolyacid anions group Into, in the ionic liquid at room temperature based on heteropolyacid anions the mass fraction of victoria blue B cation be 39%~ 51%, victoria blue B cation and heteropolyacid anions in the ionic liquid at room temperature based on heteropolyacid anions Mol ratio is 4:1;Described victoria blue B cationic chemical formula is [C33H32N3]+;Described heteropolyacid anions chemical formula For [XM12O40]4-, [XM12O40]4-Middle X is Si, S or P, and M is W or Mo.
A kind of preparation method of above-mentioned ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps 's:
First, prepare and contain [XM12O40]4-The mixed organic solvents of anion:M acid sodium is dissolved in distilled water, in stirring bar Concentrated nitric acid is added dropwise under part, continues to stir 10min~30min, then the solution of chemicals containing X is added dropwise, then condensing reflux reaction 30min ~2h, that is, contained [XM12O40]4-The mixed organic solvents of anion;
M acid sodium described in step 1 is sodium molybdate or sodium tungstate;The solution of chemicals containing X described in step 1 is dense sulphur Acid, concentration are 2.03mmol/L sodium silicate aqueous solutions or concentrated phosphoric acid;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
In victoria blue B solution described in step 2 the concentration of victoria blue B cation be 0.5mol/L~ 2.5mol/L, wherein described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise in the case where temperature is 50 DEG C and stirring condition and contains [XM12O40]4-It is cloudy In the mixed organic solvents of ion, room temperature is cooled to after mixing, stratification, lower floor's solution is collected, that is, obtains room-temperature ion liquid Body crude product;Victoria blue B cation is with containing [XM in victoria blue B solution described in step 312O40]4-Anion [XM in mixed organic solvents12O40]4-Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 2~4 times, it is dried in vacuo 8 hours at being finally 50 DEG C~80 DEG C in temperature, that is, obtains the room temperature based on heteropolyacid anions Ionic liquid;The matter of victoria blue B cation in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 It is 39%~51% to measure fraction.
It is a kind of based on the ionic liquid at room temperature of heteropolyacid anions by four n-octyl bromination ammonium cations and heteropoly acid the moon from Son forms, and the mass fraction of four n-octyl bromination ammonium cations is in the ionic liquid at room temperature based on heteropolyacid anions 29.96%, four n-octyl bromination ammonium cations and heteropoly acid are cloudy in the ionic liquid at room temperature based on heteropolyacid anions The mol ratio of ion is 4:1;Four described n-octyl bromination ammonium cation chemical formulas are [C32H68N]+;Described heteropoly acid the moon from Sub- chemical formula is [α-S2W18O62]4-
A kind of preparation method of above-mentioned ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps 's:
By Na2WO4·2H2O is dissolved in distilled water, adds CH3CN, concentration is then added dropwise under agitation is 18mol/L sulfuric acid solution, it is placed in after stirring and evenly mixing in the water-bath that temperature is 70 DEG C, adds in the case where temperature is 70 DEG C of water bath condition 13d~15d is reacted in thermal agitation, is cooled to room temperature, adds petroleum ether, be then transferred in separatory funnel, stratification, takes Layer yellow-green liquid, pours into upper strata yellow-green liquid in beaker in ventilating kitchen, then the burning that will fill upper strata yellow-green liquid Cup is placed in the water-bath that temperature is 70 DEG C, and is stirred in the case where temperature is 70 DEG C of water bath condition, and four n-octyls are then added dropwise Ammonium bromide solution, four n-octyl ammonium bromide solutions continue the stirring reaction 3h in the case where temperature is 70 DEG C of water bath condition, obtained after adding It is described based on miscellaneous to the ionic liquid of bottle-green solid solution shape, the as ionic liquid at room temperature based on heteropolyacid anions The ionic liquid at room temperature cationic of polyoxoanion is four n-octyl bromination ammonium cations, and chemical formula is [C32H68N]+, quality Fraction is 29.96%;Anion is heteropolyacid anions in the described ionic liquid at room temperature based on heteropolyacid anions, and is changed Formula is [α-S2W18O62]4-;[C in the described ionic liquid at room temperature based on heteropolyacid anions32H68N]+With [α-S2W18O62 ]4-Mol ratio be 4:1;Described Na2WO4·2H2O quality and the volume ratio of distilled water are 5.6250g:167.5mL;It is described Distilled water and concentration be 18mol/L the volume ratio of sulfuric acid solution be 167.5:37.5;Described distilled water and petroleum ether Volume ratio is 167.5:100;
Four described n-octyl ammonium bromide solutions are completed according to the following steps:Four n-octyl ammonium bromides are dissolved in acetonitrile In, four n-octyl ammonium bromide solutions are obtained, four described n-octyl ammonium bromide chemical formulas are C32H68NBr, four described n-octyls The quality of four n-octyl ammonium bromides and the volume ratio of acetonitrile are 2.3239g in ammonium bromide solution:20mL.
Advantage of the present invention:First, ionic liquid provided by the invention is prepared as substantially synthetically prepared reaction, device therefor Few, step is simple.Reaction condition is gentle, and cost is relatively low, acetonitrile solvent recoverable, is suitable for industrial production.
2nd, ionic liquid provided by the invention is ionic liquid at room temperature, and fusing point is≤10 DEG C.
3rd, it is provided by the invention equal in preparation, removal of impurities, drying process based on the ionic liquid at room temperature of heteropolyacid anions For liquid condition, and sample purity is high.
4th, ionic liquid provided by the invention can dissolve in water, acetonitrile, ethanol.And it can show good more Oxometallate electrochemical oxidation-reducing activity.
5th, ionic liquid at room temperature provided by the invention is because its anionicsite is the polyoxometallic acid that has catalytic activity Salt, such as esterification, oxidation reaction, ester exchange and condensation organic reaction can be catalyzed.
