CN105801449A - Room-temperature ionic liquid based on heteropoly acid anions and preparation method of room-temperature ionic liquid - Google Patents
Room-temperature ionic liquid based on heteropoly acid anions and preparation method of room-temperature ionic liquid Download PDFInfo
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Abstract
The invention discloses a room-temperature ionic liquid based on heteropoly acid anions and a preparation method of the room-temperature ionic liquid, relates to the room-temperature ionic liquid and the preparation method thereof, and aims to solve the problems that the variety and the number of conventional polyoxometallate ionic liquids are small and the conventional polyoxometallate ionic liquids are non-liquid at the room temperature. The room-temperature ionic liquid based on the heteropoly acid anions comprises Victoria blue B cations, the heteropoly acid anions and a solvent.; the method comprises steps as follows: step one, preparing a mixed organic solution containing [X2M18O62]<4->, [XM12O40] <4-> or [alpha-SiMo12O40]<4-> anions; step two, preparing a Victoria blue B solution; step three, performing mixing; step four, removing impurities. Or the room-temperature ionic liquid based on the heteropoly acid anions comprises tetraoctyl ammonium bromide cations, the heteropoly acid anions and the solvent; the method comprises steps as follows: Tungstic acid sodium salt dihydrate, acetonitrile and a sulfuric acid solution are adopted as raw materials to prepare an anionic mixed organic solution, a tetraoctyl ammonium bromide solution is added for stirring reaction, impurities are removed, and the room-temperature ionic liquid is obtained. The invention is mainly applied to preparation of the room-temperature ionic liquid.
Description
Technical field
The present invention relates to a kind of ionic liquid at room temperature and preparation method thereof.
Background technology
Ionic liquid refer at room temperature or < present under 100 DEG C of temperature conditionss liquid, be substantially made up of anions and canons
Salt, also referred to as low temperature molten salt.Compared with traditional liquid material, ionic liquid has feature highlighted below: (1) steams
Vapour pressure is low, non-volatile, nonflammable, to human and environment low toxicity；(2) fusing point is low, and liquid condition temperature range width (is less than
Or close to room temperature-300 DEG C), chemical stability and Heat stability is good；(3) electrochemical stability is high, and electrochemical window is wider；(4)
Solvability is strong, can dissolve inorganic matter, Organic substance and polymer；(5) two-phase or multiphase system can be formed with other solvent,
It is suitable for doing reaction medium, catalyst and separation solvent etc.；(6) reusable.At present, ionic liquid is novel as one
Solvent and medium, be widely used in organic reaction, materials synthesis and the process such as mixture separates.Especially as " green
Color solvent " replaced organic solvent to come catalyst-solvent or the product of extractive reaction mixture as reaction dissolvent, significantly drop
The use of organic solvent in low heterogeneous catalytic reaction system, can reduce what atmospheric environment and health were produced by organic solvent
Harm.
Ionic liquid is made up of organic cation and inorganic or organic anion, and common cation has quaternary ammonium salt ion, season
Salt ion, imidazolium ion etc., anion has halide ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc..Mesh
In front studied ionic liquid, cation is mainly based on glyoxaline cation, and anion is mainly with halide ion and other nothing
Machine acid ion is main.Ionic liquid can be divided into halide salt ionic liquid and the big class of new ionic liquid two by the difference of anion.Halogen
Change ionic liquid by organic cation AlCl3Or AlBr3Constituting, concrete preparation method is that SOLID ORGANIC is cationic halogenated
Salt and AlCl3Or AlBr3Being obtained by mixing, its composition is not fixed.This type of ionic liquid substantial amounts, but quick to water and air
Sense, is mainly used as reaction dissolvent and is employed.New ionic liquid is the class multifunctional ion liquid just grown up in the recent period,
There is fixing chemical composition, to water, air-stable, according to the difference of anion, such as C3F7COO-、SbF6 -、AsF6 -、
Heteropolyacid anions etc., are given, by anion, the character that new ionic liquid is more rich, as catalysis, extract and separate metal ion,
Absorption and separation gas etc..At present, the applied research of new ionic liquid is concentrated mainly on organic synthesis, catalytic reaction, separation skill
Art and utilize the aspects such as ionic liquid desulfurization.
Generally, the preparation method of organic ion liquid has one-step synthesis and two-step synthesis method.One-step synthesis is to pass through soda acid
Neutralization reaction or quaterisation one-step synthesis obtain.One-step synthesis is simple to operate, does not has by-product, product to hold very much
Easy purification.The first step of two-step synthesis method is quaternary ammonium salt to be synthesized by imidazoles and alkyl halide, second step be quaternary ammonium salt with
Lewis acid carries out reacting or carrying out displacement reaction with the alkali metal salt containing required anion or acid, obtains object ion liquid
Body.Or directly in inorganic or organic salt, add proper ratio organic cation or inorganic anion, make corresponding ionic liquid
Body (direct method).By one-step method or direct method, two-step synthesis method, the new ionic liquid of synthesis, particularly comprise miscellaneous
The ionic liquid of polyoxoanion, owing to polyoxometallate ionic charge density is high, between anions and canons, bonding action power is strong,
Make its major part at ambient temperature for solid, only exist just can present liquid under 100 DEG C or 200 DEG C of temperature conditionss.Sternly
In fact, under this kind of room temperature condition, the material for solid can not be referred to as ionic liquid to lattice.Therefore, prepare new ionic liquid,
Particularly polyoxometalate ionic liquid, not only can enrich the kind of ionic liquid, quantity, also can rely on heteropoly acid cloudy from
It is multiple that the range of application of ionic liquid is extended to chemistry, biomedicine, Food Science etc. by the new property of son imparting ionic liquid
Subject, has special significance.Meanwhile, heteropolyacid anions ionic liquid, also will abundant, expansion polyoxometallic acid
The research of salt, application category, give its new using value.
Summary of the invention
The invention aims to solve existing polyoxometalate ionic liquid kind, quantity is few and under room temperature for non-liquid
Problem, and provide a kind of ionic liquid at room temperature based on polyoxometallic acid salt ion and preparation method thereof.
A kind of ionic liquid at room temperature based on heteropolyacid anions is made up of victoria blue B cation and heteropolyacid anions,
In described ionic liquid at room temperature based on heteropolyacid anions, the mass fraction of victoria blue B cation is 50.9%, institute
Victoria blue B cation and the mol ratio of heteropolyacid anions in the ionic liquid at room temperature based on heteropolyacid anions stated
For 4:1；Described victoria blue B cationic chemical formula is [C33H32N3]+；Described heteropolyacid anions chemical formula is
[α-SiMo12O40]4-。
The preparation method of above-mentioned a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps:
One, preparation is containing [α-SiMo12O40]4-The mixed organic solvents of anion: be dissolved in distilled water by sodium molybdate, is stirring
Drip concentrated nitric acid under the conditions of mixing and concentration be 2.03mol/L sodium silicate aqueous solution, after temperature is down to room temperature, add acetonitrile,
Then it is cooled to room temperature, stratification after condensing reflux reaction 30min, collects upper solution, i.e. contained
[α-SiMo12O40]4-The mixed organic solvents of anion；The quality of described sodium molybdate with the volume ratio of distilled water is
5.5g:30mL；Described distilled water is 30:7.5 with the volume ratio of concentrated nitric acid；Described distilled water and concentration are 2.03mol/L silicic acid
The volume ratio of sodium water solution is 30:10；Described distilled water is 30:100 with the volume ratio of acetonitrile；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is 3.0mol/L, wherein
Described victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [SiMo12O40]4-
In the mixed organic solvents of anion, after mixing, be cooled to room temperature, stratification, collect lower floor's solution, i.e. obtain room temperature from
Sub-liquid crude product；In victoria blue B solution described in step 3 victoria blue B cation with contain
[α-SiMo12O40]4-[α-SiMo in the mixed organic solvents of anion12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 3 times, be finally vacuum dried 8 hours at temperature is 75 DEG C, i.e. obtain room-temperature ion based on heteropolyacid anions
Liquid；In ionic liquid at room temperature based on heteropolyacid anions described in step 4, victoria blue B cation quality contains
Amount is 50.9%.
