CN115367803B - Heteropolyblue, and preparation method and application thereof - Google Patents
Heteropolyblue, and preparation method and application thereof Download PDFInfo
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- CN115367803B CN115367803B CN202110552230.9A CN202110552230A CN115367803B CN 115367803 B CN115367803 B CN 115367803B CN 202110552230 A CN202110552230 A CN 202110552230A CN 115367803 B CN115367803 B CN 115367803B
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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Abstract
The invention relates to the field of inorganic oxide material preparation, in particular to preparation of heteropolyblue and application thereof, and the method comprises the following steps: 1) Dissolving ammonium metatungstate powder in an aqueous solution with an acidity value not lower than 0.1 mol/L; 2) And adding gallium-based liquid metal into the solution for reaction. The preparation method provided by the invention has the advantages that the preparation process is simple, the obtained tungsten-based heteropolyblue component is uniform, and mass production can be realized. The preparation environment is room temperature, the synthesis of the heteropolyblue material can be realized without any atmosphere and high temperature, and the use of vacuum or sealing capacity is completely avoided.
Description
Technical Field
The invention relates to the field of inorganic oxide material preparation, in particular to preparation and application of heteropolyblue.
Background
Tungsten-based heteropolyblue is an important class of inorganic cluster compounds in which tungsten ions are represented by W 6 + 、W 5 + Or W 4 + And the mixed valence states exist to balance the overall charge of the compound. The abundant crystal structure, tunnel structure and the special valence state lead the material to have excellent performances such as electronic and ionic conductivity, superconductivity, optical performance and the like, and the application of the material in electrochromic, water-based batteries, near infrared absorption, chemical sensors and the like is widely researched and interesting and potential application scenes.
The existing preparation method of tungsten-based heteropolyblue adopts a chemical reduction method or a hydrothermal method, and comprises the following steps of 6 + The tungsten-based heteropolyblue is obtained by hydrothermal synthesis in a salt solution, and the heteropolyblue prepared by the method has uncontrollable composition and contains a reaction precursor. And the hydrothermal synthesis method has limited synthesis amount, harsh reaction conditions, such as high temperature and high pressure conditions required in the reaction process, long time consumption, large energy consumption and poor repeatability. Therefore, an industrialized synthesis method for synthesizing tungsten-based heteropolyblue, which is low in cost, reliable and stable, is urgently needed.
Disclosure of Invention
The invention provides a preparation method of heteropolyblue, which comprises the following steps:
1) Dissolving ammonium metatungstate powder in an aqueous solution with an acidity value not lower than 0.1 mol/L;
2) And adding gallium-based liquid metal into the solution for reaction.
The invention discovers that the gallium-based liquid metal can greatly promote the mass transfer process and the reactivity between the reaction raw materials, thereby obviously reducing the synthesis temperature of the heteropolyblue material, and the gallium-based metal is convenient to separate from a system after the reaction.
Preferably, after the reaction in the step 2), drying the solution obtained after the reaction to obtain the heteropoly blue.
Preferably, the solution obtained after the reaction is subjected to a drying treatment by vacuum drying or freeze drying. Wherein vacuum drying or freeze drying reduces or avoids the formation of heteropolyblue powder which is again reduced and maintains structural integrity.
Further preferably, the temperature of the vacuum drying is 20-80 ℃ and the time is 5-72 h.
Preferably, after the reaction in the step 2), unreacted gallium-based liquid metal is removed by filtration, and then the solution obtained after the reaction is dried. Because the surface tension of the liquid metal and the surface tension of the water have great difference, the excessive liquid metal can be directly removed by filtration after the reaction is finished, and the operation is convenient.
Preferably, the step 2) controls the temperature of the reaction solution during the reaction to make the gallium-based liquid metal be in a liquid state.
Preferably, the temperature of the reaction is 20 to 40 ℃.