6th, the ionic liquid at room temperature provided by the invention based on heteropolyacid anions can be used as solar cell or lithium from The electrolyte of sub- battery.Due to ionic liquid at room temperature provided by the invention, its cationic moiety is that have having for dye sensitization performance Machine macromolecular, some visible light can be absorbed, solar cell electrolyte can not only be used as, it may have dye sensitization function.It is right Than victoria blue B dye sensitization P25 solar cells, electrolyte and sensitization are made with ionic liquid at room temperature provided by the invention Agent, the electricity conversion of battery can improve more than 13.8%.
7th, ionic liquid at room temperature provided by the invention is because its anionicsite is heteropolyacid anions, to NO2 -、H2O2 Etc. small molecule water pollutant, there is sensitive electrochemical reaction activity, wherein NO2 -Test limit be not less than 0.17mmol/L, H2O2Test limit be not less than 0.84mmol/L, can be used as monitoring NO2 -、H2O2Etc. the sensor of small molecule water pollutant.
8th, ionic liquid at room temperature provided by the invention does not dissolve in ethyl acetate, but under ultraviolet light, can not only change It dissolves polarity, it is dissolved in ethyl acetate, can also realize that water, acetonitrile, ethyl acetate dissolve each other.
Brief description of the drawings
Fig. 1 is to test an ionic liquid at room temperature infrared spectrogram based on heteropolyacid anions prepared;
Fig. 2 is cyclic voltammetry curve, and A represents the ionic liquid at room temperature based on heteropolyacid anions prepared by experiment one in figure Cyclic voltammetry curve in water, in figure B represent prepared by experiment one based on the ionic liquid at room temperature of heteropolyacid anions in second Cyclic voltammetry curve in alcohol, in figure C represent prepared by experiment one based on the ionic liquid at room temperature of heteropolyacid anions in acetonitrile In cyclic voltammetry curve;
Fig. 3 is P25 solar cell I-V curves, and A represents I- of the electrolyte I to P25 solar cell dye sensitizations in figure V curves, B represents I-V curve of the electrolyte II to P25 solar cell dye sensitizations in figure;
Fig. 4 is to test an ionic liquid at room temperature catalytic cycle volt-ampere curve based on heteropolyacid anions prepared;
Fig. 5 is P25 solar cell I-V curves, and A represents electrolyte III to P25 solar cell dye sensitizations in figure I-V curve, B represents I-V curve of the electrolyte IV to P25 solar cell dye sensitizations in figure;
Fig. 6 is to test the four ionic liquid at room temperature infrared spectrograms based on heteropolyacid anions prepared;
Fig. 7 is cyclic voltammetry curve, and A represents the ionic liquid at room temperature based on heteropolyacid anions prepared by experiment four in figure Cyclic voltammetry curve in water, in figure B represent prepared by experiment four based on the ionic liquid at room temperature of heteropolyacid anions in second Cyclic voltammetry curve in alcohol, in figure C represent prepared by experiment four based on the ionic liquid at room temperature of heteropolyacid anions in acetonitrile In cyclic voltammetry curve;
Fig. 8 is P25 solar cell I-V curves, and A represents I- of the electrolyte I to P25 solar cell dye sensitizations in figure V curves, B represents I-V curve of the electrolyte II to P25 solar cell dye sensitizations in figure;
Fig. 9 is to test the four ionic liquid at room temperature catalytic cycle volt-ampere curves based on heteropolyacid anions prepared.
Embodiment
Embodiment one:Present embodiment is a kind of ionic liquid at room temperature based on heteropolyacid anions, its feature It is to be made up of victoria blue B cation and heteropolyacid anions based on the ionic liquid at room temperature of heteropolyacid anions, it is described The ionic liquid at room temperature based on heteropolyacid anions in victoria blue B cation mass fraction be 50.9%, it is described The mol ratio of victoria blue B cation and heteropolyacid anions is 4 in ionic liquid at room temperature based on heteropolyacid anions:1; Described victoria blue B cationic chemical formula is [C33H32N3]+;Described heteropolyacid anions chemical formula for [α- SiMo12O40]4-
Embodiment two:Present embodiment is a kind of preparation side of the ionic liquid at room temperature based on heteropolyacid anions Method, it is specifically realized by the following steps:
First, prepare and contain [α-SiMo12O40]4-The mixed organic solvents of anion:Sodium molybdate is dissolved in distilled water, It is 2.03mol/L sodium silicate aqueous solutions that concentrated nitric acid and concentration are added dropwise under stirring condition, after temperature is down to room temperature, adds acetonitrile, Then room temperature is cooled to after condensing reflux reaction 30min, stratification, collects upper solution, that is, contained [α-SiMo12O40]4- The mixed organic solvents of anion;The quality of the sodium molybdate and the volume ratio of distilled water are 5.5g:30mL;The distilled water with The volume ratio of concentrated nitric acid is 30:7.5;The distilled water is 30 with the volume ratio that concentration is 2.03mol/L sodium silicate aqueous solutions: 10;The volume ratio of the distilled water and acetonitrile is 30:100;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
The concentration of victoria blue B cation is 3.0mol/L in victoria blue B solution described in step 2, wherein Described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise in the case where temperature is 50 DEG C and stirring condition and contains [SiMo12O40]4- In the mixed organic solvents of anion, room temperature is cooled to after mixing, stratification, lower floor's solution is collected, that is, obtains room-temperature ion Liquid crude product;Victoria blue B cation is with containing [α-SiMo in victoria blue B solution described in step 312O40]4-It is cloudy [α-SiMo in the mixed organic solvents of ion12O40]4-Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 3 times, it is dried in vacuo 8 hours at being finally 75 DEG C in temperature, that is, obtains the ionic liquid at room temperature based on heteropolyacid anions; Victoria blue B cation mass content is in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 50.9%.