A kind of ionic liquid at room temperature based on heteropolyacid anions is made up of victoria blue B cation and heteropolyacid anions,
In described ionic liquid at room temperature based on heteropolyacid anions, the mass fraction of victoria blue B cation is
30%～60%, in described ionic liquid at room temperature based on heteropolyacid anions, victoria blue B cation is cloudy with heteropoly acid
The mol ratio of ion is 4:1；Described victoria blue B cationic chemical formula is [C33H32N3]+；Described heteropoly acid is cloudy
Ion chemistry formula is [X2M18O62]4-, [X2M18O62]4-Middle X is Si, S or P, and M is W or Mo.
The preparation method of above-mentioned a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps:
One, preparation is containing [X2M18O62]4-The mixed organic solvents of anion: be dissolved in distilled water by M acid sodium, in stirring
Under the conditions of drip the chemicals solution Han X, after temperature is down to room temperature, add acetonitrile, then condensing reflux react 1h～2h
After be cooled to room temperature, stratification, collect upper solution, i.e. contained [X2M18O62]4-The mixed organic solvents of anion；
M acid sodium described in step one is sodium molybdate or sodium tungstate；The chemicals solution containing X described in step one is dense sulfur
Acid, concentration are 2.03mmol/L sodium silicate aqueous solution or strong phosphoric acid；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is
0.5mol/L～2.5mol/L, wherein said victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: under agitation victoria blue B solution is added dropwise to containing [X2M18O62]4-Being mixed with of anion
In machine solution, stratification after mixing, collect lower floor's solution, i.e. obtain ionic liquid at room temperature crude product；Described in step 3
In victoria blue B solution victoria blue B cation with containing [X2M18O62]4-In the mixed organic solvents of anion
[X2M18O62]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 2～4 times, be finally vacuum dried 8 hours at temperature is 50 DEG C～80 DEG C, i.e. obtain room based on heteropolyacid anions
Temperature ionic liquid；Victoria blue B cation in ionic liquid at room temperature based on heteropolyacid anions described in step 4
Mass fraction be 30%～60%.
A kind of ionic liquid at room temperature based on heteropolyacid anions is made up of victoria blue B cation and heteropolyacid anions,
In described ionic liquid at room temperature based on heteropolyacid anions, the mass fraction of victoria blue B cation is
39%～51%, in described ionic liquid at room temperature based on heteropolyacid anions, victoria blue B cation is cloudy with heteropoly acid
The mol ratio of ion is 4:1；Described victoria blue B cationic chemical formula is [C33H32N3]+；Described heteropoly acid is cloudy
Ion chemistry formula is [XM12O40]4-, [XM12O40]4-Middle X is Si, S or P, and M is W or Mo.
The preparation method of above-mentioned a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps:
One, preparation is containing [XM12O40]4-The mixed organic solvents of anion: be dissolved in distilled water by M acid sodium, in stirring
Under the conditions of drip concentrated nitric acid, continue stirring 10min～30min, then dropping the chemicals solution Han X, then condensing reflux is anti-
Answer 30min～2h, i.e. contained [XM12O40]4-The mixed organic solvents of anion；
M acid sodium described in step one is sodium molybdate or sodium tungstate；The chemicals solution containing X described in step one is dense sulfur
Acid, concentration are 2.03mmol/L sodium silicate aqueous solution or strong phosphoric acid；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is
0.5mol/L～2.5mol/L, wherein said victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [XM12O40]4-Cloudy
In the mixed organic solvents of ion, it is cooled to room temperature, stratification after mixing, collects lower floor's solution, i.e. obtain room-temperature ion
Liquid crude product；In victoria blue B solution described in step 3 victoria blue B cation with containing [XM12O40]4-Cloudy
[XM in the mixed organic solvents of ion12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 2～4 times, be finally vacuum dried 8 hours at temperature is 50 DEG C～80 DEG C, i.e. obtain room based on heteropolyacid anions
Temperature ionic liquid；Victoria blue B cation in ionic liquid at room temperature based on heteropolyacid anions described in step 4
Mass fraction be 39%～51%.
A kind of ionic liquid at room temperature based on heteropolyacid anions is by four n-octyl bromination ammonium cation and heteropolyacid anions groups
Becoming, in described ionic liquid at room temperature based on heteropolyacid anions, the mass fraction of four n-octyl bromination ammonium cations is
29.96%, in described ionic liquid at room temperature based on heteropolyacid anions, four n-octyl bromination ammonium cations are cloudy with heteropoly acid
The mol ratio of ion is 4:1；Four described n-octyl bromination ammonium cation chemical formulas are [C32H68N]+；Described heteropoly acid
Anion chemical formula is [α-S2W18O62]4-。
The preparation method of above-mentioned a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps:
By Na2WO4·2H2O is dissolved in distilled water, adds CH3CN, dropping concentration is the most under agitation
The sulfuric acid solution of 18mol/L, stirring and evenly mixing is placed in the water-bath that temperature is 70 DEG C, under the water bath condition that temperature is 70 DEG C
Heated and stirred reaction 13d～15d, is cooled to room temperature, adds petroleum ether, be then transferred in separatory funnel, stratification,
Take upper strata yellow-green liquid, in ventilating kitchen, upper strata yellow-green liquid is poured in beaker, then upper strata yellow-green liquid will be filled
Beaker be placed in the water-bath that temperature is 70 DEG C, and under the water bath condition that temperature is 70 DEG C stir, be just then added dropwise over four
Octyl group ammonium bromide solution, four n-octyl ammonium bromide solution continue stirring reaction under the water bath condition that temperature is 70 DEG C after adding
3h, obtains the ionic liquid of bottle-green solid solution shape, is ionic liquid at room temperature based on heteropolyacid anions, described
Ionic liquid at room temperature cationic based on heteropolyacid anions is four n-octyl bromination ammonium cations, and chemical formula is
[C32H68N]+, mass fraction is 29.96%；In described ionic liquid at room temperature based on heteropolyacid anions, anion is miscellaneous
Polyoxoanion, and chemical formula is [α-S2W18O62]4-；In described ionic liquid at room temperature based on heteropolyacid anions
[C32H68N]+With [α-S2W18O62]4-Mol ratio be 4:1；Described Na2WO4·2H2The quality of O and the volume ratio of distilled water
For 5.6250g:167.5mL；Described distilled water and concentration be the volume ratio of the sulfuric acid solution of 18mol/L be 167.5:37.5；
Described distilled water is 167.5:100 with the volume ratio of petroleum ether；
Four described n-octyl ammonium bromide solution complete according to the following steps: be dissolved in acetonitrile by four n-octyl ammonium bromide,
To four n-octyl ammonium bromide solution, four described n-octyl ammonium bromide chemical formulas are C32H68NBr, four described n-Octyl Bromides
Changing the quality of four n-octyl ammonium bromide and the volume ratio of acetonitrile in ammonium salt solution is 2.3239g:20mL.