Preferably, the mass percentage of the gallium metal in the gallium-based liquid metal is 68.5-75.5%, and preferably, the gallium-based liquid metal is gallium indium alloy or gallium indium tin alloy.
Preferably, the mass ratio of the ammonium meta-tungstate powder to the gallium-based liquid metal is 1:0.2 to 1.
The acid according to the invention includes, but is not limited to, one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, acetic acid, citric acid, preferably hydrochloric acid or sulfuric acid. Wherein the acid concentration value is not less than 0.1.
The mass ratio of the acid to the ammonium meta-tungstate powder is 20:1-2:1, and more preferably 20:1-10:1.
In another aspect, the invention provides heteropolyblues prepared by the method of the invention.
In another aspect, the invention provides the use of the heteropolyblue of the invention in the preparation of a color changing paper and an acid sensor.
The invention has the following beneficial effects:
1) The preparation method provided by the invention has the advantages that the preparation process is simple, the obtained tungsten-based heteropolyblue component has uniform particle size, and mass production can be realized.
2) The preparation environment of the invention is room temperature, the synthesis of the heteropolyblue material can be realized without any atmosphere and high temperature, the use of vacuum or sealing capacity is completely avoided, and the application range of the heteropolyblue can be very conveniently enlarged, such as the preparation of the heteropolyblue into color-changing paper, the induction of the pH change in the environment and the like;
the liquid metal reduction method disclosed by the invention has the advantages of simple equipment, easy operation, large yield, mass production, no waste in the synthesis process and no waste of raw materials. Liquid metal reduction processes are compared to chemical and hydrothermal/solvothermal processes: the chemical reaction preparation process is complex, multiple reaction precursors are needed, and the synthesis period is long. The synthesis temperature of heteropolyblue by a hydrothermal/solvothermal method is relatively high (160-250 ℃), and the reaction temperature is far higher than the boiling point of water/solvent, so that the reaction must be carried out in a high-pressure sealing capacity; in addition, the hydrothermal/solvothermal method has the advantages of low concentration of reaction raw materials, low yield and long synthesis period (1-3 d), and the waste organic solvent and other auxiliary agents produced by the production have certain pollution to the environment, so that the method does not have the problems and is convenient to prepare and apply in various occasions.
Drawings
FIG. 1 is a diagram of the acidic solution reaction process of the AMT of example 1;
FIG. 2 is a UV-Vis diagram of a heteropolyblue material of example 1
FIG. 3 is an XRD pattern for the heteropolyblue material of example 2;
FIG. 4 is an SEM image of a heteropolyblue material of example 2;
FIG. 5 is a macroscopic physical diagram of the heteropolyblue material of example 3;
FIG. 6 is an XPS diagram of a heteropolyblue material of example 3;
FIG. 7 is a schematic view of the color-changing paper structure of example 5;
FIG. 8 is a graphical representation of the surface patterning of color shifting paper of example 5;
FIG. 9 is a schematic diagram of the preparation of an acid sensor of example 6;
FIG. 10 is a diagram showing the structure of an acid sensor in example 6.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the present invention, but are not intended to limit the scope of the invention.
The raw material components used in the invention are all available commercially, and the reagents used in the examples of the invention are all chemically pure.
Example 1
The embodiment provides a tungsten-based heteropolyblue material, which is prepared by the following steps:
1) Mixing 30 μm AMT powder with hydrochloric acid with concentration value of 1mol/L according to mass ratio of 1:10, selecting mixed solution temperature of 20deg.C, and placing into glass beaker;
2) Adding 50uL of liquid metal (Ga 75.5%, in 24.5%) into the mixed solution, standing the solution, and reacting for 30min;
3) Separating the liquid metal from the mixed solution, placing the separated liquid metal in 1mol/L hydrochloric acid for recycling, placing the separated solution in a vacuum drying oven, and drying at 60 ℃ for 24 hours. The preparation process of the AMT acid solution and the preparation process of the heteropolyblue reaction for preparing the dropwise liquid metal are shown in figure 1. Wherein the UV-Vis diagram of fig. 2 demonstrates the successful synthesis of heteropolyblue in this example.