Embodiment three:Present embodiment be it is a kind of based on the ionic liquid at room temperature of heteropolyacid anions by Wei Duoli Sub- blue B cations and heteropolyacid anions form, Victoria in the ionic liquid at room temperature based on heteropolyacid anions The mass fraction of blue B cations is 30%~60%, Wei Duoli in the ionic liquid at room temperature based on heteropolyacid anions The mol ratio of sub- blue B cations and heteropolyacid anions is 4:1;Described victoria blue B cationic chemical formula is [C33H32N3]+;Described heteropolyacid anions chemical formula is [X2M18O62]4-, [X2M18O62]4-Middle X is Si, S or P, M be W or Mo。
Embodiment four:Present embodiment is a kind of preparation side of the ionic liquid at room temperature based on heteropolyacid anions Method, it is specifically realized by the following steps:
First, prepare and contain [X2M18O62]4-The mixed organic solvents of anion:M acid sodium is dissolved in distilled water, stirred Under the conditions of be added dropwise the solution of chemicals containing X, after temperature is down to room temperature, add acetonitrile, then condensing reflux react 1h~2h after it is cold But to room temperature, stratification, upper solution is collected, that is, is contained [X2M18O62]4-The mixed organic solvents of anion;
M acid sodium described in step 1 is sodium molybdate or sodium tungstate;The solution of chemicals containing X described in step 1 is dense sulphur Acid, concentration are 2.03mmol/L sodium silicate aqueous solutions or concentrated phosphoric acid;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
In victoria blue B solution described in step 2 the concentration of victoria blue B cation be 0.5mol/L~ 2.5mol/L, wherein described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise under agitation and contains [X2M18O62]4-Anion is mixed with In machine solution, stratification after mixing, lower floor's solution is collected, that is, obtains ionic liquid at room temperature crude product;Tieed up described in step 3 Victoria blue B cation is with containing [X in more Leah indigo plant B solutions2M18O62]4-[X in the mixed organic solvents of anion2M18O62]4- Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 2~4 times, it is dried in vacuo 8 hours at being finally 50 DEG C~80 DEG C in temperature, that is, obtains the room temperature based on heteropolyacid anions Ionic liquid;The matter of victoria blue B cation in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 It is 30%~60% to measure fraction.
Embodiment five:Present embodiment be it is a kind of based on the ionic liquid at room temperature of heteropolyacid anions by Wei Duoli Sub- blue B cations and heteropolyacid anions form, Victoria in the ionic liquid at room temperature based on heteropolyacid anions The mass fraction of blue B cations is 39%~51%, Wei Duoli in the ionic liquid at room temperature based on heteropolyacid anions The mol ratio of sub- blue B cations and heteropolyacid anions is 4:1;Described victoria blue B cationic chemical formula is [C33H32N3]+;Described heteropolyacid anions chemical formula is [XM12O40]4-, [XM12O40]4-Middle X is Si, S or P, and M is W or Mo.
Embodiment six:Present embodiment is a kind of preparation side of the ionic liquid at room temperature based on heteropolyacid anions Method, it is specifically realized by the following steps:
First, prepare and contain [XM12O40]4-The mixed organic solvents of anion:M acid sodium is dissolved in distilled water, in stirring bar Concentrated nitric acid is added dropwise under part, continues to stir 10min~30min, then the solution of chemicals containing X is added dropwise, then condensing reflux reaction 30min ~2h, that is, contained [XM12O40]4-The mixed organic solvents of anion;
M acid sodium described in step 1 is sodium molybdate or sodium tungstate;The solution of chemicals containing X described in step 1 is dense sulphur Acid, concentration are 2.03mmol/L sodium silicate aqueous solutions or concentrated phosphoric acid;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
In victoria blue B solution described in step 2 the concentration of victoria blue B cation be 0.5mol/L~ 2.5mol/L, wherein described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise in the case where temperature is 50 DEG C and stirring condition and contains [XM12O40]4-It is cloudy In the mixed organic solvents of ion, room temperature is cooled to after mixing, stratification, lower floor's solution is collected, that is, obtains room-temperature ion liquid Body crude product;Victoria blue B cation is with containing [XM in victoria blue B solution described in step 312O40]4-Anion [XM in mixed organic solvents12O40]4-Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 2~4 times, it is dried in vacuo 8 hours at being finally 50 DEG C~80 DEG C in temperature, that is, obtains the room temperature based on heteropolyacid anions Ionic liquid;The matter of victoria blue B cation in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 It is 39%~51% to measure fraction.
Embodiment seven:Present embodiment is a kind of just pungent by four based on the ionic liquid at room temperature of heteropolyacid anions Bromide ammonium cation and heteropolyacid anions form, and four is just pungent in the ionic liquid at room temperature based on heteropolyacid anions The mass fraction of bromide ammonium cation is 29.96%, and four just in the ionic liquid at room temperature based on heteropolyacid anions The mol ratio of octyl group bromination ammonium cation and heteropolyacid anions is 4:1;Four described n-octyl bromination ammonium cation chemical formulas For [C32H68N]+;Described heteropolyacid anions chemical formula is [α-S2W18O62]4-
Embodiment eight:Present embodiment is a kind of preparation side of the ionic liquid at room temperature based on heteropolyacid anions Method, it is specifically realized by the following steps:
By Na2WO4·2H2O is dissolved in distilled water, adds CH3CN, concentration is then added dropwise under agitation is 18mol/L sulfuric acid solution, it is placed in after stirring and evenly mixing in the water-bath that temperature is 70 DEG C, adds in the case where temperature is 70 DEG C of water bath condition 13d~15d is reacted in thermal agitation, is cooled to room temperature, adds petroleum ether, be then transferred in separatory funnel, stratification, takes Layer yellow-green liquid, pours into upper strata yellow-green liquid in beaker in ventilating kitchen, then the burning that will fill upper strata yellow-green liquid Cup is placed in the water-bath that temperature is 70 DEG C, and is stirred in the case where temperature is 70 DEG C of water bath condition, and four n-octyls are then added dropwise Ammonium bromide solution, four n-octyl ammonium bromide solutions continue the stirring reaction 3h in the case where temperature is 70 DEG C of water bath condition, obtained after adding It is described based on miscellaneous to the ionic liquid of bottle-green solid solution shape, the as ionic liquid at room temperature based on heteropolyacid anions The ionic liquid at room temperature cationic of polyoxoanion is four n-octyl bromination ammonium cations, and chemical formula is [C32H68N]+, quality Fraction is 29.96%;Anion is heteropolyacid anions in the described ionic liquid at room temperature based on heteropolyacid anions, and is changed Formula is [α-S2W18O62]4-;[C in the described ionic liquid at room temperature based on heteropolyacid anions32H68N]+With [α-S2W18O62 ]4-Mol ratio be 4:1;Described Na2WO4·2H2O quality and the volume ratio of distilled water are 5.6250g:167.5mL;It is described Distilled water and concentration be 18mol/L the volume ratio of sulfuric acid solution be 167.5:37.5;Described distilled water and petroleum ether Volume ratio is 167.5:100;
Four described n-octyl ammonium bromide solutions are completed according to the following steps:Four n-octyl ammonium bromides are dissolved in acetonitrile In, four n-octyl ammonium bromide solutions are obtained, four described n-octyl ammonium bromide chemical formulas are C32H68NBr, four described n-octyls The quality of four n-octyl ammonium bromides and the volume ratio of acetonitrile are 2.3239g in ammonium bromide solution:20mL.