The invention have the advantages that one, ionic liquid that the present invention provides be prepared as the most synthetically prepared reaction, device therefor is few,
Step is simple.Reaction condition is gentle, and cost is relatively low, acetonitrile solvent recoverable, is suitable for commercial production.
Two, the ionic liquid that the present invention provides is ionic liquid at room temperature, and fusing point is≤10 DEG C.
Three, the ionic liquid at room temperature based on heteropolyacid anions that the present invention provides is in preparation, remove impurity, dry run
Liquid condition, and sample purity is high.
Four, ionic liquid equal solubilized in water, acetonitrile, ethanol that the present invention provides.And all can show good how gold
Belong to oxygen hydrochlorate electrochemical oxidation-reducing activity.
Five, the present invention provide ionic liquid at room temperature due to its anionicsite be have catalysis activity polyoxometallate,
Can be catalyzed such as organic reactions such as esterification, oxidation reaction, ester exchange and condensations.
Six, the ionic liquid at room temperature based on heteropolyacid anions that the present invention provides can be used as solaode or lithium-ion electric
The electrolyte in pond.Due to the present invention provide its cationic moiety of ionic liquid at room temperature be have dye sensitization performance organic greatly
Molecule, can absorb some visible light, can not only be used as solaode electrolyte, it may have dye sensitization function.Contrast
Victoria blue B dye sensitization P25 solaode, makees electrolyte and sensitization with the ionic liquid at room temperature that the present invention provides
Agent, the electricity conversion of battery can improve more than 13.8%.
Seven, the present invention provide ionic liquid at room temperature due to its anionicsite be heteropolyacid anions, to NO2 -、H2O2
Deng micromolecular water body pollution thing, there is sensitive electrochemical reaction activity, wherein NO2 -Detection limit be not less than
0.17mmol/L, H2O2Detection limit be not less than 0.84mmol/L, can as monitoring NO2 -、H2O2Dirty Deng micromolecular water body
The sensor of dye thing.
Eight, the ionic liquid at room temperature that the present invention provides is insoluble in ethyl acetate, but under ultraviolet light irradiates, can not only change it
Dissolve polarity so that it is be dissolved in ethyl acetate, also can realize water, acetonitrile, the dissolving each other of ethyl acetate.
Accompanying drawing explanation
Fig. 1 is the ionic liquid at room temperature infrared spectrogram based on heteropolyacid anions of test one preparation；
Fig. 2 is cyclic voltammetry curve, and in figure, A represents the ionic liquid at room temperature based on heteropolyacid anions of test one preparation
Cyclic voltammetry curve in water, in figure, B represents that the ionic liquid at room temperature based on heteropolyacid anions of test one preparation exists
Cyclic voltammetry curve in ethanol, in figure, C represents that the ionic liquid at room temperature based on heteropolyacid anions of test one preparation exists
Cyclic voltammetry curve in acetonitrile；
Fig. 3 is P25 solar cell I-V curve, and in figure, A represents that electrolyte I is to P25 solaode dye sensitization
I-V curve, in figure, B represents the electrolyte II I-V curve to P25 solaode dye sensitization；
Fig. 4 is the ionic liquid at room temperature catalytic cycle volt-ampere curve based on heteropolyacid anions of test one preparation；
Fig. 5 is P25 solar cell I-V curve, and in figure, A represents that electrolyte III is to P25 solaode dye sensitization
I-V curve, in figure, B represents the electrolyte IV I-V curve to P25 solaode dye sensitization；
Fig. 6 is the ionic liquid at room temperature infrared spectrogram based on heteropolyacid anions of test four preparation；
Fig. 7 is cyclic voltammetry curve, and in figure, A represents the ionic liquid at room temperature based on heteropolyacid anions of test four preparation
Cyclic voltammetry curve in water, in figure, B represents that the ionic liquid at room temperature based on heteropolyacid anions of test four preparation exists
Cyclic voltammetry curve in ethanol, in figure, C represents that the ionic liquid at room temperature based on heteropolyacid anions of test four preparation exists
Cyclic voltammetry curve in acetonitrile；
Fig. 8 is P25 solar cell I-V curve, and in figure, A represents that electrolyte I is to P25 solaode dye sensitization
I-V curve, in figure, B represents the electrolyte II I-V curve to P25 solaode dye sensitization；
Fig. 9 is the ionic liquid at room temperature catalytic cycle volt-ampere curve based on heteropolyacid anions of test four preparation.
Detailed description of the invention
Detailed description of the invention one: present embodiment is a kind of ionic liquid at room temperature based on heteropolyacid anions, it is characterised in that
Ionic liquid at room temperature based on heteropolyacid anions is made up of victoria blue B cation and heteropolyacid anions, described
In ionic liquid at room temperature based on heteropolyacid anions, the mass fraction of victoria blue B cation is 50.9%, described base
In the ionic liquid at room temperature of heteropolyacid anions, victoria blue B cation is 4:1 with the mol ratio of heteropolyacid anions；
Described victoria blue B cationic chemical formula is [C33H32N3]+；Described heteropolyacid anions chemical formula is
[α-SiMo12O40]4-。
Detailed description of the invention two: present embodiment is the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions,
It is specifically realized by the following steps:
One, preparation is containing [α-SiMo12O40]4-The mixed organic solvents of anion: be dissolved in distilled water by sodium molybdate, is stirring
Drip concentrated nitric acid under the conditions of mixing and concentration be 2.03mol/L sodium silicate aqueous solution, after temperature is down to room temperature, add acetonitrile,
Then it is cooled to room temperature, stratification after condensing reflux reaction 30min, collects upper solution, i.e. contained
[α-SiMo12O40]4-The mixed organic solvents of anion；The quality of described sodium molybdate with the volume ratio of distilled water is
5.5g:30mL；Described distilled water is 30:7.5 with the volume ratio of concentrated nitric acid；Described distilled water and concentration are 2.03mol/L silicic acid
The volume ratio of sodium water solution is 30:10；Described distilled water is 30:100 with the volume ratio of acetonitrile；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is 3.0mol/L, wherein
Described victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [SiMo12O40]4-
In the mixed organic solvents of anion, after mixing, be cooled to room temperature, stratification, collect lower floor's solution, i.e. obtain room temperature from
Sub-liquid crude product；In victoria blue B solution described in step 3 victoria blue B cation with contain
[α-SiMo12O40]4-[α-SiMo in the mixed organic solvents of anion12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 3 times, be finally vacuum dried 8 hours at temperature is 75 DEG C, i.e. obtain room-temperature ion based on heteropolyacid anions
Liquid；In ionic liquid at room temperature based on heteropolyacid anions described in step 4, victoria blue B cation quality contains
Amount is 50.9%.
