CN107652186B - Application of room-temperature ionic liquid based on heteropoly acid anions - Google Patents

Application of room-temperature ionic liquid based on heteropoly acid anions Download PDF

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CN107652186B
CN107652186B CN201710852368.4A CN201710852368A CN107652186B CN 107652186 B CN107652186 B CN 107652186B CN 201710852368 A CN201710852368 A CN 201710852368A CN 107652186 B CN107652186 B CN 107652186B
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CN107652186A (en
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李春香
徐晟�
雷斌
袁青
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Harbin Institute of Technology
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    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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Abstract

An application of room temperature ionic liquid based on heteropoly acid anions relates to an application of room temperature ionic liquid. The invention aims to solve the problems that the existing polyoxometallate ionic liquid is small in type and quantity and is in a non-liquid state at room temperature. The room temperature ionic liquid based on heteropoly acid anions is used as a sensor of L-cysteine.

Description

Application of room-temperature ionic liquid based on heteropoly acid anions
Technical Field
The invention relates to application of room-temperature ionic liquid, which is a divisional application of room-temperature ionic liquid based on heteropoly acid anions and a preparation method thereof, wherein the application date of the room-temperature ionic liquid is 2016, 4 and 12, and the application number of the room-temperature ionic liquid is 201610224764.8.
Background
The ionic liquid is salt which is liquid at room temperature or at the temperature of less than 100 ℃ and is basically composed of anions and cations, and is also called low-temperature molten salt. Compared with the traditional liquid material, the ionic liquid has the following outstanding characteristics: (1) low steam pressure, non-volatilization, difficult combustion and low toxicity to people and environment; (2) the melting point is low, the liquid state temperature range is wide (lower than or close to room temperature-300 ℃), and the chemical stability and the thermal stability are good; (3) the electrochemical stability is high, and the electrochemical window is wide; (4) the dissolving capacity is strong, and inorganic substances, organic substances and polymers can be dissolved; (5) can form a two-phase or multi-phase system with other solvents, and is suitable for being used as a reaction medium, a catalyst, a separation solvent and the like; (6) can be repeatedly used. At present, ionic liquid is widely applied to processes such as organic reaction, material synthesis and mixture separation as a novel solvent and medium. Particularly, the catalyst is used as a green solvent to replace an organic solvent to dissolve the catalyst or extract a product of a reaction mixture, so that the use of the organic solvent in a heterogeneous catalytic reaction system is greatly reduced, and the harm of the organic solvent to the atmospheric environment and the human health can be reduced.
The ionic liquid is composed of organic cations and inorganic or organic anions, wherein common cations comprise quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazole salt ions and the like, and anions comprise halogen ions, tetrafluoroborate ions, hexafluorophosphate ions and the like. In the ionic liquid studied at present, cations are mainly imidazole cations, and anions are mainly halogen ions and other inorganic acid ions. The ionic liquid can be divided into two main types of halide salt ionic liquid and new ionic liquid according to the difference of anions. The halide ionic liquid is prepared from organic cation AlCl3Or AlBr3The specific preparation method is to mix solid organic cation halide salt with AlCl3Or AlBr3The components are not fixed. Such ionic liquids are large in quantity, but sensitive to water and air, and are mainly used as reaction solvents. The new ionic liquid is a kind of multifunctional ionic liquid which has been developed recently, has fixed chemical composition, is stable to water and air, and is different according to anions, such as C3F7COO-、SbF6 -、AsF6 -And heteropoly acid anions and the like, and the anions endow the novel ionic liquid with richer properties, such as catalysis, extraction and separation of metal ions, absorption and separation of gas and the like. At present, the application research of the new ionic liquid mainly focuses on the aspects of organic synthesis, catalytic reaction, separation technology, desulfurization by using the ionic liquid and the like.
Generally, the organic ionic liquid is prepared by a one-step synthesis method and a two-step synthesis method. The one-step synthesis method is obtained through one-step synthesis through acid-base neutralization reaction or quaternization reaction. The one-step synthesis method is simple to operate, has no by-products, and is easy to purify products. The first step of the two-step synthesis method is to synthesize quaternary ammonium salt by the reaction of imidazole and alkyl halide, and the second step is to react the quaternary ammonium salt with Lewis acid or perform replacement reaction with alkali metal salt or acid containing required anions to obtain the target ionic liquid. Or directly adding organic cation or inorganic anion with proper proportion into inorganic or organic salt to prepare corresponding ionic liquid (direct method). The new ionic liquid synthesized by one-step or direct method and two-step synthesis method, especially the ionic liquid containing heteropoly acid anion, is solid at room temperature mostly and can be in liquid state only at the temperature of more than 100 ℃ or 200 ℃ due to the high charge density of the polyoxometallate ion and strong bonding force between anion and cation. Strictly speaking, such substances that are solid at room temperature cannot be referred to as ionic liquids. Therefore, the preparation of the new ionic liquid, particularly the polyoxometallate ionic liquid, not only can enrich the variety and the quantity of the ionic liquid, but also can expand the application range of the ionic liquid to a plurality of subjects such as chemistry, biomedicine, food science and the like by means of the new property of the ionic liquid given by the heteropoly acid anions, and has special significance. Meanwhile, the heteropoly acid anion ionic liquid can enrich and expand the research and application range of polyoxometallate and endow the polyoxometallate with new application value.
Disclosure of Invention
The invention aims to solve the problems that the existing polyoxometallate ionic liquid is small in type and quantity and is not in a liquid state at room temperature, and provides application of the room-temperature ionic liquid based on polyoxometallate ions.