Using following verification experimental verifications effect of the present invention
Experiment one:A kind of preparation method of the ionic liquid at room temperature based on heteropolyacid anions, specifically according to the following steps Complete:
First, prepare and contain [α-SiMo12O40]4-The mixed organic solvents of anion:5.5g sodium molybdates are dissolved in 30mL distillations In water, it is 2.03mmol/L sodium silicate aqueous solutions that 7.5mL concentrated nitric acids and 10mL concentration are added dropwise under agitation, treats that temperature is down to After room temperature, 100mL acetonitriles are added, are then cooled to room temperature after condensing reflux reaction 30min, stratification,
Upper solution is collected, that is, is contained [α-SiMo12O40]4-The mixed organic solvents of anion;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
The concentration of victoria blue B cation is 3.0mol/L in victoria blue B solution described in step 2, wherein Described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise in the case where temperature is 50 DEG C and stirring condition and contains [SiMo12O40]4- In the mixed organic solvents of anion, room temperature is cooled to after mixing, stratification, lower floor's solution is collected, that is, obtains room-temperature ion Liquid crude product;Victoria blue B cation is with containing [SiMo in victoria blue B solution described in step 312O40]4-It is cloudy from [α-SiMo in the mixed organic solvents of son12O40]4-Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 3 times, it is dried in vacuo 8 hours at being finally 75 DEG C in temperature, that is, obtains the ionic liquid at room temperature based on heteropolyacid anions; Victoria blue B cation mass content is in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 50.9%.
The ionic liquid at room temperature based on heteropolyacid anions prepared using infrared spectrometer to experiment one is detected, and is examined Survey result as shown in figure 1, Fig. 1 be test one prepare the ionic liquid at room temperature infrared spectrogram based on heteropolyacid anions, lead to Fig. 1 is crossed to can be seen that by this method preparation based on the ionic liquid at room temperature of heteropolyacid anions by heteropolyacid anions and Wei Duo Leah indigo plant B cation compositions, purity is high, without any impurity.
Respectively in water, ethanol and acetonitrile as medium, detection experiment one prepare based on the room temperature of heteropolyacid anions from Cyclic voltamogram of the sub- liquid in water, ethanol and acetonitrile, as shown in Fig. 2 Fig. 2 is cyclic voltammetry curve, A represents examination in figure The cyclic voltammetry curve based on the ionic liquid at room temperature of heteropolyacid anions in water of a preparation is tested, B represents experiment one in figure The cyclic voltammetry curve in ethanol of the ionic liquid at room temperature based on heteropolyacid anions prepared, C represents the system of experiment one in figure The standby cyclic voltammetry curve based on the ionic liquid at room temperature of heteropolyacid anions in acetonitrile, experiment one can be seen that by Fig. 2 The ionic liquid at room temperature based on heteropolyacid anions prepared can dissolve in water, ethanol, acetonitrile, ionize, and keep well Anionic electrodeposition chemism.
Acetonitrile is added in the ionic liquid at room temperature based on heteropolyacid anions prepared to experiment one, configuration obtains electrolyte I and electrolyte II, [C in described electrolyte I33H32N3]4[α-SiMo12O40] concentration be 0.05mmol/L, described electrolysis [C in liquid II33H32N3]4[α-SiMo12O40] concentration be 0.5mmol/L, using electrolyte I and electrolyte II respectively to P25 too Positive energy battery carries out dye sensitization, and test result is as shown in figure 3, Fig. 3 is P25 solar cell I-V curves, and A represents electricity in figure I-V curve of the liquid I to P25 solar cell dye sensitizations is solved, B represents that electrolyte II is quick to P25 solar cell dyestuffs in figure The I-V curve of change, it can be seen that the ionic liquid at room temperature based on heteropolyacid anions prepared by experiment one cannot be only used for by Fig. 3 Solar cell electrolyte, and due to the absorption based on the ionic liquid at room temperature of heteropolyacid anions to visible ray, its Inorganic sensitized dose of use can be used as.Ionic liquid at room temperature usage amount based on heteropolyacid anions is higher, solar cell photoelectric Efficiency is higher.
An ionic liquid at room temperature based on heteropolyacid anions prepared will be tested to be added to the water, obtain room-temperature ion liquid Body-H2O mixed liquors, described ionic liquid at room temperature-H2[C in O mixed liquors33H32N3]4[α-SiMo12O40] concentration be 2mmol/ L, to ionic liquid at room temperature-H2H is added in O mixed liquors2O2, obtain various concentrations and contain H2O2Solution, containing H2O2H in solution2O2Concentration 0mmol/L, 4mmol/L, 8mmol/L, 12mmol/L and 16mmol/L are followed successively by, detects and contains in the case where sweep speed is 50mV/s H2O2The catalytic cycle C-V characteristic of solution, as shown in figure 4, Fig. 4 is catalytic cycle volt-ampere curve, H is from top to bottom contained in figure2O2 H in solution2O2Concentration is followed successively by 0mmol/L, 4mmol/L, 8mmol/L, 12mmol/L and 16mmol/L, can be seen by Fig. 4 Go out, with H in catalystic converter system2O2Concentration increases, and the ionic liquid at room temperature based on heteropolyacid anions is located at -0.5V The oxidation peak current of left and right constantly increases with the reduction peak current positioned at 1.0V or so, illustrate heteropoly acid the moon in ionic liquid from Son is constantly reduced, and minimum H2O2Response concentration is not higher than 0.89mmol/L, it was demonstrated that the room-temperature ion based on heteropolyacid anions Liquid can be used as H2O2Sensor.