Example 2
The embodiment provides a tungsten-based heteropolyblue material, which is prepared by the following steps:
1) Mixing 30 mu m AMT powder with hydrochloric acid with a concentration value of 3mol/L according to a mass ratio of 1:10, selecting the temperature of the mixed solution to be 20 ℃, and placing the mixed solution into a glass beaker;
2) Adding 100 mu L of liquid metal (Ga 75.5%, in 24.5%) into the mixed solution, standing the solution, and reacting for 30min;
3) Separating the liquid metal from the mixed solution, placing the separated liquid metal in 1mol/L hydrochloric acid for recycling, placing the separated solution in a vacuum drying oven, and drying at 40 ℃ for 72 hours. The heteropolyblue SEM image prepared is shown in FIG. 3, XRD is shown in FIG. 4, and the successful synthesis of heteropolyblue in this example can be obtained from FIGS. 3 and 4.
Example 3
The embodiment provides a tungsten-based heteropolyblue material, which is prepared by the following steps:
1) Mixing 30 mu m AMT powder with hydrochloric acid with concentration value of 0.5mol/L according to mass ratio of 1:10, selecting mixed solution temperature of 20 ℃, and placing into a glass beaker;
2) Adding 100 mu L of liquid metal (Ga 68.5%, in 21.5% and Sn 10%) into the mixed solution, standing the solution, and reacting for 30min;
3) Separating the liquid metal from the mixed solution, placing the separated liquid metal in 1mol/L hydrochloric acid for recycling, placing the separated solution in a freeze drying box, and freeze drying for 120h at the temperature of minus 50 ℃. The embodiment of the heteropolyblue powder prepared is shown in FIG. 5, the XPS is shown in FIG. 6, and the successful synthesis of heteropolyblue in this example can be obtained from FIGS. 5 and 6.
Example 4
In comparison with example 1, the difference is that the liquid metal is eutectic gallium indium tin (ga68.5%, in21.5%, sn 10%), and heteropolyblue can also be successfully synthesized.
Example 5
The embodiment provides a tungsten-based heteropolyblue material prepared based on the above, which is used in the field of color-changing paper writing, and the preparation method comprises the following steps:
weighing 5g of PEG, adding the PEG into 50mL of deionized water, and stirring and mixing uniformly at 50 ℃ to obtain a transparent colorless solution; uniformly dripping the solution into cellulose paper to wet the paper, and then drying at 70 ℃ for 1h; weighing 2.5g of PEG, adding into 50ml of deionized water, stirring and mixing uniformly at 50 ℃, then adding 2.5g of AMT powder into the solution, and stirring uniformly to obtain a transparent colorless solution; the solution is evenly dripped into cellulose paper to moisten the paper, and then the paper is dried for 1h at 70 ℃ to prepare the modified cellulose paper. The preparation process is schematically shown in figure 7. Wherein I is a cellulose paper substrate, II is cellulose paper containing 10% PEG as a protective layer, and III is a color developing layer containing amt. The liquid metal EGaInSn pen is used as a reducing agent, and patterning is carried out on the surface of the paper. The surface color change was then achieved using a 0.5mol/L acid spray of hydrochloric acid, and FIG. 8 shows the patterning of the surface of the prepared paper.
Example 6
The embodiment provides an application of the tungsten-based heteropolyblue material prepared based on the above in writing of color-changing paper and preparation of an acid sensor, and the preparation method is as follows:
weighing 5g of PEG, adding the PEG into 50mL of deionized water, and stirring and mixing uniformly at 50 ℃ to obtain a transparent colorless solution; uniformly dripping the solution into cellulose paper to wet the paper, and then drying at 70 ℃ for 1h; weighing 2.5g of PEG, adding into 50ml of deionized water, stirring and mixing uniformly at 50 ℃, then adding 2.5g of AMT powder into the solution, and stirring uniformly to obtain a transparent colorless solution; the solution is evenly dripped into cellulose paper to moisten the paper, and then the paper is dried for 1h at 70 ℃ to prepare the modified cellulose paper. The preparation process is schematically shown in figure 7.