Detailed description of the invention three: present embodiment is that a kind of ionic liquid at room temperature based on heteropolyacid anions is by Victoria blue
B cation and heteropolyacid anions composition, victoria blue B in described ionic liquid at room temperature based on heteropolyacid anions
The mass fraction of cation is 30%～60%, Victoria blue in described ionic liquid at room temperature based on heteropolyacid anions
B cation is 4:1 with the mol ratio of heteropolyacid anions；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 is W or Mo.
Detailed description of the invention four: present embodiment is the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions,
It is specifically realized by the following steps:
One, preparation is containing [X2M18O62]4-The mixed organic solvents of anion: be dissolved in distilled water by M acid sodium, in stirring
Under the conditions of drip the chemicals solution Han X, after temperature is down to room temperature, add acetonitrile, then condensing reflux react 1h～2h
After be cooled to room temperature, stratification, collect upper solution, i.e. contained [X2M18O62]4-The mixed organic solvents of anion；
M acid sodium described in step one is sodium molybdate or sodium tungstate；The chemicals solution containing X described in step one is dense sulfur
Acid, concentration are 2.03mmol/L sodium silicate aqueous solution or strong phosphoric acid；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is
0.5mol/L～2.5mol/L, wherein said victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: under agitation victoria blue B solution is added dropwise to containing [X2M18O62]4-Being mixed with of anion
In machine solution, stratification after mixing, collect lower floor's solution, i.e. obtain ionic liquid at room temperature crude product；Described in step 3
In victoria blue B solution victoria blue B cation with containing [X2M18O62]4-In the mixed organic solvents of anion
[X2M18O62]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 2～4 times, be finally vacuum dried 8 hours at temperature is 50 DEG C～80 DEG C, i.e. obtain room based on heteropolyacid anions
Temperature ionic liquid；Victoria blue B cation in ionic liquid at room temperature based on heteropolyacid anions described in step 4
Mass fraction be 30%～60%.
Detailed description of the invention five: present embodiment is that a kind of ionic liquid at room temperature based on heteropolyacid anions is by Victoria blue
B cation and heteropolyacid anions composition, victoria blue B in described ionic liquid at room temperature based on heteropolyacid anions
The mass fraction of cation is 39%～51%, Victoria blue in described ionic liquid at room temperature based on heteropolyacid anions
B cation is 4:1 with the mol ratio of heteropolyacid anions；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,
M is W or Mo.
Detailed description of the invention six: present embodiment is the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions,
It is specifically realized by the following steps:
One, preparation is containing [XM12O40]4-The mixed organic solvents of anion: be dissolved in distilled water by M acid sodium, in stirring
Under the conditions of drip concentrated nitric acid, continue stirring 10min～30min, then dropping the chemicals solution Han X, then condensing reflux is anti-
Answer 30min～2h, i.e. contained [XM12O40]4-The mixed organic solvents of anion；
M acid sodium described in step one is sodium molybdate or sodium tungstate；The chemicals solution containing X described in step one is dense sulfur
Acid, concentration are 2.03mmol/L sodium silicate aqueous solution or strong phosphoric acid；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is
0.5mol/L～2.5mol/L, wherein said victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [XM12O40]4-Cloudy
In the mixed organic solvents of ion, it is cooled to room temperature, stratification after mixing, collects lower floor's solution, i.e. obtain room-temperature ion
Liquid crude product；In victoria blue B solution described in step 3 victoria blue B cation with containing [XM12O40]4-Cloudy
[XM in the mixed organic solvents of ion12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 2～4 times, be finally vacuum dried 8 hours at temperature is 50 DEG C～80 DEG C, i.e. obtain room based on heteropolyacid anions
Temperature ionic liquid；Victoria blue B cation in ionic liquid at room temperature based on heteropolyacid anions described in step 4
Mass fraction be 39%～51%.
Detailed description of the invention seven: present embodiment is that a kind of ionic liquid at room temperature based on heteropolyacid anions is by four n-Octyl Bromides
Change ammonium cation and heteropolyacid anions composition, four n-Octyl Bromides in described ionic liquid at room temperature based on heteropolyacid anions
The mass fraction changing ammonium cation is 29.96%, four n-octyls in described ionic liquid at room temperature based on heteropolyacid anions
Ammonium bromide cation is 4:1 with the mol ratio of heteropolyacid anions；Four described n-octyl bromination ammonium cation chemical formulas are
[C32H68N]+；Described heteropolyacid anions chemical formula is [α-S2W18O62]4-。
Detailed description of the invention eight: present embodiment is the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions,
It is specifically realized by the following steps:
By Na2WO4·2H2O is dissolved in distilled water, adds CH3CN, dropping concentration is the most under agitation
The sulfuric acid solution of 18mol/L, stirring and evenly mixing is placed in the water-bath that temperature is 70 DEG C, under the water bath condition that temperature is 70 DEG C
Heated and stirred reaction 13d～15d, is cooled to room temperature, adds petroleum ether, be then transferred in separatory funnel, stratification,
Take upper strata yellow-green liquid, in ventilating kitchen, upper strata yellow-green liquid is poured in beaker, then upper strata yellow-green liquid will be filled
Beaker be placed in the water-bath that temperature is 70 DEG C, and under the water bath condition that temperature is 70 DEG C stir, be just then added dropwise over four
Octyl group ammonium bromide solution, four n-octyl ammonium bromide solution continue stirring reaction under the water bath condition that temperature is 70 DEG C after adding
3h, obtains the ionic liquid of bottle-green solid solution shape, is ionic liquid at room temperature based on heteropolyacid anions, described
Ionic liquid at room temperature cationic based on heteropolyacid anions is four n-octyl bromination ammonium cations, and chemical formula is
[C32H68N]+, mass fraction is 29.96%；In described ionic liquid at room temperature based on heteropolyacid anions, anion is miscellaneous
Polyoxoanion, and chemical formula is [α-S2W18O62]4-；In described ionic liquid at room temperature based on heteropolyacid anions
[C32H68N]+With [α-S2W18O62]4-Mol ratio be 4:1；Described Na2WO4·2H2The quality of O and the volume ratio of distilled water
For 5.6250g:167.5mL；Described distilled water and concentration be the volume ratio of the sulfuric acid solution of 18mol/L be 167.5:37.5；
Described distilled water is 167.5:100 with the volume ratio of petroleum ether；
Four described n-octyl ammonium bromide solution complete according to the following steps: be dissolved in acetonitrile by four n-octyl ammonium bromide,
To four n-octyl ammonium bromide solution, four described n-octyl ammonium bromide chemical formulas are C32H68NBr, four described n-Octyl Bromides
Changing the quality of four n-octyl ammonium bromide and the volume ratio of acetonitrile in ammonium salt solution is 2.3239g:20mL.