Under ultraviolet light experiment one prepare the ionic liquid at room temperature based on heteropolyacid anions realize water, acetonitrile and Ethyl acetate dissolves each other because, experiment one prepare the ionic liquid at room temperature based on heteropolyacid anions in heteropoly acid the moon from Son absorbs ultraviolet light and itself reduction reaction (M occurs6+→M5+), so that heteropolyacid anions " group " surface charge density Change, and then change the size of anions and canons charge attraction power in ionic liquid, so that its polarity changes, it is real The ionic liquid at room temperature based on heteropolyacid anions that now prepared by experiment one realizes that water, acetonitrile and ethyl acetate dissolve each other.Additional Oxidant such as H2O2Or under conditions of visible ray illumination, the ionic liquid at room temperature based on heteropolyacid anions of the preparation of experiment one Middle heteropolyacid anions partial reduction state (M5+) oxidation reaction (M occurs5+→M6+) so that heteropolyacid anions " group " surface Charge density reparation, realize that the ionic liquid at room temperature based on heteropolyacid anions prepared by experiment one realizes water, acetonitrile and acetic acid Ethyl ester is layered.Experiment one prepare based on the ionic liquid at room temperature of heteropolyacid anions under the conditions of additional change in polarity it is reversible Process, it is catalyst extraction in catalytic reaction process, the economic sector extraction of workshop-sink (material), there is provided a kind of simpler Method.
Experiment two:A kind of preparation method of the ionic liquid at room temperature based on heteropolyacid anions, specifically according to the following steps Complete:
First, prepare and contain [S2Mo18O62]4-The mixed organic solvents of anion:6.3g sodium molybdates are dissolved in 20mL distilled water In, the 5mL concentrated sulfuric acids are added dropwise under agitation, after temperature is down to room temperature, add 100mL acetonitriles, then condensing reflux reacts Room temperature is cooled to after 2h, stratification, upper solution is collected, that is, is contained [S2Mo18O62]4-The mixed organic solvents of anion;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
The concentration of victoria blue B cation is 3.0mol/L in victoria blue B solution described in step 2, wherein Described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise under agitation and contains [S2Mo18O62]4-The mixing of anion In organic solution, stratification after mixing, lower floor's solution is collected, that is, obtains ionic liquid at room temperature crude product;Described in step 3 Victoria blue B cation is with containing [S in victoria blue B solution2Mo18O62]4-In the mixed organic solvents of anion [S2Mo18O62]4-Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 3 times, it is dried in vacuo 8 hours at being finally 75 DEG C in temperature, that is, obtains the ionic liquid at room temperature based on heteropolyacid anions; Victoria blue B cation mass content is in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 40.3%.
Experiment one is utilized to prepare as catalyst based on the ionic liquid at room temperature of heteropolyacid anions using the preparation of experiment two The ionic liquid at room temperature catalytic esterification based on heteropolyacid anions, the catalytic selectivity of esterification and catalysis yield are such as Shown in table 1, understand that the ionic liquid at room temperature based on heteropolyacid anions prepared by experiment one is urged esterification by table 1 It is high to change activity, is reacted available for Industrial Catalysis.
Table 1
Reaction raw materials A Reaction raw materials B Yield Selectivity
Citric acid N-butanol 96.4 98
Lactic acid N-butanol 89.5 100
Acetic acid N-butanol 94.5 100
Acetic acid Glycerine 84.5 89
Acetic acid Ethylene glycol 97.7 93
Experiment three:A kind of preparation method of the ionic liquid at room temperature based on heteropolyacid anions, specifically according to the following steps Complete:
First, prepare and contain [SiW12O40]4-The mixed organic solvents of anion:7.9g sodium tungstates are dissolved in 30mL distilled water In, 7.5mL concentrated nitric acids are added dropwise under agitation, continue to stir 30min, then it is 2.03mmol/L sodium metasilicate that 10mL concentration, which is added dropwise, The aqueous solution, then condensing reflux reaction 2h, that is, contained [SiW12O40]4-The mixed organic solvents of anion;
2nd, victoria blue B solution is prepared:Victoria blue B powder is dissolved in solvent, it is molten to obtain victoria blue B Liquid;
Victoria blue B powder chemical formula described in step 2 is C33H32N3Cl;
The concentration of victoria blue B cation is 3.0mol/L in victoria blue B solution described in step 2, wherein Described victoria blue B cationic chemical formula is [C33H32N3]+
Solvent described in step 2 is acetonitrile;
3rd, mix:Victoria blue B solution is added dropwise in the case where temperature is 50 DEG C and stirring condition and contains [SiW12O40]4-It is cloudy In the mixed organic solvents of ion, room temperature is cooled to after mixing, stratification, lower floor's solution is collected, that is, obtains room-temperature ion liquid Body crude product;Victoria blue B cation is with containing [SiW in victoria blue B solution described in step 312O40]4-Anion [SiW in mixed organic solvents12O40]4-Mol ratio be 4:1;
4th, clean:Rotary evaporation processing is carried out to ionic liquid at room temperature crude product, handled 2 hours, then using petroleum ether Cleaning 3 times, it is dried in vacuo 8 hours at being finally 75 DEG C in temperature, that is, obtains the ionic liquid at room temperature based on heteropolyacid anions; Victoria blue B cation mass content is in the ionic liquid at room temperature based on heteropolyacid anions described in step 4 39.6%.