The room-temperature ionic liquid based on the heteropoly acid anions consists of victoria blue B cations and heteropoly acid anions, wherein the mass fraction of the victoria blue B cations in the room-temperature ionic liquid based on the heteropoly acid anions is 50.9%, and the molar ratio of the victoria blue B cations to the heteropoly acid anions in the room-temperature ionic liquid based on the heteropoly acid anions is 4: 1; the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+The chemical formula of heteropoly acid anion is [ α -SiMo12O40]4-。
The preparation method of the room-temperature ionic liquid based on heteropoly acid anions comprises the following steps:
firstly, preparing the catalyst containing [ α -SiMo12O40]4-Dissolving sodium molybdate in distilled water, dropwise adding concentrated nitric acid and 2.03mol/L sodium silicate aqueous solution under stirring, cooling to room temperature, adding acetonitrile, performing condensation reflux reaction for 30min, cooling to room temperature, standing for layering, and collecting the upper layer solution to obtain a mixed organic solution containing [ α -SiMo12O40]4-Mixed organic solutions of anions; the volume ratio of the mass of the sodium molybdate to the distilled water is 5.5g to 30 mL; the volume ratio of the distilled water to the concentrated nitric acid is 30: 7.5; the volume ratio of the distilled water to the sodium silicate aqueous solution with the concentration of 2.03mol/L is 30: 10; the volume ratio of the distilled water to the acetonitrile is 30: 100;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 3.0mol/L, wherein the chemical formula of the Victoria blue B cation is [ C [ ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding the Victoria blue B solution into the solution containing [ SiMo ] at the temperature of 50 ℃ under stirring12O40]4-Mixing the anions in the mixed organic solution, cooling to room temperature, standing for layering, and collecting the lower layer solution to obtain room temperature ionic liquid crude product, wherein Victoria blue B cations and the solution containing [ α -SiMo ] in the Victoria blue B solution in the third step12O40]4-Mixed organic solution of anions [ α -SiMo ]12O40]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning for 3 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 75 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the content of the Victoria blue B cation in the room-temperature ionic liquid based on heteropoly acid anions in the fourth step is 50.9 percent by mass.
The room-temperature ionic liquid based on the heteropoly acid anions consists of victoria blue B cations and heteropoly acid anions, wherein the mass fraction of the victoria blue B cations in the room-temperature ionic liquid based on the heteropoly acid anions is 30-60%, and the molar ratio of the victoria blue B cations to the heteropoly acid anions in the room-temperature ionic liquid based on the heteropoly acid anions is 4: 1; the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+(ii) a The chemical formula of the heteropoly acid anion is [ X ]2M18O62]4-，[X2M18O62]4-Wherein X is Si, S or P, and M is W or Mo.
The preparation method of the room-temperature ionic liquid based on heteropoly acid anions comprises the following steps:
preparation of a catalyst containing [ X2M18O62]4-Mixed organic solution of anions: dissolving sodium M in distilled water, dropwise adding a chemical solution containing X under the stirring condition, adding acetonitrile after the temperature is reduced to room temperature, then carrying out condensation reflux reaction for 1-2 h, cooling to room temperature, standing for layering, and collecting an upper-layer solution to obtain a solution containing [ X [2M18O62]4-Mixed organic solutions of anions;
the sodium M in the first step is sodium molybdate or sodium tungstate; the chemical solution containing X in the step one is concentrated sulfuric acid, sodium silicate aqueous solution with the concentration of 2.03mmol/L or concentrated phosphoric acid;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 0.5-2.5 mol/L, wherein the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding the Victoria blue B solution into the solution containing [ X ] under stirring2M18O62]4-Mixing the anion and the organic solution, standing for layering, and collecting the lower layer solution to obtain a room-temperature ionic liquid crude product; the Victoria blue B cation in the Victoria blue B solution in the third step and the complex containing [ X2M18O62]4-Mixed organic solution of anions [ X ]2M18O62]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning the crude product for 2-4 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 50-80 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the mass fraction of the Victoria blue B cation in the room-temperature ionic liquid based on heteropoly acid anions in the step four is 30-60%.
The room-temperature ionic liquid based on the heteropoly acid anions consists of victoria blue B cations and heteropoly acid anions, wherein the mass fraction of the victoria blue B cations in the room-temperature ionic liquid based on the heteropoly acid anions is 39% -51%, and the molar ratio of the victoria blue B cations to the heteropoly acid anions in the room-temperature ionic liquid based on the heteropoly acid anions is 4: 1; the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+(ii) a The heteropoly acid anion has the chemical formula of [ XM12O40]4-，[XM12O40]4-Wherein X is Si, S or P, and M is W or Mo.
The preparation method of the room-temperature ionic liquid based on heteropoly acid anions comprises the following steps:
one, preparation of a composition containing [ XM12O40]4-Mixed organic solution of anions: dissolving sodium M in distilled water, dripping concentrated nitric acid under the stirring condition, continuously stirring for 10-30 min, dripping a chemical solution containing X, and then condensing and refluxing for 30-2 h to obtain the product containing [ XM12O40]4-Mixed organic solutions of anions;
the sodium M in the first step is sodium molybdate or sodium tungstate; the chemical solution containing X in the step one is concentrated sulfuric acid, sodium silicate aqueous solution with the concentration of 2.03mmol/L or concentrated phosphoric acid;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 0.5-2.5 mol/L, wherein the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding Victoria blue B solution into [ XM ] solution at 50 deg.C under stirring12O40]4-Mixing the anion and the organic solution, cooling to room temperature, standing for layering, and collecting the lower layer solution to obtain a room-temperature ionic liquid crude product; the Victoria blue B cation in the Victoria blue B solution in the third step is mixed with [ XM12O40]4-Mixed organic solution of anions [ XM12O40]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning the crude product for 2-4 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 50-80 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the mass fraction of the Victoria blue B cations in the room-temperature ionic liquid based on heteropoly acid anions in the fourth step is 39-51%.