Use following verification experimental verification effect of the present invention
Test one: the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps
:
One, preparation is containing [α-SiMo12O40]4-The mixed organic solvents of anion: 5.5g sodium molybdate is dissolved in 30mL distillation
In water, dropping 7.5mL concentrated nitric acid and 10mL concentration are 2.03mmol/L sodium silicate aqueous solution under agitation, treat temperature
After degree is down to room temperature, adds 100mL acetonitrile, be then cooled to room temperature after condensing reflux reaction 30min, stratification,
Collect upper solution, i.e. contained [α-SiMo12O40]4-The mixed organic solvents of anion；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is 3.0mol/L, wherein
Described victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [SiMo12O40]4-
In the mixed organic solvents of anion, after mixing, be cooled to room temperature, stratification, collect lower floor's solution, i.e. obtain room temperature from
Sub-liquid crude product；In victoria blue B solution described in step 3 victoria blue B cation with containing [SiMo12O40]4-
[α-SiMo in the mixed organic solvents of anion12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 3 times, be finally vacuum dried 8 hours at temperature is 75 DEG C, i.e. obtain room-temperature ion based on heteropolyacid anions
Liquid；In ionic liquid at room temperature based on heteropolyacid anions described in step 4, victoria blue B cation quality contains
Amount is 50.9%.
Utilize infrared spectrometer that the ionic liquid at room temperature based on heteropolyacid anions of test one preparation is detected, detection knot
Fruit, as it is shown in figure 1, Fig. 1 is the ionic liquid at room temperature infrared spectrogram based on heteropolyacid anions of test one preparation, passes through
Fig. 1 can be seen that the ionic liquid at room temperature based on heteropolyacid anions prepared by this method is by heteropolyacid anions and Wei Duo
Leah indigo plant B cation composition, purity is high, without any impurity.
Respectively at water, ethanol and acetonitrile as medium, the room-temperature ion liquid based on heteropolyacid anions of detection test one preparation
Body Cyclic voltamogram in water, ethanol and acetonitrile, as in figure 2 it is shown, Fig. 2 is cyclic voltammetry curve, A table in figure
Showing the ionic liquid at room temperature based on heteropolyacid anions testing preparation cyclic voltammetry curve in water, in figure, B represents
The ionic liquid at room temperature based on heteropolyacid anions of test one preparation cyclic voltammetry curve in ethanol, in figure, C represents
The ionic liquid at room temperature based on heteropolyacid anions of test one preparation cyclic voltammetry curve in acetonitrile, can be seen by Fig. 2
The ionic liquid at room temperature based on heteropolyacid anions going out test one preparation can dissolve in water, ethanol, acetonitrile, ionize, and
Keep good anionic electrodeposition chemism.
Adding acetonitrile in the ionic liquid at room temperature based on heteropolyacid anions of test one preparation, configuration obtains electrolyte I He
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, utilize electrolyte I and electrolyte II respectively to P25
Solaode carries out dye sensitization, and test result is as it is shown on figure 3, Fig. 3 is P25 solar cell I-V curve, in figure
A represents the electrolyte I I-V curve to P25 solaode dye sensitization, and in figure, B represents electrolyte II to P25 too
Sun can the I-V curve of battery dye sensitization, by Fig. 3 can be seen that the room temperature based on heteropolyacid anions of test one preparation from
Sub-liquid cannot be only used for solaode electrolyte, and owing to ionic liquid at room temperature based on heteropolyacid anions is to visible
The Absorption of light, it can be as inorganic sensitized dose of use.Ionic liquid at room temperature usage amount based on heteropolyacid anions is the highest,
Solar cell photoelectric efficiency is the highest.
The ionic liquid at room temperature based on heteropolyacid anions of test one preparation is added to the water, obtains ionic liquid at room temperature
-H2O mixed liquor, described ionic liquid at room temperature-H2[C in O mixed liquor33H32N3]4[α-SiMo12O40] concentration be
2mmol/L, to ionic liquid at room temperature-H2O mixed liquor adds H2O2, obtain variable concentrations containing H2O2Solution, containing H2O2
H in solution2O2Concentration is followed successively by 0mmol/L, 4mmol/L, 8mmol/L, 12mmol/L and 16mmol/L,
Scanning speed is that under 50mV/s, detection contains H2O2The catalytic cycle C-V characteristic of solution, as shown in Figure 4, Fig. 4 is catalysis
Cyclic voltammetry curve, from top to bottom containing H in figure2O2H in solution2O2Concentration be followed successively by 0mmol/L, 4mmol/L, 8
Mmol/L, 12mmol/L and 16mmol/L, as seen in Figure 4, along with H in catalystic converter system2O2Concentration
Increase, the oxidation peak current being positioned at about-0.5V of ionic liquid at room temperature based on heteropolyacid anions be positioned at 1.0V
The reduction peak current of left and right constantly increases, and illustrates that the heteropolyacid anions in ionic liquid is constantly reduced, and minimum H2O2
Response concentration is not higher than 0.89mmol/L, it was demonstrated that ionic liquid at room temperature based on heteropolyacid anions can be as H2O2Sensing
Device.
The ionic liquid at room temperature based on heteropolyacid anions testing a preparation under ultraviolet light irradiates realizes water, acetonitrile and acetic acid
Ethyl ester dissolves each other, this is because, in the ionic liquid at room temperature based on heteropolyacid anions of test one preparation, heteropolyacid anions is inhaled
Receive ultraviolet light and self reduction reaction (M occurs6+→M5+), so that heteropolyacid anions " group " surface charge density is sent out
Changing, and then change the size of anions and canons charge attraction power in ionic liquid, so that its polarity changes, real
The ionic liquid at room temperature based on heteropolyacid anions of now test one preparation realizes water, acetonitrile and ethyl acetate and dissolves each other.Additional
Oxidant such as H2O2Or under conditions of visible ray illumination, the room-temperature ion liquid based on heteropolyacid anions of test one preparation
Heteropolyacid anions partial reduction state (M in body5+) there is oxidation reaction (M5+→M6+) so that heteropolyacid anions " collection
Group " surface charge density reparation, it is achieved the ionic liquid at room temperature based on heteropolyacid anions of test one preparation realizes water, second
Nitrile and ethyl acetate layering.Ionic liquid at room temperature based on heteropolyacid anions polarity under the conditions of additional of test one preparation becomes
The reversible process changed, extracts for catalyst extraction in catalytic reaction process, the economic sector of workshop-sink (expecting), it is provided that
A kind of simpler method.
Test two: the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps
:
One, preparation is containing [S2Mo18O62]4-The mixed organic solvents of anion: 6.3g sodium molybdate is dissolved in 20mL distilled water
In, dropping 5mL concentrated sulphuric acid under agitation, after temperature is down to room temperature, adds 100mL acetonitrile, then condense back
It is cooled to room temperature, stratification after stream reaction 2h, collects upper solution, i.e. contained [S2Mo18O62]4-Mixing of anion
Close organic solution；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is 3.0mol/L, wherein
Described victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: under agitation victoria blue B solution is added dropwise to containing [S2Mo18O62]4-Being mixed with of anion
In machine solution, stratification after mixing, collect lower floor's solution, i.e. obtain ionic liquid at room temperature crude product；Described in step 3
In victoria blue B solution victoria blue B cation with containing [S2Mo18O62]4-In the mixed organic solvents of anion
[S2Mo18O62]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 3 times, be finally vacuum dried 8 hours at temperature is 75 DEG C, i.e. obtain room-temperature ion based on heteropolyacid anions
Liquid；In ionic liquid at room temperature based on heteropolyacid anions described in step 4, victoria blue B cation quality contains
Amount is 40.3%.