Using experiment one and experiment three prepare based on the ionic liquid at room temperature of heteropolyacid anions as catalyst, utilize examination The ionic liquid at room temperature catalytic esterification based on heteropolyacid anions of one and the preparation of experiment three are tested, partial esterification reaction is urged Change selectivity and catalysis yield is as shown in table 2, experiment one is understood by table 2 and prepared by experiment three based on heteropolyacid anions Ionic liquid at room temperature is high to esterification catalytic activity, available for Industrial Catalysis esterification.
Table 2
Catalyst Reaction raw materials A Reaction raw materials B Yield Selectivity
[C33H32N3]4[SiMo12O40] Citric acid N-butanol 98.1 96
[C33H32N3]4[SiMo12O40] Acetic acid N-butanol 96.7 98
[C33H32N3]4[SiMo12O40] Acetic acid Glycerine 91.2 83
[C33H32N3]4[SiW12O40] Citric acid N-butanol 93.8 100
[C33H32N3]4[SiW12O40] Acetic acid N-butanol 91.4 97
[C33H32N3]4[SiW12O40] Acetic acid Glycerine 95.5 96
Acetonitrile is added in the ionic liquid at room temperature based on heteropolyacid anions prepared to experiment one, configuration obtains electrolyte III, acetonitrile is added into the ionic liquid at room temperature based on heteropolyacid anions of the preparation of experiment three, configuration obtains electrolyte IV, institute [C in the electrolyte III stated33H32N3]4[SiMo12O40] concentration be 0.5mmol/L, [C in described electrolyte IV33H32N3]4 [SiW12O40] concentration be 0.5mmol/L, using solve liquid III and electrolyte IV respectively to P25 solar cells carry out dyestuff it is quick Change, test result is as shown in figure 5, Fig. 5 is P25 solar cell I-V curves, and A represents electrolyte III to P25 solar-electricities in figure The I-V curve of pond dye sensitization, B represents that electrolyte IV to the I-V curve of P25 solar cell dye sensitizations, passes through Fig. 5 in figure It can be seen that the ionic liquid at room temperature based on heteropolyacid anions prepared by experiment one and experiment three cannot be only used for solar cell Electrolyte, and due to the absorption based on the ionic liquid at room temperature of heteropolyacid anions to visible ray, it can be used as inorganic Sensitizer uses.[C33H32N3]4[SiMo12O40] solar cell photoelectric efficiency ratio [C33H32N3]4[SiW12O40] high.
Experiment four:A kind of preparation method of the ionic liquid at room temperature based on heteropolyacid anions, specifically according to the following steps Complete:
By 5.6250g Na2WO4·2H2O is dissolved in 167.5mL distilled water, adds 100mL CH3CN, then stirring The sulfuric acid solution that 37.5mL concentration is 18mol/L is added dropwise under the conditions of mixing, is placed in after stirring and evenly mixing in the water-bath that temperature is 70 DEG C, Heating stirring reacts 14d under the water bath condition that temperature is 70 DEG C, is cooled to room temperature, adds 100mL petroleum ethers, be then transferred to In separatory funnel, stratification, upper strata yellow-green liquid is taken, pour into upper strata yellow-green liquid in beaker in ventilating kitchen, then The beaker for filling upper strata yellow-green liquid is placed in the water-bath that temperature is 70 DEG C, and stirred in the case where temperature is 70 DEG C of water bath condition Mix, four n-octyl ammonium bromide solutions are then added dropwise, it is 70 DEG C that four n-octyl ammonium bromide solutions, which continue after adding in temperature, Stirring reaction 3h under water bath condition, obtain the ionic liquid of bottle-green solid solution shape, the as room based on heteropolyacid anions Temperature ionic liquid, the ionic liquid at room temperature cationic based on heteropolyacid anions be four n-octyl ammonium bromide sun from Son, chemical formula are [C32H68N]+, mass fraction 29.96%;In the described ionic liquid at room temperature based on heteropolyacid anions Anion is heteropolyacid anions, and chemical formula is [α-S2W18O62]4-;The described room-temperature ion based on heteropolyacid anions [C in liquid32H68N]+With [α-S2W18O62]4-Mol ratio be 4:1;
Four described n-octyl ammonium bromide solutions are completed according to the following steps:The n-octyl ammonium bromides of 2.3239g tetra- is molten In 20mL acetonitriles, four n-octyl ammonium bromide solutions are obtained, four described n-octyl ammonium bromide chemical formulas are C32H68NBr。
The ionic liquid at room temperature based on heteropolyacid anions prepared using infrared spectrometer to experiment four is detected, and is examined Survey result as shown in fig. 6, Fig. 6 be test four prepare the ionic liquid at room temperature infrared spectrograms based on heteropolyacid anions, lead to Cross Fig. 6 can be seen that by this method prepare based on the ionic liquid at room temperature of heteropolyacid anions by heteropolyacid anions and four just Octyl group bromination ammonium cation forms, and purity is high, without any impurity.
Respectively in water, ethanol and acetonitrile as medium, detection experiment four prepare based on the room temperature of heteropolyacid anions from Cyclic voltamogram of the sub- liquid in water, ethanol and acetonitrile, as shown in fig. 7, Fig. 7 is cyclic voltammetry curve, A represents examination in figure The cyclic voltammetry curve based on the ionic liquid at room temperature of heteropolyacid anions in water of four preparations is tested, B represents experiment four in figure The cyclic voltammetry curve in ethanol of the ionic liquid at room temperature based on heteropolyacid anions prepared, C represents the system of experiment four in figure The standby cyclic voltammetry curve based on the ionic liquid at room temperature of heteropolyacid anions in acetonitrile, experiment four can be seen that by Fig. 7 The ionic liquid at room temperature based on heteropolyacid anions prepared can dissolve in water, ethanol, acetonitrile, ionize, and keep well Anionic electrodeposition chemism.