The room-temperature ionic liquid based on the heteropoly acid anions consists of tetra-n-octyl ammonium bromide cations and heteropoly acid anions, wherein the mass fraction of the tetra-n-octyl ammonium bromide cations in the room-temperature ionic liquid based on the heteropoly acid anions is 29.96 percent, and the molar ratio of the tetra-n-octyl ammonium bromide cations to the heteropoly acid anions in the room-temperature ionic liquid based on the heteropoly acid anions is 4: 1; the chemical formula of the tetra-n-octyl ammonium bromide cation is [ C ]32H68N]+The chemical formula of heteropoly acid anion is [ α -S2W18O62]4-。
The preparation method of the room-temperature ionic liquid based on heteropoly acid anions comprises the following steps:
mixing Na2WO4·2H2Dissolving O in distilled water, and adding CH3CN, dripping 18mol/L sulfuric acid solution under the stirring condition, uniformly stirring, placing in a water bath at the temperature of 70 ℃, heating and stirring for reaction for 13-15 d under the water bath at the temperature of 70 ℃, cooling to room temperature, adding petroleum ether, transferring to a separating funnel, standing for layering, taking upper yellow-green liquid, pouring the upper yellow-green liquid into a beaker in a ventilated kitchen, placing the beaker containing the upper yellow-green liquid into the water bath at the temperature of 70 ℃, stirring under the water bath at the temperature of 70 ℃, then dripping tetra-n-octyl ammonium bromide solution, continuing stirring and reacting for 3 hours under the water bath at the temperature of 70 ℃ after the tetra-n-octyl ammonium bromide solution is added, obtaining dark green solid solution ionic liquid, namely the room temperature ionic liquid based on heteropoly acid anions, wherein cations in the room temperature ionic liquid based on heteropoly acid anions are tetra-n-octyl ammonium bromide cations, has a chemical formula of [ C32H68N]+29.96 percent by mass, wherein the anion in the room-temperature ionic liquid based on the heteropoly acid anion is heteropoly acid anion and has the chemical formula of [ α -S%2W18O62]4-(ii) a The described room temperature separation based on heteropoly acid anionsIn the seed liquid [ C32H68N]+And [ α -S2W18O62]4-In a molar ratio of 4: 1; said Na2WO4·2H2The volume ratio of the mass of O to the volume of distilled water is 5.6250g:167.5 mL; the volume ratio of the distilled water to the sulfuric acid solution with the concentration of 18mol/L is 167.5: 37.5; the volume ratio of the distilled water to the petroleum ether is 167.5: 100;
the tetra-n-octyl ammonium bromide solution is prepared by the following steps: dissolving tetra-n-octyl ammonium bromide in acetonitrile to obtain tetra-n-octyl ammonium bromide solution, wherein the chemical formula of the tetra-n-octyl ammonium bromide is C32H68NBr, the ratio of the mass of tetra-n-octylammonium bromide to the volume of acetonitrile in the tetra-n-octylammonium bromide solution is 2.3239g:20 mL.
The invention has the advantages that: firstly, the preparation of the ionic liquid provided by the invention is a basic synthesis preparation reaction, the used equipment is less, and the steps are simple. The reaction condition is mild, the cost is low, and the acetonitrile solvent can be recycled, so that the method is suitable for industrial production.
Secondly, the ionic liquid provided by the invention is room-temperature ionic liquid, and the melting point is less than or equal to 10 ℃.
And thirdly, the room-temperature ionic liquid based on heteropoly acid anions provided by the invention is in a liquid state in the processes of preparation, impurity removal and drying, and the purity of a sample is high.
Fourthly, the ionic liquid provided by the invention can be dissolved in water, acetonitrile and ethanol. And all can show good polyoxometallate electrochemical oxidation-reduction activity.
And fifthly, the room-temperature ionic liquid can catalyze organic reactions such as esterification, oxidation reaction, ester exchange, condensation and the like because the anion part of the room-temperature ionic liquid is polyoxometallate with catalytic activity.
Sixthly, the room-temperature ionic liquid based on heteropoly acid anions provided by the invention can be used as electrolyte of a solar battery or a lithium ion battery. The cation part of the room-temperature ionic liquid provided by the invention is an organic macromolecule with dye sensitization performance, can absorb part of visible light, and not only can be used as solar cell electrolyte, but also has the dye sensitization function. Compared with a Victoria blue B dye-sensitized P25 solar cell, the room-temperature ionic liquid provided by the invention is used as an electrolyte and a sensitizer, and the photoelectric conversion efficiency of the cell can be improved by more than 13.8%.
Seventhly, the room-temperature ionic liquid provided by the invention is NO because the anion part of the room-temperature ionic liquid is heteropoly acid anion2 -、H2O2The water body pollutants with small molecules have sensitive electrochemical reaction activity, wherein NO is contained in the water body pollutants2 -The detection limit of (A) is not less than 0.17mmol/L, H2O2The detection limit of (2) is not less than 0.84mmol/L, and the product can be used for monitoring NO2 -、H2O2And the like, small molecular water pollutants.
The room-temperature ionic liquid provided by the invention is insoluble in ethyl acetate, but under the irradiation of ultraviolet light, the solubility polarity of the ionic liquid can be changed, so that the ionic liquid is dissolved in ethyl acetate, and mutual solubility of water, acetonitrile and ethyl acetate can be realized.
Drawings
FIG. 1 is a graph of the infrared spectrum of a room temperature ionic liquid based on heteropoly acid anions prepared in experiment one;
FIG. 2 is a cyclic voltammogram, wherein A represents a cyclic voltammogram of a prepared room temperature heteropolyacid anion-based ionic liquid in water, B represents a cyclic voltammogram of a prepared room temperature heteropolyacid anion-based ionic liquid in ethanol, and C represents a cyclic voltammogram of a prepared room temperature heteropolyacid anion-based ionic liquid in acetonitrile;
FIG. 3 is an I-V curve of a P25 solar cell, wherein A represents an I-V curve of an electrolyte I on the dye sensitization of a P25 solar cell, and B represents an I-V curve of an electrolyte II on the dye sensitization of a P25 solar cell;
FIG. 4 is a plot of room temperature ionic liquid catalytic cyclic voltammetry based on heteropoly acid anions prepared in run one;
FIG. 5 is an I-V curve of a P25 solar cell, wherein A represents an I-V curve of electrolyte III for dye sensitization of a P25 solar cell, and B represents an I-V curve of electrolyte IV for dye sensitization of a P25 solar cell;
FIG. 6 is a graph of the infrared spectrum of a room temperature ionic liquid based on heteropolyacid anions prepared in experiment four;
FIG. 7 is a cyclic voltammogram, wherein A represents the cyclic voltammogram of a heteropolyacid anion-based room-temperature ionic liquid prepared in test IV in water, wherein B represents the cyclic voltammogram of a heteropolyacid anion-based room-temperature ionic liquid prepared in test IV in ethanol, and wherein C represents the cyclic voltammogram of a heteropolyacid anion-based room-temperature ionic liquid prepared in test IV in acetonitrile;
FIG. 8 is an I-V curve of a P25 solar cell, wherein A represents an I-V curve of an electrolyte I on the dye sensitization of a P25 solar cell, and B represents an I-V curve of an electrolyte II on the dye sensitization of a P25 solar cell;
FIG. 9 is a room temperature ionic liquid catalytic cyclic voltammogram based on heteropolyacid anions prepared for run four.