Using the ionic liquid at room temperature based on heteropolyacid anions of test two preparation as catalyst, utilize the base of test one preparation
In the ionic liquid at room temperature catalytic esterification of heteropolyacid anions, the catalytic selectivity of esterification and catalysis productivity such as table 1
Shown in, understand the ionic liquid at room temperature based on heteropolyacid anions of test one preparation to esterification catalytic by table 1
Activity is high, can be used for Industrial Catalysis reaction.
Table 1
| Reaction raw materials A | Reaction raw materials B | Productivity | Selectivity |
| Citric acid | N-butyl alcohol | 96.4 | 98 |
| Lactic acid | N-butyl alcohol | 89.5 | 100 |
| Acetic acid | N-butyl alcohol | 94.5 | 100 |
| Acetic acid | Glycerol | 84.5 | 89 |
| Acetic acid | Ethylene glycol | 97.7 | 93 |
Test three: the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps
:
One, preparation is containing [SiW12O40]4-The mixed organic solvents of anion: 7.9g sodium tungstate is dissolved in 30mL distilled water
In, dropping 7.5mL concentrated nitric acid under agitation, continues stirring 30min, then to drip 10mL concentration is 2.03mmol/L
Sodium silicate aqueous solution, then condensing reflux reaction 2h, is i.e. contained [SiW12O40]4-The mixed organic solvents of anion；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B
Solution；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is 3.0mol/L, wherein
Described victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [SiW12O40]4-Cloudy
In the mixed organic solvents of ion, it is cooled to room temperature, stratification after mixing, collects lower floor's solution, i.e. obtain room-temperature ion
Liquid crude product；In victoria blue B solution described in step 3 victoria blue B cation with containing [SiW12O40]4-Cloudy
[SiW in the mixed organic solvents of ion12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 3 times, be finally vacuum dried 8 hours at temperature is 75 DEG C, i.e. obtain room-temperature ion based on heteropolyacid anions
Liquid；In ionic liquid at room temperature based on heteropolyacid anions described in step 4, victoria blue B cation quality contains
Amount is 39.6%.
Using test one and test three preparation ionic liquid at room temperature based on heteropolyacid anions as catalyst, utilize test one
With the ionic liquid at room temperature catalytic esterification based on heteropolyacid anions of test three preparation, the catalysis choosing of partial esterification reaction
Selecting property and catalysis productivity are as shown in table 2, understand test one and the room based on heteropolyacid anions of test three preparation by table 2
Temperature ionic liquid is high to esterification catalytic activity, can be used for Industrial Catalysis esterification.
Table 2
| Catalyst | Reaction raw materials A | Reaction raw materials B | Productivity | Selectivity |
| [C33H32N3]4[SiMo12O40] | Citric acid | N-butyl alcohol | 98.1 | 96 |
| [C33H32N3]4[SiMo12O40] | Acetic acid | N-butyl alcohol | 96.7 | 98 |
| [C33H32N3]4[SiMo12O40] | Acetic acid | Glycerol | 91.2 | 83 |
| [C33H32N3]4[SiW12O40] | Citric acid | N-butyl alcohol | 93.8 | 100 |
| [C33H32N3]4[SiW12O40] | Acetic acid | N-butyl alcohol | 91.4 | 97 |
| [C33H32N3]4[SiW12O40] | Acetic acid | Glycerol | 95.5 | 96 |
Adding acetonitrile in the ionic liquid at room temperature based on heteropolyacid anions of test one preparation, configuration obtains electrolyte III,
Adding acetonitrile in the ionic liquid at room temperature based on heteropolyacid anions of test three preparation, configuration obtains electrolyte IV, described
Electrolyte III in [C33H32N3]4[SiMo12O40] concentration be 0.5mmol/L, in described electrolyte IV
[C33H32N3]4[SiW12O40] concentration be 0.5mmol/L, utilize solve liquid III and electrolyte IV respectively to P25 solaode
Carrying out dye sensitization, test result is as it is shown in figure 5, Fig. 5 is P25 solar cell I-V curve, and in figure, A represents electricity
Solving the liquid III I-V curve to P25 solaode dye sensitization, in figure, B represents that electrolyte IV is to P25 solaode
The I-V curve of dye sensitization, by Fig. 5 can be seen that test one and test three preparation room temperatures based on heteropolyacid anions from
Sub-liquid cannot be only used for solaode electrolyte, and owing to ionic liquid at room temperature based on heteropolyacid anions is to visible
The Absorption of light, it can be as inorganic sensitized dose of use.[C33H32N3]4[SiMo12O40] solar cell photoelectric efficiency
Than [C33H32N3]4[SiW12O40] high.
Test four: the preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, is specifically realized by the following steps
:
By 5.6250g Na2WO4·2H2O is dissolved in 167.5mL distilled water, adds 100mL CH3CN, is then stirring
Dripping 37.5mL concentration under the conditions of mixing is the sulfuric acid solution of 18mol/L, and stirring and evenly mixing is placed in the water-bath that temperature is 70 DEG C,
Under the water bath condition that temperature is 70 DEG C, heated and stirred reaction 14d, is cooled to room temperature, adds 100mL petroleum ether, then
It is transferred in separatory funnel, stratification, takes upper strata yellow-green liquid, in ventilating kitchen, pour upper strata yellow-green liquid into burning
In Bei, then the beaker filling upper strata yellow-green liquid is placed in the water-bath that temperature is 70 DEG C, and in the water-bath that temperature is 70 DEG C
Under the conditions of stir, be then added dropwise over four n-octyl ammonium bromide solution, four n-octyl ammonium bromide solution continue in temperature after adding
It is stirring reaction 3h under the water bath condition of 70 DEG C, obtains the ionic liquid of bottle-green solid solution shape, be based on heteropoly acid cloudy
The ionic liquid at room temperature of ion, described ionic liquid at room temperature cationic based on heteropolyacid anions is four n-octyl brominations
Ammonium cation, chemical formula is [C32H68N]+, mass fraction is 29.96%；Described room temperature based on heteropolyacid anions from
In sub-liquid, anion is heteropolyacid anions, and chemical formula is [α-S2W18O62]4-；Described is based on heteropolyacid anions
[C in ionic liquid at room temperature32H68N]+With [α-S2W18O62]4-Mol ratio be 4:1；
Four described n-octyl ammonium bromide solution complete according to the following steps: be dissolved in by 2.3239g tetra-n-octyl ammonium bromide
In 20mL acetonitrile, obtaining four n-octyl ammonium bromide solution, four described n-octyl ammonium bromide chemical formulas are C32H68NBr。
Utilize infrared spectrometer that the ionic liquid at room temperature based on heteropolyacid anions of test four preparation is detected, detection knot
As shown in Figure 6, Fig. 6 is the ionic liquid at room temperature infrared spectrogram based on heteropolyacid anions of test four preparation to fruit, passes through
Fig. 6 by heteropolyacid anions and four just can be seen that the ionic liquid at room temperature based on heteropolyacid anions prepared by this method
Octyl group bromination ammonium cation forms, and purity is high, without any impurity.
Respectively at water, ethanol and acetonitrile as medium, the room-temperature ion liquid based on heteropolyacid anions of detection test four preparation
Body Cyclic voltamogram in water, ethanol and acetonitrile, as it is shown in fig. 7, Fig. 7 is cyclic voltammetry curve, A table in figure
Showing the ionic liquid at room temperature based on heteropolyacid anions testing four preparations cyclic voltammetry curve in water, in figure, B represents
The ionic liquid at room temperature based on heteropolyacid anions of test four preparation cyclic voltammetry curve in ethanol, in figure, C represents
The ionic liquid at room temperature based on heteropolyacid anions of test four preparation cyclic voltammetry curve in acetonitrile, can be seen by Fig. 7
The ionic liquid at room temperature based on heteropolyacid anions going out test four preparation can dissolve in water, ethanol, acetonitrile, ionize, and
Keep good anionic electrodeposition chemism.
To test four preparation ionic liquid at room temperature based on heteropolyacid anions in add acetonitrile, configuration obtain 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, utilize electrolyte III and electrolyte IV respectively to P25
Solaode carries out dye sensitization, and as shown in Figure 8, Fig. 8 is P25 solar cell I-V curve to test result, in figure
A represents the electrolyte III I-V curve to P25 solaode dye sensitization, and in figure, B represents electrolyte IV to P25 too
Sun can the I-V curve of battery dye sensitization, by Fig. 8 can be seen that the room temperatures based on heteropolyacid anions of test four preparation from
Sub-liquid cannot be only used for solaode electrolyte, and owing to ionic liquid at room temperature based on heteropolyacid anions is to visible
The Absorption of light, it can be as inorganic sensitized dose of use.Ionic liquid at room temperature usage amount based on heteropolyacid anions is the highest,
Solar cell photoelectric efficiency is the highest.
The ionic liquid at room temperature based on heteropolyacid anions of test four preparation is added to the water, obtains ionic liquid at room temperature
-H2O mixed liquor, described ionic liquid at room temperature-H2[C in O mixed liquor32H68N]4[α-S2W18O62] concentration be
2mmol/L, to ionic liquid at room temperature-H2O mixed liquor adds Cys, obtains variable concentrations containing Cys
Solution, containing Cys concentration in Cys solution be followed successively by 0mmol/L, 2mmol/L, 4mmol/L, 5
Mmol/L and 7mmol/L, under scanning speed is 50mV/s, the detection catalytic cycle volt-ampere containing Cys solution is special
Property, as it is shown in figure 9, Fig. 9 is catalytic cycle volt-ampere curve, from the bottom to top containing L-half Guang in Cys solution in figure
Propylhomoserin concentration is followed successively by 0mmol/L, 2mmol/L, 4mmol/L, 5mmol/L and 7mmol/L, permissible by Fig. 9
Find out, along with the increasing of Cys concentration in catalystic converter system, ionic liquid at room temperature based on heteropolyacid anions
The reduction peak current being positioned at about 1.22V constantly increase, illustrate that the heteropolyacid anions in ionic liquid is the most oxidized,
And minimum Cys response concentration is not higher than 0.5mmol/L, it was demonstrated that ionic liquid at room temperature based on heteropolyacid anions can
Sensor as Cys.
Claims (8)
1. an ionic liquid at room temperature based on heteropolyacid anions, it is characterised in that room-temperature ion based on heteropolyacid anions
Liquid is made up of victoria blue B cation and heteropolyacid anions, described room-temperature ion liquid based on heteropolyacid anions
In body, the mass fraction of victoria blue B cation is 50.9%, described ionic liquid at room temperature based on heteropolyacid anions
Middle victoria blue B cation is 4:1 with the mol ratio of heteropolyacid anions；Described victoria blue B cationic chemical
Formula is [C33H32N3]+；Described heteropolyacid anions chemical formula is [α-SiMo12O40]4-。
The preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, its feature exists
Preparation method in a kind of ionic liquid at room temperature based on heteropolyacid anions completes according to the following steps:
One, preparation is containing [α-SiMo12O40]4-The mixed organic solvents of anion: be dissolved in distilled water by sodium molybdate, in stirring
Under the conditions of to drip concentrated nitric acid and concentration be 2.03mol/L sodium silicate aqueous solution, after temperature is down to room temperature, add acetonitrile, then
It is cooled to room temperature, stratification after condensing reflux reaction 30min, collects upper solution, i.e. contained [α-SiMo12O40]4-
The mixed organic solvents of anion；The quality of described sodium molybdate and the volume ratio of distilled water are 5.5g:30mL；Described distilled water with
The volume ratio of concentrated nitric acid is 30:7.5；Described distilled water and concentration be the volume ratio of 2.03mol/L sodium silicate aqueous solution be 30:10；
Described distilled water is 30:100 with the volume ratio of acetonitrile；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B molten
Liquid；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is 3.0mol/L, Qi Zhongsuo
The victoria blue B cationic chemical formula stated is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [SiMo12O40]4-Cloudy
In the mixed organic solvents of ion, it is cooled to room temperature, stratification after mixing, collects lower floor's solution, i.e. obtain room-temperature ion
Liquid crude product；In victoria blue B solution described in step 3 victoria blue B cation with containing [α-SiMo12O40]4-
[α-SiMo in the mixed organic solvents of anion12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 3 times, be finally vacuum dried 8 hours at temperature is 75 DEG C, i.e. obtain room-temperature ion liquid based on heteropolyacid anions
Body；In ionic liquid at room temperature based on heteropolyacid anions described in step 4, victoria blue B cation mass content is
50.9%.
3. an ionic liquid at room temperature based on heteropolyacid anions, it is characterised in that room-temperature ion based on heteropolyacid anions
Liquid is made up of victoria blue B cation and heteropolyacid anions, described room-temperature ion liquid based on heteropolyacid anions
In body, the mass fraction of victoria blue B cation is 30%～60%, described room-temperature ion liquid based on heteropolyacid anions
In body, victoria blue B cation is 4:1 with the mol ratio of heteropolyacid anions；Described victoria blue B cationization
Formula is [C33H32N3]+；Described heteropolyacid anions chemical formula is [X2M18O62]4-, [X2M18O62]4-Middle X is Si, S
Or P, M are W or Mo.
The preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, its feature exists
Preparation method in a kind of ionic liquid at room temperature based on heteropolyacid anions completes according to the following steps:
One, preparation is containing [X2M18O62]4-The mixed organic solvents of anion: be dissolved in distilled water by M acid sodium, at stirring bar
Drip the chemicals solution Han X under part, after temperature is down to room temperature, add acetonitrile, then cold after condensing reflux reaction 1h～2h
But to room temperature, stratification, collect upper solution, i.e. contained [X2M18O62]4-The mixed organic solvents of anion；
M acid sodium described in step one is sodium molybdate or sodium tungstate；The chemicals solution containing X described in step one be concentrated sulphuric acid,
Concentration is 2.03mol/L sodium silicate aqueous solution or strong phosphoric acid；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B molten
Liquid；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In victoria blue B solution described in step 2, the concentration of victoria blue B cation is
0.5mol/L～2.5mol/L, wherein said victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: under agitation victoria blue B solution is added dropwise to containing [X2M18O62]4-The mixing of anion is organic
In solution, stratification after mixing, collect lower floor's solution, i.e. obtain ionic liquid at room temperature crude product；Tie up described in step 3
In many Leahs indigo plant B solution victoria blue B cation with containing [X2M18O62]4-In the mixed organic solvents of anion
[X2M18O62]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 2～4 times, be finally vacuum dried 8 hours at temperature is 50 DEG C～80 DEG C, i.e. obtain room based on heteropolyacid anions
Temperature ionic liquid；Victoria blue B cation in ionic liquid at room temperature based on heteropolyacid anions described in step 4
Mass fraction is 30%～60%.
5. an ionic liquid at room temperature based on heteropolyacid anions, it is characterised in that room-temperature ion based on heteropolyacid anions
Liquid is made up of victoria blue B cation and heteropolyacid anions, described room-temperature ion liquid based on heteropolyacid anions
In body, the mass fraction of victoria blue B cation is 39%～51%, described room-temperature ion liquid based on heteropolyacid anions
In body, victoria blue B cation is 4:1 with the mol ratio of heteropolyacid anions；Described victoria blue B cationization
Formula is [C33H32N3]+；Described heteropolyacid anions chemical formula is [XM12O40]4-, [XM12O40]4-Middle X is Si, S
Or P, M are W or Mo.
The preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, its feature exists
Preparation method in a kind of ionic liquid at room temperature based on heteropolyacid anions completes according to the following steps:
One, preparation is containing [XM12O40]4-The mixed organic solvents of anion: be dissolved in distilled water by M acid sodium, at stirring bar
Drip concentrated nitric acid under part, continue stirring 10min～30min, then dropping chemicals solution Han X, then condensing reflux reaction
30min～2h, is i.e. contained [XM12O40]4-The mixed organic solvents of anion；
M acid sodium described in step one is sodium molybdate or sodium tungstate；The chemicals solution containing X described in step one be concentrated sulphuric acid,
Concentration is 2.03mol/L sodium silicate aqueous solution or strong phosphoric acid；
Two, victoria blue B solution is prepared: be dissolved in solvent by victoria blue B powder body, obtain victoria blue B molten
Liquid；
Victoria blue B powder body chemical formula described in step 2 is C33H32N3Cl；
In titan yellow solution described in step 2, the concentration of victoria blue B cation is 0.5mol/L～2.5mol/L, wherein
Described victoria blue B cationic chemical formula is [C33H32N3]+；
Solvent described in step 2 is acetonitrile；
Three, mixing: be 50 DEG C in temperature and under stirring condition, victoria blue B solution be added dropwise to containing [XM12O40]4-Cloudy from
In the mixed organic solvents of son, it is cooled to room temperature, stratification after mixing, collects lower floor's solution, i.e. obtain room-temperature ion liquid
Body crude product；In victoria blue B solution described in step 3 victoria blue B cation with containing [XM12O40]4-Anion
Mixed organic solvents in [XM12O40]4-Mol ratio be 4:1；
Four, remove impurity: ionic liquid at room temperature crude product carries out rotary evaporation process, processes 2 hours, then uses petroleum ether
Clean 2～4 times, be finally vacuum dried 8 hours at temperature is 50 DEG C～80 DEG C, i.e. obtain room based on heteropolyacid anions
Temperature ionic liquid；Victoria blue B cation in ionic liquid at room temperature based on heteropolyacid anions described in step 4
Mass fraction is 39%～51%.
7. an ionic liquid at room temperature based on heteropolyacid anions, it is characterised in that room-temperature ion based on heteropolyacid anions
Liquid is made up of four n-octyl bromination ammonium cations and heteropolyacid anions, described room-temperature ion based on heteropolyacid anions
In liquid, the mass fraction of four n-octyl bromination ammonium cations is 29.96%, described room-temperature ion based on heteropolyacid anions
In liquid, four n-octyl bromination ammonium cations are 4:1 with the mol ratio of heteropolyacid anions；Described four n-octyl ammonium bromide sun from
Sub-chemical formula is [C32H68N]+；Described heteropolyacid anions chemical formula is [α-S2W18O62]4-。
The preparation method of a kind of ionic liquid at room temperature based on heteropolyacid anions, its feature exists
Preparation method in a kind of ionic liquid at room temperature based on heteropolyacid anions completes according to the following steps:
By Na2WO4·2H2O is dissolved in distilled water, adds CH3CN, dropping concentration is the most under agitation
The sulfuric acid solution of 18mol/L, stirring and evenly mixing is placed in the water-bath that temperature is 70 DEG C, under the water bath condition that temperature is 70 DEG C
Heated and stirred is reacted 13～15 days, is cooled to room temperature, adds petroleum ether, is then transferred in separatory funnel, stratification,
Take upper strata yellow-green liquid, in ventilating kitchen, upper strata yellow-green liquid is poured in beaker, then upper strata yellow-green liquid will be filled
Beaker be placed in the water-bath that temperature is 70 DEG C, and under the water bath condition that temperature is 70 DEG C stir, be just then added dropwise over four
Octyl group ammonium bromide solution, four n-octyl ammonium bromide solution continue to stir reaction 3 under the water bath condition that temperature is 70 DEG C after adding
Hour, obtain the ionic liquid of bottle-green solid solution shape, be ionic liquid at room temperature based on heteropolyacid anions, described
Ionic liquid at room temperature cationic based on heteropolyacid anions be four n-octyl bromination ammonium cations, chemical formula is
[C32H68N]+, mass fraction is 29.96%；In described ionic liquid at room temperature based on heteropolyacid anions, anion is miscellaneous
Polyoxoanion, and chemical formula is [α-S2W18O62]4-；In described ionic liquid at room temperature based on heteropolyacid anions
[C32H68N]+With [α-S2W18O62]4-Mol ratio be 4:1；Described Na2WO4·2H2The quality of O and the volume ratio of distilled water
For 5.6250g:167.5mL；Described distilled water and concentration be the volume ratio of the sulfuric acid solution of 18mol/L be 167.5:37.5；
Described distilled water is 167.5:100 with the volume ratio of petroleum ether；
Four described n-octyl ammonium bromide solution complete according to the following steps: be dissolved in acetonitrile by four n-octyl ammonium bromide,
To four n-octyl ammonium bromide solution, four described n-octyl ammonium bromide chemical formulas are C32H68NBr, four described n-octyl brominations
In ammonium salt solution, the quality of four n-octyl ammonium bromide and the volume ratio of acetonitrile are 2.3239g:20mL.
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