Acetonitrile is added in the ionic liquid at room temperature based on heteropolyacid anions prepared to experiment four, configuration obtains electrolyte III and electrolyte IV, [C in described electrolyte III32H68N]4[α-S2W18O62] concentration be 0.05mmol/L, described electrolysis [C in liquid IV32H68N]4[α-S2W18O62] concentration be 0.5mmol/L, using electrolyte III and electrolyte IV respectively to P25 too Positive energy battery carries out dye sensitization, and test result is as shown in figure 8, Fig. 8 is P25 solar cell I-V curves, and A represents electricity in figure I-V curve of the liquid III to P25 solar cell dye sensitizations is solved, B represents that electrolyte IV is quick to P25 solar cell dyestuffs in figure The I-V curve of change, it can be seen that the ionic liquid at room temperature based on heteropolyacid anions prepared by experiment four cannot be only used for by Fig. 8 Solar cell electrolyte, and due to the absorption based on the ionic liquid at room temperature of heteropolyacid anions to visible ray, its Inorganic sensitized dose of use can be used as.Ionic liquid at room temperature usage amount based on heteropolyacid anions is higher, solar cell photoelectric Efficiency is higher.
Four ionic liquid at room temperature based on heteropolyacid anions prepared will be tested to be added to the water, obtain room-temperature ion liquid Body-H2O mixed liquors, described ionic liquid at room temperature-H2[C in O mixed liquors32H68N]4[α-S2W18O62] concentration be 2mmol/L, To ionic liquid at room temperature-H2Cys are added in O mixed liquors, obtain various concentrations solution containing Cys, containing L- half Cys concentration is followed successively by 0mmol/L, 2mmol/L, 4mmol/L, 5mmol/L and 7mmol/L in cystine solution, is sweeping Speed is retouched to detect the catalytic cycle C-V characteristic of the solution containing Cys under 50mV/s, is followed as shown in figure 9, Fig. 9 is catalysis Ring volt-ampere curve, in figure from the bottom to top in solution containing Cys Cys concentration be followed successively by 0mmol/L, 2mmol/L, 4mmol/L, 5mmol/L and 7mmol/L, as seen in Figure 9, with the increasing of Cys concentration in catalystic converter system Height, the reduction peak current positioned at 1.22V or so of the ionic liquid at room temperature based on heteropolyacid anions constantly increase, and illustrate ion Heteropolyacid anions in liquid are constantly oxidized, and minimum Cys response concentration is not higher than 0.5mmol/L, it was demonstrated that base Can be as the sensor of Cys in the ionic liquid at room temperature of heteropolyacid anions.

Claims (2)

  1. A kind of 1. ionic liquid at room temperature based on heteropolyacid anions, it is characterised in that the room-temperature ion based on heteropolyacid anions Liquid is made up of four n-octyl bromination ammonium cations and heteropolyacid anions, the room-temperature ion based on heteropolyacid anions In liquid the mass fraction of four n-octyl bromination ammonium cations be 29.96%, it is described based on the room temperature of heteropolyacid anions from The mol ratio of four n-octyl bromination ammonium cations and heteropolyacid anions is 4 in sub- liquid:1;Four described n-octyl ammonium bromides Cationic chemical formula is [C32H68N]+;Described heteropolyacid anions chemical formula is [α-S2W18O62]4-
  2. 2. a kind of preparation method of the ionic liquid at room temperature based on heteropolyacid anions as claimed in claim 1, its feature exist Completed according to the following steps in a kind of preparation method of the ionic liquid at room temperature based on heteropolyacid anions:
    By Na2WO4·2H2O is dissolved in distilled water, adds CH3CN, it is 18mol/L that concentration is then added dropwise under agitation Sulfuric acid solution, it is the heating stirring in the case where temperature is 70 DEG C of water bath condition in 70 DEG C of water-bath that temperature is placed in after stirring and evenly mixing Reaction 13~15 days, is cooled to room temperature, adds petroleum ether, be then transferred in separatory funnel, stratification, take upper strata yellowish green Color liquid, upper strata yellow-green liquid is poured into beaker in ventilating kitchen, then the beaker for filling upper strata yellow-green liquid is placed in Temperature is in 70 DEG C of water-bath, and is stirred in the case where temperature is 70 DEG C of water bath condition, and four n-octyl ammonium bromides are then added dropwise Solution, four n-octyl ammonium bromide solutions continue stirring reaction 3 hours in the case where temperature is 70 DEG C of water bath condition, obtain depth after adding The ionic liquid of the solid solution shape of green, the as ionic liquid at room temperature based on heteropolyacid anions, it is described based on heteropoly acid The ionic liquid at room temperature cationic of anion is four n-octyl bromination ammonium cations, and chemical formula is [C32H68N]+, mass fraction For 29.96%;Anion is heteropolyacid anions in the described ionic liquid at room temperature based on heteropolyacid anions, and chemical formula For [α-S2W18O62]4-;[C in the described ionic liquid at room temperature based on heteropolyacid anions32H68N]+With [α-S2W18O62]4-'s Mol ratio is 4:1;Described Na2WO4·2H2O quality and the volume ratio of distilled water are 5.6250g:167.5mL;Described steaming The volume ratio for the sulfuric acid solution that distilled water is 18mol/L with concentration is 167.5:37.5;Described distilled water and the volume of petroleum ether Than for 167.5:100;
    Four described n-octyl ammonium bromide solutions are completed according to the following steps:Four n-octyl ammonium bromides are dissolved in acetonitrile, obtained To four n-octyl ammonium bromide solutions, four described n-octyl ammonium bromide chemical formulas are C32H68NBr, four described n-octyl brominations The quality of four n-octyl ammonium bromides and the volume ratio of acetonitrile are 2.3239g in ammonium salt solution:20mL.