Detailed Description
The first embodiment is as follows: the embodiment is room-temperature ionic liquid based on heteropoly acid anions, which is characterized in that the room-temperature ionic liquid based on heteropoly acid anions consists of victoria blue B cations and heteropoly acid anions, the mass fraction of the victoria blue B cations in the room-temperature ionic liquid based on heteropoly acid anions is 50.9%, and the molar ratio of the victoria blue B cations to the heteropoly acid anions in the room-temperature ionic liquid based on heteropoly acid anions is 4: 1; the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+The chemical formula of heteropoly acid anion is [ α -SiMo12O40]4-。
The second embodiment is as follows: the embodiment is a preparation method of room-temperature ionic liquid based on heteropoly acid anions, which is specifically completed by the following steps:
firstly, preparing the catalyst containing [ α -SiMo12O40]4-Mixed organic solution of anions: dissolving sodium molybdate in distilled water, and dropwise adding concentrated nitric acid and 2.03mol/L concentration while stirringCooling sodium silicate water solution to room temperature, adding acetonitrile, condensing, refluxing for 30min, cooling to room temperature, standing for layering, and collecting the upper layer solution to obtain the final product containing [ α -SiMo12O40]4-Mixed organic solutions of anions; the volume ratio of the mass of the sodium molybdate to the distilled water is 5.5g to 30 mL; the volume ratio of the distilled water to the concentrated nitric acid is 30: 7.5; the volume ratio of the distilled water to the sodium silicate aqueous solution with the concentration of 2.03mol/L is 30: 10; the volume ratio of the distilled water to the acetonitrile is 30: 100;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 3.0mol/L, wherein the chemical formula of the Victoria blue B cation is [ C [ ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding the Victoria blue B solution into the solution containing [ SiMo ] at the temperature of 50 ℃ under stirring12O40]4-Mixing the anions in the mixed organic solution, cooling to room temperature, standing for layering, and collecting the lower layer solution to obtain room temperature ionic liquid crude product, wherein Victoria blue B cations and the solution containing [ α -SiMo ] in the Victoria blue B solution in the third step12O40]4-Mixed organic solution of anions [ α -SiMo ]12O40]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning for 3 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 75 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the content of the Victoria blue B cation in the room-temperature ionic liquid based on heteropoly acid anions in the fourth step is 50.9 percent by mass.
Detailed DescriptionThirdly, the method comprises the following steps: the embodiment is that the room-temperature ionic liquid based on heteropoly acid anions consists of victoria blue B cations and heteropoly acid anions, the mass fraction of the victoria blue B cations in the room-temperature ionic liquid based on the heteropoly acid anions is 30-60%, and the molar ratio of the victoria blue B cations to the heteropoly acid anions in the room-temperature ionic liquid based on the heteropoly acid anions is 4: 1; the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+(ii) a The chemical formula of the heteropoly acid anion is [ X ]2M18O62]4-，[X2M18O62]4-Wherein X is Si, S or P, and M is W or Mo.
The fourth concrete implementation mode: the embodiment is a preparation method of room-temperature ionic liquid based on heteropoly acid anions, which is specifically completed by the following steps:
preparation of a catalyst containing [ X2M18O62]4-Mixed organic solution of anions: dissolving sodium M in distilled water, dropwise adding a chemical solution containing X under the stirring condition, adding acetonitrile after the temperature is reduced to room temperature, then carrying out condensation reflux reaction for 1-2 h, cooling to room temperature, standing for layering, and collecting an upper-layer solution to obtain a solution containing [ X [2M18O62]4-Mixed organic solutions of anions;
the sodium M in the first step is sodium molybdate or sodium tungstate; the chemical solution containing X in the step one is concentrated sulfuric acid, sodium silicate aqueous solution with the concentration of 2.03mmol/L or concentrated phosphoric acid;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 0.5-2.5 mol/L, wherein the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding the Victoria blue B solution into the solution containing [ X ] under stirring2M18O62]4-Mixing the anion and the organic solution, standing for layering, and collecting the lower layer solution to obtain a room-temperature ionic liquid crude product; the Victoria blue B cation in the Victoria blue B solution in the third step and the complex containing [ X2M18O62]4-Mixed organic solution of anions [ X ]2M18O62]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning the crude product for 2-4 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 50-80 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the mass fraction of the Victoria blue B cation in the room-temperature ionic liquid based on heteropoly acid anions in the step four is 30-60%.
The fifth concrete implementation mode: the embodiment is that the room-temperature ionic liquid based on heteropoly acid anions consists of victoria blue B cations and heteropoly acid anions, the mass fraction of the victoria blue B cations in the room-temperature ionic liquid based on the heteropoly acid anions is 39% -51%, and the molar ratio of the victoria blue B cations to the heteropoly acid anions in the room-temperature ionic liquid based on the heteropoly acid anions is 4: 1; the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+(ii) a The heteropoly acid anion has the chemical formula of [ XM12O40]4-，[XM12O40]4-Wherein X is Si, S or P, and M is W or Mo.
The sixth specific implementation mode: the embodiment is a preparation method of room-temperature ionic liquid based on heteropoly acid anions, which is specifically completed by the following steps:
one, preparation of a composition containing [ XM12O40]4-Mixed organic solution of anions: dissolving sodium M in distilled water, and dropwise adding while stirringNitric acid, continuously stirring for 10min to 30min, then dripping the chemical solution containing X, and then condensing and refluxing for reaction for 30min to 2h to obtain the product containing [ XM12O40]4-Mixed organic solutions of anions;
the sodium M in the first step is sodium molybdate or sodium tungstate; the chemical solution containing X in the step one is concentrated sulfuric acid, sodium silicate aqueous solution with the concentration of 2.03mmol/L or concentrated phosphoric acid;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 0.5-2.5 mol/L, wherein the chemical formula of the Victoria blue B cation is [ C ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding Victoria blue B solution into [ XM ] solution at 50 deg.C under stirring12O40]4-Mixing the anion and the organic solution, cooling to room temperature, standing for layering, and collecting the lower layer solution to obtain a room-temperature ionic liquid crude product; the Victoria blue B cation in the Victoria blue B solution in the third step is mixed with [ XM12O40]4-Mixed organic solution of anions [ XM12O40]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning the crude product for 2-4 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 50-80 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the mass fraction of the Victoria blue B cations in the room-temperature ionic liquid based on heteropoly acid anions in the fourth step is 39-51%.
The seventh embodiment: the present embodiment is a room temperature ion based on heteropoly acid anionsThe liquid consists of tetra-n-octyl ammonium bromide cations and heteropoly acid anions, the mass fraction of the tetra-n-octyl ammonium bromide cations in the room-temperature ionic liquid based on the heteropoly acid anions is 29.96 percent, and the molar ratio of the tetra-n-octyl ammonium bromide cations to the heteropoly acid anions in the room-temperature ionic liquid based on the heteropoly acid anions is 4: 1; the chemical formula of the tetra-n-octyl ammonium bromide cation is [ C ]32H68N]+The chemical formula of heteropoly acid anion is [ α -S2W18O62]4-。
The specific implementation mode is eight: the embodiment is a preparation method of room-temperature ionic liquid based on heteropoly acid anions, which is specifically completed by the following steps:
mixing Na2WO4·2H2Dissolving O in distilled water, and adding CH3CN, dripping 18mol/L sulfuric acid solution under the stirring condition, uniformly stirring, placing in a water bath at the temperature of 70 ℃, heating and stirring for reaction for 13-15 d under the water bath at the temperature of 70 ℃, cooling to room temperature, adding petroleum ether, transferring to a separating funnel, standing for layering, taking upper yellow-green liquid, pouring the upper yellow-green liquid into a beaker in a ventilated kitchen, placing the beaker containing the upper yellow-green liquid into the water bath at the temperature of 70 ℃, stirring under the water bath at the temperature of 70 ℃, then dripping tetra-n-octyl ammonium bromide solution, continuing stirring and reacting for 3 hours under the water bath at the temperature of 70 ℃ after the tetra-n-octyl ammonium bromide solution is added, obtaining dark green solid solution ionic liquid, namely the room temperature ionic liquid based on heteropoly acid anions, wherein cations in the room temperature ionic liquid based on heteropoly acid anions are tetra-n-octyl ammonium bromide cations, has a chemical formula of [ C32H68N]+29.96 percent by mass, wherein the anion in the room-temperature ionic liquid based on the heteropoly acid anion is heteropoly acid anion and has the chemical formula of [ α -S%2W18O62]4-(ii) a In the room-temperature ionic liquid based on heteropoly acid anions [ C32H68N]+And [ α -S2W18O62]4-In a molar ratio of 4: 1; said Na2WO4·2H2The volume ratio of the mass of O to the volume of distilled water is 5.6250g:167.5 mL; the volume ratio of the distilled water to the sulfuric acid solution with the concentration of 18mol/L is 167.5: 37.5; the volume ratio of the distilled water to the petroleum ether is 167.5: 100;
the tetra-n-octyl ammonium bromide solution is prepared by the following steps: dissolving tetra-n-octyl ammonium bromide in acetonitrile to obtain tetra-n-octyl ammonium bromide solution, wherein the chemical formula of the tetra-n-octyl ammonium bromide is C32H68NBr, the ratio of the mass of tetra-n-octylammonium bromide to the volume of acetonitrile in the tetra-n-octylammonium bromide solution is 2.3239g:20 mL.
The following tests were carried out to confirm the effects of the present invention
Test one: a preparation method of room temperature ionic liquid based on heteropoly acid anions comprises the following steps:
firstly, preparing the catalyst containing [ α -SiMo12O40]4-Dissolving 5.5g of sodium molybdate in 30mL of distilled water, dropwise adding 7.5mL of concentrated nitric acid and 10mL of sodium silicate aqueous solution with the concentration of 2.03mmol/L under the stirring condition, adding 100mL of acetonitrile after the temperature is reduced to room temperature, then carrying out condensation reflux reaction for 30min, cooling to room temperature, standing for layering, and collecting the upper-layer solution to obtain the mixed organic solution containing [ α -SiMo12O40]4-Mixed organic solutions of anions;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 3.0mol/L, wherein the chemical formula of the Victoria blue B cation is [ C [ ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: at a temperature of 50 ℃ under stirringDropwise adding the Victoria blue B solution into the solution containing [ SiMo ]12O40]4-Mixing the anion and the organic solution, cooling to room temperature, standing for layering, and collecting the lower layer solution to obtain a room-temperature ionic liquid crude product; the Victoria blue B cation in the Victoria blue B solution in the third step and the solution containing [ SiMo ]12O40]4-Mixed organic solution of anions [ α -SiMo ]12O40]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning for 3 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 75 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the content of the Victoria blue B cation in the room-temperature ionic liquid based on heteropoly acid anions in the fourth step is 50.9 percent by mass.
The room-temperature ionic liquid based on the heteropoly acid anions prepared in the first test is detected by an infrared spectrometer, the detection result is shown in figure 1, figure 1 is an infrared spectrogram of the room-temperature ionic liquid based on the heteropoly acid anions prepared in the first test, and figure 1 shows that the room-temperature ionic liquid based on the heteropoly acid anions prepared by the method consists of the heteropoly acid anions and Victoria blue B cations, is high in purity and does not contain any impurities.
The cyclic voltammetry characteristics of the room-temperature ionic liquid based on heteropoly acid anions prepared in the test-one in water, ethanol and acetonitrile are respectively detected in water, ethanol and acetonitrile as media, as shown in figure 2, figure 2 is a cyclic voltammetry curve, wherein A represents the cyclic voltammetry curve of the room-temperature ionic liquid based on heteropoly acid anions prepared in the test-one in water, B represents the cyclic voltammetry curve of the room-temperature ionic liquid based on heteropoly acid anions prepared in the test-one in ethanol, and C represents the cyclic voltammetry curve of the room-temperature ionic liquid based on heteropoly acid anions prepared in the test-one in acetonitrile, and the room-temperature ionic liquid based on heteropoly acid anions prepared in the test-one can be dissolved and ionized in water, ethanol and acetonitrile and can keep good anion electrochemical activity through figure 2.
Adding acetonitrile into room-temperature ionic liquid based on heteropoly acid anions prepared in the first test to prepare electrolyte I and electrolyte II, wherein [ C ] in the electrolyte I33H32N3]4[α-SiMo12O40]The concentration of (A) is 0.05mmol/L, and [ C ] in the electrolyte II33H32N3]4[α-SiMo12O40]The concentration of the heteropoly acid anion-based room-temperature ionic liquid is 0.5mmol/L, the P25 solar cell is respectively subjected to dye sensitization by utilizing an electrolyte I and an electrolyte II, the test result is shown in figure 3, figure 3 is a P25 solar cell I-V curve, A in the figure shows the I-V curve of the electrolyte I for the dye sensitization of the P25 solar cell, B in the figure shows the I-V curve of the electrolyte II for the dye sensitization of the P25 solar cell, and the room-temperature ionic liquid based on the heteropoly acid anion prepared in the test I can be used as the electrolyte of the solar cell and can be used as an inorganic sensitizer due to the absorption effect of the room-temperature ionic liquid based on the heteropoly acid anion on visible light through figure 3. The higher the usage amount of the room-temperature ionic liquid based on heteropoly acid anions, the higher the photoelectric efficiency of the solar cell.
The room temperature ionic liquid based on heteropoly acid anions prepared in the first test is added into water to obtain room temperature ionic liquid-H2O mixed solution, the room temperature ionic liquid-H2In O mixed liquor [ C33H32N3]4[α-SiMo12O40]The concentration of (a) is 2mmol/L, and the ionic liquid-H is added to room temperature2Adding H into the O mixed solution2O2To obtain different concentrations of H2O2Solution of H2O2H in solution2O2The concentration is 0mmol/L, 4mmol/L, 8mmol/L, 12mmol/L and 16mmol/L in sequence, and the content of H is detected at a scanning speed of 50mV/s2O2The catalytic cyclic voltammetry characteristics of the solution are shown in FIG. 4, where FIG. 4 is a catalytic cyclic voltammetry curve containing H from top to bottom2O2H in solution2O2The concentration is 0mmol/L, 4mmol/L, 8mmol/L, 12mmol/L and 16mmol/L in sequence, and as can be seen from figure 4, H in the catalytic reaction system2O2Increase in concentration based on impuritiesThe oxidation peak current of the room-temperature ionic liquid of polyacid anions at about-0.5V and the reduction peak current at about 1.0V are increased, which shows that the heteropolyacid anions in the ionic liquid are reduced continuously, and the lowest H is2O2The response concentration is not higher than 0.89mmol/L, and the room-temperature ionic liquid based on heteropoly acid anions can be used as H2O2The sensor of (1).
The room-temperature ionic liquid based on heteropoly acid anions prepared in the first test realizes mutual solubility of water, acetonitrile and ethyl acetate under the irradiation of ultraviolet light, because the heteropoly acid anions in the room-temperature ionic liquid based on heteropoly acid anions prepared in the first test absorb the ultraviolet light to generate self-reduction reaction (M)6+→M5+) So that the surface charge density of the heteropoly acid anion group is changed, and the sizes of the negative and positive ion charge attraction in the ionic liquid are changed, so that the polarity of the ionic liquid is changed, and the room-temperature ionic liquid based on the heteropoly acid anion prepared in the first test realizes mutual solubility of water, acetonitrile and ethyl acetate. In addition of an oxidizing agent such as H2O2Or under the condition of visible light illumination, testing the reduction state (M) of heteropoly acid anion part in the room-temperature ionic liquid based on heteropoly acid anion prepared in the first step5+) Oxidation reaction (M) takes place5+→M6+) So that the surface charge density of the heteropoly acid anion group is repaired, and the room-temperature ionic liquid based on heteropoly acid anions prepared in the first test realizes the layering of water, acetonitrile and ethyl acetate. Experiment I shows that the reversible process of the prepared room-temperature ionic liquid based on heteropoly acid anions with polarity change under the external condition provides a simpler method for extracting a catalyst and economic components of factory waste liquid (materials) in the catalytic reaction process.
And (2) test II: a preparation method of room temperature ionic liquid based on heteropoly acid anions comprises the following steps:
preparation of a catalyst containing [ S ]2Mo18O62]4-Mixed organic solution of anions: dissolving 6.3g of sodium molybdate in 20mL of distilled water, dropwise adding 5mL of concentrated sulfuric acid under stirring, cooling to room temperature, and adding 100mL of acetonitrile, then cooling to room temperature after condensing reflux reaction for 2h, standing for layering, and collecting the upper layer solution to obtain the product containing [ S ]2Mo18O62]4-Mixed organic solutions of anions;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 3.0mol/L, wherein the chemical formula of the Victoria blue B cation is [ C [ ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding the Victoria blue B solution into the solution containing [ S ] under stirring2Mo18O62]4-Mixing the anion and the organic solution, standing for layering, and collecting the lower layer solution to obtain a room-temperature ionic liquid crude product; the Victoria blue B cation and the [ S ] in the Victoria blue B solution in the third step2Mo18O62]4-Mixed organic solution of anions [ S ]2Mo18O62]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning for 3 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 75 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the content of the Victoria blue B cation in the room-temperature ionic liquid based on heteropoly acid anions in the fourth step is 40.3 percent by mass.
The room temperature ionic liquid based on heteropoly acid anions prepared in the second test is used as a catalyst, the room temperature ionic liquid based on heteropoly acid anions prepared in the first test is used for catalyzing esterification, the catalysis selectivity and the catalysis yield of the esterification are shown in the table 1, and the room temperature ionic liquid based on heteropoly acid anions prepared in the first test has high catalysis activity on the esterification and can be used for industrial catalysis reaction through the table 1.
TABLE 1
Reaction raw material A Reaction raw material B Yield of Selectivity is
Citric acid N-butanol 96.4 98
Lactic acid N-butanol 89.5 100
Acetic acid N-butanol 94.5 100
Acetic acid Glycerol 84.5 89
Acetic acid Ethylene glycol 97.7 93
And (3) test III: a preparation method of room temperature ionic liquid based on heteropoly acid anions comprises the following steps:
firstly, preparing a catalyst containing [ SiW12O40]4-Mixed organic solution of anions: dissolving 7.9g of sodium tungstate in 30mL of distilled water, dropwise adding 7.5mL of concentrated nitric acid under the stirring condition, continuously stirring for 30min, dropwise adding 10mL of sodium silicate aqueous solution with the concentration of 2.03mmol/L, and then carrying out condensation reflux reaction for 2h to obtain the product containing [ SiW ]12O40]4-Mixed organic solutions of anions;
secondly, preparing a Victoria blue B solution: dissolving Victoria blue B powder in a solvent to obtain a Victoria blue B solution;
the chemical formula of the Victoria blue B powder in the step two is C33H32N3Cl；
The concentration of the Victoria blue B cation in the Victoria blue B solution in the step two is 3.0mol/L, wherein the chemical formula of the Victoria blue B cation is [ C [ ]33H32N3]+；
The solvent in the second step is acetonitrile;
thirdly, mixing: dropwise adding the Victoria blue B solution into the solution containing SiW at 50 deg.C under stirring12O40]4-Mixing the anion and the organic solution, cooling to room temperature, standing for layering, and collecting the lower layer solution to obtain a room-temperature ionic liquid crude product; the Victoria blue B cation in the Victoria blue B solution in the third step is mixed with the solution containing [ SiW ]12O40]4-Mixed organic solution of anions [ SiW ]12O40]4-In a molar ratio of 4: 1;
fourthly, removing impurities: carrying out rotary evaporation treatment on the room-temperature ionic liquid crude product for 2 hours, then cleaning for 3 times by using petroleum ether, and finally carrying out vacuum drying for 8 hours at the temperature of 75 ℃ to obtain room-temperature ionic liquid based on heteropoly acid anions; the content of the Victoria blue B cation in the room-temperature ionic liquid based on heteropoly acid anions in the fourth step is 39.6 percent by mass.
The room temperature ionic liquid based on heteropoly acid anions prepared in the first test and the third test is used as a catalyst, the room temperature ionic liquid based on heteropoly acid anions prepared in the first test and the third test is used for catalyzing esterification reaction, the catalytic selectivity and the catalytic yield of partial esterification reaction are shown in table 2, and the room temperature ionic liquid based on heteropoly acid anions prepared in the first test and the third test has high catalytic activity on esterification reaction through table 2 and can be used for industrial catalytic esterification reaction.
TABLE 2
Catalyst and process for preparing same Reaction raw material A Reaction raw material B Yield of Selectivity is
[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 Glycerol 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 Glycerol 95.5 96
Adding acetonitrile into room temperature ionic liquid based on heteropoly acid anions prepared in the first test to prepare electrolyte III,adding acetonitrile into room-temperature ionic liquid based on heteropoly acid anions prepared in the third test to prepare electrolyte IV, wherein [ C ] in the electrolyte III33H32N3]4[SiMo12O40]The concentration of (A) is 0.5mmol/L, and [ C ] in the electrolyte IV33H32N3]4[SiW12O40]The concentration of the heteropoly acid anion-based room-temperature ionic liquid is 0.5mmol/L, dye sensitization is respectively carried out on a P25 solar cell by utilizing an electrolyte III and an electrolyte IV, the test result is shown in figure 5, figure 5 is an I-V curve of the P25 solar cell, A in the figure represents an I-V curve of the electrolyte III for dye sensitization of the P25 solar cell, B in the figure represents an I-V curve of the electrolyte IV for dye sensitization of the P25 solar cell, and the room-temperature ionic liquid based on the heteropoly acid anion prepared in the first test and the third test can be used as the electrolyte of the solar cell and can be used as an inorganic sensitizer due to the absorption effect of the room-temperature ionic liquid based on the heteropoly acid anion on visible light through figure 5. [ C ]33H32N3]4[SiMo12O40]Photoelectric efficiency ratio of solar cell [ C ]33H32N3]4[SiW12O40]High.
And (4) testing: a preparation method of room temperature ionic liquid based on heteropoly acid anions comprises the following steps:
5.6250g of Na2WO4·2H2O was dissolved in 167.5mL of distilled water and 100mL of CH was added3Adding 37.5mL of 18mol/L sulfuric acid solution dropwise under the stirring condition, uniformly stirring, placing in a water bath at the temperature of 70 ℃, heating and stirring for reaction for 14d under the water bath at the temperature of 70 ℃, cooling to room temperature, adding 100mL of petroleum ether, transferring to a separating funnel, standing for layering, taking the upper yellow-green liquid, pouring the upper yellow-green liquid into a beaker in a ventilation kitchen, placing the beaker containing the upper yellow-green liquid into the water bath at the temperature of 70 ℃, stirring under the water bath at the temperature of 70 ℃, then adding the tetra-n-octyl ammonium bromide solution dropwise, continuing to add the tetra-n-octyl ammonium bromide solution in the water bath at the temperature of 70 ℃ after finishing adding the tetra-n-octyl ammonium bromide solutionStirring and reacting for 3h under the condition to obtain dark green solid solution-shaped ionic liquid, namely the room-temperature ionic liquid based on heteropoly acid anions, wherein cations in the room-temperature ionic liquid based on heteropoly acid anions are tetra-n-octyl ammonium bromide cations and have a chemical formula of [ C32H68N]+29.96 percent by mass, wherein the anion in the room-temperature ionic liquid based on the heteropoly acid anion is heteropoly acid anion and has the chemical formula of [ α -S%2W18O62]4-(ii) a In the room-temperature ionic liquid based on heteropoly acid anions [ C32H68N]+And [ α -S2W18O62]4-In a molar ratio of 4: 1;
the tetra-n-octyl ammonium bromide solution is prepared by the following steps: 2.3239g of tetra-n-octylammonium bromide is dissolved in 20mL of acetonitrile to obtain a tetra-n-octylammonium bromide solution, wherein the chemical formula of the tetra-n-octylammonium bromide is C32H68NBr。
The room-temperature ionic liquid based on heteropoly acid anions prepared in the fourth test is detected by an infrared spectrometer, the detection result is shown in fig. 6, fig. 6 is an infrared spectrogram of the room-temperature ionic liquid based on heteropoly acid anions prepared in the fourth test, and the room-temperature ionic liquid based on heteropoly acid anions prepared by the method is composed of heteropoly acid anions and tetra-n-octyl ammonium bromide cations, and can be seen through fig. 6, so that the room-temperature ionic liquid based on heteropoly acid anions is high in purity and does not contain any impurities.
The cyclic voltammetry characteristics of the room-temperature ionic liquid based on heteropoly acid anions prepared by the test four in water, ethanol and acetonitrile are respectively detected in water, ethanol and acetonitrile, as shown in fig. 7, fig. 7 is a cyclic voltammetry curve, wherein A represents the cyclic voltammetry curve of the room-temperature ionic liquid based on heteropoly acid anions prepared by the test four in water, B represents the cyclic voltammetry curve of the room-temperature ionic liquid based on heteropoly acid anions prepared by the test four in ethanol, and C represents the cyclic voltammetry curve of the room-temperature ionic liquid based on heteropoly acid anions prepared by the test four in acetonitrile, and the room-temperature ionic liquid based on heteropoly acid anions prepared by the test four can be dissolved and ionized in water, ethanol and acetonitrile and can keep good anion electrochemical activity through fig. 7.
Adding acetonitrile into room-temperature ionic liquid based on heteropoly acid anions prepared in the fourth test to prepare electrolyte III and electrolyte IV, wherein [ C ] in the electrolyte III32H68N]4[α-S2W18O62]The concentration of (A) is 0.05mmol/L, and [ C ] in the electrolyte IV32H68N]4[α-S2W18O62]The concentration of the heteropoly acid anion-based room-temperature ionic liquid is 0.5mmol/L, the P25 solar cell is respectively subjected to dye sensitization by utilizing an electrolyte III and an electrolyte IV, the test result is shown in figure 8, figure 8 is an I-V curve of the P25 solar cell, A in the figure represents an I-V curve of the electrolyte III for dye sensitization of the P25 solar cell, B in the figure represents an I-V curve of the electrolyte IV for dye sensitization of the P25 solar cell, and the room-temperature ionic liquid based on heteropoly acid anions prepared in the experiment IV can be used as the electrolyte of the solar cell and can be used as an inorganic sensitizer due to the absorption effect of the room-temperature ionic liquid based on heteropoly acid anions on visible light. The higher the usage amount of the room-temperature ionic liquid based on heteropoly acid anions, the higher the photoelectric efficiency of the solar cell.
Adding the room-temperature ionic liquid based on heteropoly acid anions prepared in the fourth test into water to obtain room-temperature ionic liquid-H2O mixed solution, the room temperature ionic liquid-H2In O mixed liquor [ C32H68N]4[α-S2W18O62]The concentration of (a) is 2mmol/L, and the ionic liquid-H is added to room temperature2Adding L-cysteine into the O mixed solution to obtain L-cysteine-containing solutions with different concentrations, wherein the concentrations of the L-cysteine in the L-cysteine-containing solutions are 0mmol/L, 2mmol/L, 4mmol/L, 5mmol/L and 7mmol/L in sequence, and detecting the catalytic cyclic voltammetry characteristics of the L-cysteine-containing solutions at a scanning speed of 50mV/s, as shown in FIG. 9, FIG. 9 is a catalytic cyclic voltammetry curve, wherein the concentrations of the L-cysteine in the L-cysteine-containing solutions from bottom to top are 0mmol/L, 2mmol/L, 4mmol/L, 5mmol/L and 7mmol/L in sequence, and as can be seen from FIG. 9, as the concentration of the L-cysteine in the catalytic reaction system increases, based on the increase of the L-cysteine concentration in the catalytic reaction systemThe reduction peak current of the room-temperature ionic liquid of the heteropoly acid anions, which is about 1.22V, is continuously increased, which indicates that the heteropoly acid anions in the ionic liquid are continuously oxidized, and the lowest L-cysteine response concentration is not higher than 0.5mmol/L, and proves that the room-temperature ionic liquid based on the heteropoly acid anions can be used as a sensor of L-cysteine.

Claims (1)

1. The application of the room temperature ionic liquid based on heteropoly acid anions is characterized in that the room temperature ionic liquid based on heteropoly acid anions is used as a sensor of L-cysteine; the melting point of the room-temperature ionic liquid based on heteropoly acid anions is less than or equal to 10 ℃;
the room-temperature ionic liquid based on heteropoly acid anions is prepared by the following steps:
mixing Na2WO4•2H2Dissolving O in distilled water, and adding CH3CN, dripping 18mol/L sulfuric acid solution under the stirring condition, uniformly stirring, placing in a water bath at the temperature of 70 ℃, heating and stirring for reaction for 13-15 days under the water bath condition at the temperature of 70 ℃, cooling to room temperature, adding petroleum ether, transferring to a separating funnel, standing for layering, taking upper yellow-green liquid, pouring the upper yellow-green liquid into a beaker in a ventilated kitchen, placing the beaker containing the upper yellow-green liquid in the water bath at the temperature of 70 ℃, stirring under the water bath condition at the temperature of 70 ℃, then dripping tetra-n-octyl ammonium bromide solution, continuing stirring and reacting for 3 hours under the water bath condition at the temperature of 70 ℃ after the tetra-n-octyl ammonium bromide solution is added, obtaining dark green ionic liquid which is solid solution and is room temperature ionic liquid based on heteropoly acid anions, wherein cations in the room temperature ionic liquid based on heteropoly acid anions are tetra-n-octyl ammonium cations, has a chemical formula of [ C32H68N]+29.96 percent by mass, wherein the anion in the room-temperature ionic liquid based on the heteropoly acid anion is heteropoly acid anion and has the chemical formula of [ α -S%2W18O62]4-(ii) a In the room-temperature ionic liquid based on heteropoly acid anions [ C32H68N]+And [ α -S2W18O62]4-In a molar ratio of 4: 1; said Na2WO4•2H2The volume ratio of the mass of O to the volume of distilled water is 5.6250g:167.5 mL; the volume ratio of the distilled water to the sulfuric acid solution with the concentration of 18mol/L is 167.5: 37.5; the volume ratio of the distilled water to the petroleum ether is 167.5: 100; the tetra-n-octyl ammonium bromide solution is prepared by the following steps: dissolving tetra-n-octyl ammonium bromide in acetonitrile to obtain tetra-n-octyl ammonium bromide solution, wherein the chemical formula of the tetra-n-octyl ammonium bromide is C32H68NBr, the ratio of the mass of tetra-n-octylammonium bromide to the volume of acetonitrile in the tetra-n-octylammonium bromide solution is 2.3239g:20 mL.
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