Cutting the modified paper into a size of 3cm multiplied by 6cm, and uniformly coating the paper surface by adopting liquid metal EGaInSn as a reducing agent to prepare the acid sensor. Then 0.5mol/L hydrochloric acid is adopted to spray on the surface of the paper, so as to realize the change of the surface color, the color development process is shown in figure 9, and the color development effect is shown in figure 10.
Comparative example 1
The difference compared with example 1 is that aluminum particles are used as the reaction raw material.
The method comprises the following specific steps:
1) Mixing 30 mu m AMT powder with hydrochloric acid with concentration value of 0.5mol/L according to mass ratio of 1:10, selecting mixed solution temperature of 20 ℃, and placing into a glass beaker;
2) Adding 2g of aluminum particles (particle size 40 μm) into the mixed solution, standing the solution, and reacting for 30min;
after the aluminum powder is adopted, the solution turns from colorless to turbid and finally turns into blue. This is because aluminum powder is added into the solution, a large amount of hydrogen is generated, unnecessary substances are introduced, experimental observation is disturbed, and the convenient application is not facilitated. In addition, aluminum particles react with AMT, and subsequent separation treatment cannot be performed, resulting in an increase in reaction cost and a dangerous coefficient of performance (hydrogen is flammable and explosive).
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A process for the preparation of heteropolyblue comprising the steps of:
1) Dissolving ammonium metatungstate powder in an aqueous solution with an acid concentration value not lower than 0.1 mol/L;
2) And adding gallium-based liquid metal into the solution for reaction.
2. The preparation method according to claim 1, wherein the heteropolyblue is obtained by drying the solution obtained after the reaction in step 2).
3. The method according to claim 2, wherein the solution obtained after the reaction is subjected to a drying treatment by vacuum drying or freeze drying; wherein the temperature of the vacuum drying is 20-80 ℃ and the time is 5-72 h.
4. The preparation method according to claim 2, wherein after the reaction in step 2), unreacted gallium-based liquid metal is removed by filtration, and the solution obtained after the reaction is dried.
5. The method according to claim 1, wherein the step 2) controls the temperature of the reaction solution during the reaction so that the gallium-based liquid metal is in a liquid state.
6. The process according to claim 5, wherein the temperature of the reaction is 20 to 40 ℃.
7. The preparation method according to claim 1, wherein the gallium-based liquid metal comprises 68.5-75.5 mass% of gallium, and the gallium-based liquid metal is gallium indium alloy or gallium indium tin alloy.
8. The preparation method according to claim 6, wherein the mass ratio of the ammonium meta-tungstate powder to the gallium-based liquid metal is 1:0.2 to 1.
9. Heteropolyblue obtainable by the process according to any one of claims 1 to 8.
10. Use of heteropolyblue according to claim 9 for the preparation of a colour change paper and an acid sensor.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2615399A1 (en) * | 1976-04-08 | 1977-10-27 | Gni I Pi Redkometallitscheskoj | Gallium copper tin dental filler alloy - prepd. using copper tin alloy of critical size and increased amt. of liq. gallium tin alloy |
| CN101497460A (en) * | 2009-03-09 | 2009-08-05 | 东北师范大学 | Method for preparing heteropoly blue micrometre tube and use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2615399A1 (en) * | 1976-04-08 | 1977-10-27 | Gni I Pi Redkometallitscheskoj | Gallium copper tin dental filler alloy - prepd. using copper tin alloy of critical size and increased amt. of liq. gallium tin alloy |
| CN101497460A (en) * | 2009-03-09 | 2009-08-05 | 东北师范大学 | Method for preparing heteropoly blue micrometre tube and use thereof |
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