CN201710852368.4A 2016-04-12 2016-04-12 Application of room-temperature ionic liquid based on heteropoly acid anions Active CN107652186B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201710852368.4A CN107652186B (en) 2016-04-12 2016-04-12 Application of room-temperature ionic liquid based on heteropoly acid anions
CN201610224764.8A CN105801449B (en) 2016-04-12 2016-04-12 Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710852368.4A CN107652186B (en) 2016-04-12 2016-04-12 Application of room-temperature ionic liquid based on heteropoly acid anions

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201610224764.8A Division CN105801449B (en) 2016-04-12 2016-04-12 Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107652186A true CN107652186A (en) 2018-02-02
CN107652186B CN107652186B (en) 2020-06-09

Family

ID=56460912

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201710852368.4A Active CN107652186B (en) 2016-04-12 2016-04-12 Application of room-temperature ionic liquid based on heteropoly acid anions
CN201610224764.8A Active CN105801449B (en) 2016-04-12 2016-04-12 Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201610224764.8A Active CN105801449B (en) 2016-04-12 2016-04-12 Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof

Country Status (1)

Country Link
CN (2) CN107652186B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112144073A (en) * 2020-10-10 2020-12-29 哈尔滨工业大学 Electrocatalytic reduction of CO under heteropolyacid ionic liquid-indium double-catalytic system2Method for preparing ethanolic acid

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107265722B (en) * 2017-08-08 2020-09-01 哈尔滨工业大学 Method for realizing desulfurization of sodium sulfide-containing wastewater by using polyacid ionic liquid

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102225899A (en) * 2011-04-14 2011-10-26 东北师范大学 Ionic liquid based on Dawson-type polyoxometalate and synthesis method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010103531A2 (en) * 2009-03-09 2010-09-16 Megafine Pharma (P) Ltd. A new method for the preparation of cinacalcet and new intermediates thereof
TWI426956B (en) * 2011-10-27 2014-02-21
CN103288739B (en) * 2013-06-19 2015-06-17 陕西师范大学 Complex of heteropoly tungstic acid anions and alkyl imidazolium cations and preparation method
CN103357434B (en) * 2013-07-18 2014-10-22 吕涛 Synthesizing method of heteropolyacid imidazolium salt catalyst
CN103664656A (en) * 2013-12-24 2014-03-26 大连工业大学 Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid
CN104610192A (en) * 2014-12-26 2015-05-13 哈尔滨工业大学 Room-temperature ionic liquid based on polyoxometallate and preparation method of room-temperature ionic liquid
CN105153203B (en) * 2015-08-28 2017-06-06 太原科技大学 A kind of organic inorganic hybridization compound of isopolymolybdic acid salt and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102225899A (en) * 2011-04-14 2011-10-26 东北师范大学 Ionic liquid based on Dawson-type polyoxometalate and synthesis method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JI HU ET AL.: "Homogeneous-phase catalytic H2O2 oxidation of isobutyraldehyde using Keggin, Dawson and transition metal-substituted lacunary heteropolyanions", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 *
SUSAN A. JANSEN ET AL.: "Stability and acidity contributions of heteropolymetalates: a theoretical study of the Keggin and Dawson ions", 《SUPRAMOLECULAR SCIENCE》 *
TOSHITAKA HORI ET AL: "Preparation of a Yellow Heteropoly Molybdosulfate", 《CHEMISTRY LETTERS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112144073A (en) * 2020-10-10 2020-12-29 哈尔滨工业大学 Electrocatalytic reduction of CO under heteropolyacid ionic liquid-indium double-catalytic system2Method for preparing ethanolic acid
CN112144073B (en) * 2020-10-10 2021-10-08 哈尔滨工业大学 Electrocatalytic reduction of CO under heteropolyacid ionic liquid-indium double-catalytic system2Method for preparing ethanolic acid

Also Published As

Publication number Publication date
CN107652186B (en) 2020-06-09
CN105801449B (en) 2017-11-14
CN105801449A (en) 2016-07-27

Similar Documents

Publication Publication Date Title
CN104610192A (en) Room-temperature ionic liquid based on polyoxometallate and preparation method of room-temperature ionic liquid
CN105801449B (en) Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof
CN105037303A (en) Method for preparing 2,5-furandicarboxylic acid from 5-hydroxymethyl furfural
CN101775615A (en) BiVO4 nano photoelectrode and application thereof in hydrogen production from water splitting
CN107011371A (en) A kind of siliceous glyoxaline ion liquid and its preparation method and application
CN102176387B (en) Methods for preparing porous spherical titanium dioxide paste and sensitized photo-anode
CN107828236A (en) It is a kind of using hydrazides as zinc protoporphyrin dye sensitizing agent of anchoring group and preparation method thereof
CN104231007B (en) Amphiphilic benzimidazole ruthenium complex for dye-sensitized solar cell and preparation method of amphiphilic benzimidazole ruthenium complex
CN105418511A (en) 1-butyl-3-methylimidazole naphthoic formate ionic liquid and preparation method and application thereof
CN104496928A (en) Method for preparing quaternary ammonium salt ionic liquid without halogen ions and sodium ions
CN102941119A (en) Preparation method for silicon dioxide loading heteropoly cesium catalyst
CN108796548B (en) The method that electro-catalysis reduction carbon dioxide prepares formic acid and acetic acid in heteropolyacid anions-acetonitrile-water ternary electrolyte system
CN107970912A (en) A kind of Alpha&#39;s bismuth oxide/pucherite and preparation method
CN104588025B (en) A kind of self assembly near-spherical Sm2o3the preparation method of/CuO nano-complex
CN102592831B (en) Cobalt ion liquid redox couple and preparation and application thereof
CN102074375B (en) Preparation method for high-cyclical-stability composite capacitor material
CN102659572A (en) Preparation method of dehydroabietic acid
CN107383003B (en) A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing quinacridone
CN104576081B (en) Anti-condensation curable type electrolyte and ultracapacitor
CN108107091B (en) A kind of preparation method and application of chirality MOF membrane material
CN105646589B (en) That detects lead ion contains manganese compound and its preparation method and application
CN102942487B (en) Method for preparing o-nitrophenol through phenol nitration selectivity
CN104987748B (en) Organic dye, preparation method thereof and application thereof
CN105859666A (en) Photoelectric oxidative synthesis method of 2,5-furyldiformic acid
CN100570900C (en) Be used for phosphoric acid ester electrolyte solvent of DSSC and uses thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant