CN110240902B - Preparation method of tungsten oxide quantum dot material - Google Patents
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Abstract
The invention provides a preparation method of a tungsten oxide quantum dot material, which comprises the following steps: A. preparing a precursor: adding a tungsten source into a solvent containing polyol, heating and stirring at 60-140 ℃ for 1-4 hours to obtain a reaction precursor; B. and B, placing the reaction precursor obtained in the step A into a reaction kettle, reacting for 5-24 hours at the temperature of 150-250 ℃, and cooling to obtain the tungsten oxide quantum dot polyalcohol solution. The invention has the beneficial effects that: the synthesis method is simple and efficient, the raw materials are wide in source, cheap and easy to obtain, the template removing step with extremely complex operation process is omitted, the negative influence of residual templates on the properties and the use of the tungsten oxide quantum dots is avoided, multi-step filtration is not needed, the yield of the water-soluble quantum dots is improved, the prepared tungsten oxide quantum dots are water-soluble, have no organic matter coating on the surface, are highly dispersed, have narrow particle size distribution, and can be stored for a long time.
Description
Technical Field
The invention relates to a preparation method of a tungsten oxide quantum dot material, in particular to a tungsten oxide quantum dot material with high dispersion, uniform appearance and adjustable size and a liquid phase preparation method thereof, belonging to the technical field of new nano materials.
Background
Tungsten oxide has excellent electrical and optical properties as an important semiconductor material, and is widely applied to the fields of intelligent color-changing intelligent windows, photocatalysis, solar cells, sensors and photo-thermal treatment. Semiconductor nanocrystals, i.e., quantum dots, are collections of atoms and molecules on a nanometer scale, and such zero-dimensional systems behave physically, like atoms, as regards optical and electrical properties, and are therefore often referred to as "artificial atoms," in which electrons exhibit discrete energy level structures like electrons in atoms. The semiconductor quantum dots have unique physical and chemical properties, and have wide application prospects in the aspects of magnetics, electrics, optics, catalysis, chemical sensing, biomedicine and the like. Tungsten oxide quantum dot materials have received much attention in recent years due to their unique physicochemical properties. Liu et al (appl. surf. Sci.2019,480,404.) synthesized tungsten oxide quantum dots containing oxygen vacancies by a hydrothermal method, and proved that the tungsten oxide quantum dots have more excellent photochromic performance. Cong et al (adv. Mater.2014,26,4260.) synthesized tungsten oxide quantum dots by a two-step method, and grafted a conductive organic substance onto the surface of the quantum dots by a surface ligand replacement method, and found that the tungsten oxide quantum dots have more excellent electrochemical properties compared with bulk tungsten oxide materials. Epifani et al (ACS appl. Mater. interfaces 2014,6, 16808-. Although tungsten oxide quantum dots have proved to have good application prospects in many fields, the lag of the tungsten oxide quantum dot synthesis method leads to the difficulty in large-area application and popularization of tungsten oxide quantum dot materials.
Chinese patent (CN104789218A) firstly reacts an inorganic tungsten compound with an organic ligand at a certain temperature to generate an organic tungsten precursor, then the organic tungsten-free precursor reacts with an organic solvent at a high temperature, and tungsten oxide quantum dots are obtained by separation after the reaction is finished. Although the tungsten oxide quantum dots can be obtained by the method, the surfaces of the tungsten oxide quantum dots are coated with a layer of water-insoluble long-chain organic matter which is difficult to remove, so that the conductivity and the biocompatibility of the tungsten oxide quantum dots are greatly reduced, and the practical application range of the tungsten oxide quantum dots is limited. Chinese patent (CN104861971A) prepares a tungsten oxide quantum dot material by taking tungsten sulfide as a raw material, and the specific process comprises the steps of firstly forming a suspension of tungsten sulfide solid in distilled water by an ultrasonic method, filtering the suspension to obtain a filter cake, then suspending the filter cake in the distilled water and placing the filter cake in a high-temperature hydrothermal kettle for reaction, and finally filtering a product after the hydrothermal reaction to obtain a filtrate, namely a tungsten oxide quantum dot aqueous solution. The method obtains the water-soluble tungsten oxide quantum dots, and the surfaces of the tungsten oxide quantum dots do not contain the coating of long-chain organic matters, so that the method is beneficial to the application of the tungsten oxide quantum dots. However, the method has serious waste of raw materials, the tungsten oxide quantum dot aqueous solution is obtained after two times of filtration, the utilization rate of the raw materials and the production cost are high, and the method is not beneficial to large-scale production. Chinese patent (CN107416906A) takes tungsten disulfide as a precursor, and utilizes the strong oxidizing property of hydrogen peroxide to oxidize the tungsten disulfide in an alcohol dispersion liquid by a solvothermal method to obtain the fluorescent tungsten oxide quantum dot. However, the method uses hydrogen peroxide as an oxidant, which not only easily corrodes equipment, but also causes troubles for post-treatment of reaction liquid and causes certain harm to the environment. Watanabe et al (chem.Commun.,2013,49,8477.) successfully synthesized tungsten oxide quantum dots with controllable size using nanoporous silicon as a reaction template. The method has low tungsten oxide quantum dot yield, and the template is difficult to remove, thereby bringing great difficulty to subsequent application. Wang et al (j. mater. chem.c,2015,3,3280.) synthesized tungsten oxide quantum dots by a microwave solvothermal method using tungsten chloride as a tungsten source and ethylene glycol as a reaction solvent. The process is simple, but the concentration of reactants is extremely low, tungsten chloride is expensive and has strong corrosivity, the tungsten chloride is extremely easy to react with water vapor in the air, the reaction process is difficult to control, the production cost is increased, and the tungsten chloride is not easy to industrially produce. In conclusion, the existing synthesis method of the tungsten oxide quantum dots has many problems, and the large-area popularization and application of the tungsten oxide quantum dots are greatly limited, so that the development of the simple and efficient synthesis method of the tungsten oxide quantum dots has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-efficiency, simple and low-cost preparation method of tungsten oxide quantum dots.
In order to achieve the purpose, the invention provides a preparation method of a tungsten oxide quantum dot material, which comprises the following steps:
A. preparing a precursor: adding a tungsten source into a solvent containing polyol, heating and stirring at 60-140 ℃ for 1-4 hours to obtain a reaction precursor;
B. and B, placing the reaction precursor obtained in the step A into a reaction kettle, reacting for 5-24 hours at the temperature of 150-250 ℃, and cooling to obtain the tungsten oxide quantum dot polyalcohol solution.
The method of the invention omits the use of a template, avoids the performance reduction of the tungsten oxide quantum dots caused by the template which is not removed, can obtain the tungsten oxide quantum dot material without separation steps such as filtration with serious loss, and has high yield and little harm to the environment. The obtained tungsten oxide quantum dots have water solubility, do not have the coating of long-chain organic matters on the surface, are highly dispersed, have narrow particle size distribution and adjustable particle size, and can be stored for a long time.
In the preparation method of the tungsten oxide quantum dot material, the tungsten source is at least one of tungstic acid, ammonium tungstate, ammonium metatungstate and ammonium paratungstate.
In the preparation method of the tungsten oxide quantum dot material, the polyalcohol is at least one of pentaerythritol, propylene glycol, xylitol, sorbitol, ethylene glycol, glycerol, 2-methyl-1, 3-propanediol, diethylene glycol, trihydroxyethane, butanediol and trihydroxypropane.
In the preparation method of the tungsten oxide quantum dot material, in the step A, the mass concentration range of the tungsten source in the polyalcohol solvent is 0.1-2 mol/L, and preferably 0.5-1 mol/L.
In the preparation method of the tungsten oxide quantum dot material, the heating temperature in the step A is preferably 100 ℃, and the heating time is preferably 4 hours.
In the preparation method of the tungsten oxide quantum dot material, the reaction temperature in the step B is preferably 200 ℃, and the reaction time is preferably 16 h.
The invention has the beneficial effects that: the synthesis method is simple and efficient, the raw materials are wide in source, cheap and easy to obtain, the template removing step with extremely complex operation process is omitted, the negative influence of residual templates on the properties and the use of the tungsten oxide quantum dots is avoided, multi-step filtration is not needed, the yield of the water-soluble quantum dots is improved, the prepared tungsten oxide quantum dots are water-soluble, have no organic matter coating on the surface, are highly dispersed, have narrow particle size distribution, and can be stored for a long time.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of tungsten oxide quantum dots, which is a target product obtained in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the target product tungsten oxide quantum dots obtained in example 1 at different scales;
FIG. 3 is a diagram of the UV-VIS absorption spectrum of the target product tungsten oxide quantum dots obtained in example 1;
FIG. 4 is an X-ray photoelectron spectrum (XPS) of a target product tungsten oxide quantum dot obtained in example 1;
FIG. 5 is an optical photograph of the target product tungsten oxide quantum dots obtained in example 1 in a polyol;
FIG. 6 is a Transmission Electron Microscope (TEM) photograph of the target product tungsten oxide quantum dots obtained in example 2;
FIG. 7 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 3;
FIG. 8 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 4;
FIG. 9 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 5;
FIG. 10 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 6;
FIG. 11 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 7;
FIG. 12 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 8;
FIG. 13 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 9;
FIG. 14 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 10;
FIG. 15 is a Transmission Electron Microscope (TEM) photograph of the target tungsten oxide quantum dots obtained in example 11.
Detailed Description
For a further enhancement of the understanding of the present invention, preferred embodiments of the present invention are described below in conjunction with examples, but it is to be understood that the descriptions of the examples are intended to further illustrate features and advantages of the present invention, and are not intended to limit the claims of the present invention.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art. All the raw materials of the present invention are not particularly limited in their purity, and analytical purification is preferably employed in the present invention.
The production process of the present invention is schematically illustrated below.
First, a tungsten source is added to a solvent containing a polyol. The tungsten source used may be at least one of tungstic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate. The polyhydric alcohol can be at least one of pentaerythritol, propylene glycol, xylitol, sorbitol, ethylene glycol, glycerol, 2-methyl-1, 3-propanediol, diethylene glycol, trihydroxyethane, butanediol, and trihydroxypropane. The polyol-containing solvent may also include water, wherein the volume ratio of polyol to water may be 1: (2-4). Pentaerythritol, xylitol, sorbitol, trihydroxyethane and trihydroxypropane are solid at normal temperature, and are dissolved in water to form a polyol aqueous solution, and then a tungsten source is added.
In the preparation method, a tungsten-oxygen bond in the tungsten source in the step A and a hydroxyl group of polyhydric alcohol form bonding to obtain a reaction precursor of the tungsten oxide quantum dot; in the reaction process, the polyhydric alcohol is coated on the surface of the tungsten oxide crystal nucleus to limit the length of the tungsten oxide crystal nucleus and prevent the tungsten oxide nano particles from agglomerating, so that the monodisperse tungsten oxide quantum dot polyhydric alcohol solution with extremely small size can be obtained. And in the step B, under the condition that extra high pressure is not needed, the solvent generates pressure in a high-temperature closed environment, so that the reaction is promoted.
The mass concentration of the tungsten source in the polyol-containing solvent is in the range of 0.1 to 2mol/L, preferably 0.5 to 1mol/L, and more preferably 1 mol/L. Under the same reaction condition, the higher the concentration of the tungsten source, the shorter the required reaction time, and the larger the particle size of the generated particles.
And then stirring for 1-4 h at 60-140 ℃, wherein the stirring speed can be 200-800 r/min, so that the tungsten source and the polyhydric alcohol are fully reacted and mixed to obtain a reaction precursor.
And then placing the obtained reaction precursor into a reaction kettle with a stirring function, stirring and reacting for 5-24 h at 150-250 ℃, and cooling to room temperature after the reaction is finished to obtain the polyol tungsten oxide quantum dot solution. The stirring speed can be 300-600 r/min.
The Chinese patent CN104861971A takes tungsten disulfide as a raw material, and the tungsten oxide quantum dot aqueous solution is prepared by an ultrasonic filtration hydrothermal reaction method, but the concentration of the reaction precursor tungsten disulfide is only 0.15mg/ml, and the tungsten oxide quantum dot aqueous solution can be obtained only by filtering twice, most reaction raw materials are filtered, the concentration of the obtained tungsten oxide quantum dots is extremely low, and the raw materials are wasted seriously. The method has high utilization rate of raw materials, the concentration of the precursor tungsten source is preferably 1mol/L, the tungsten source and the reaction solvent are directly mixed, and the tungsten oxide quantum dot polyalcohol solution is obtained through solvothermal reaction, so that the utilization rate of the raw materials is close to 100 percent, and the production cost is greatly reduced. Therefore, the preparation method of the tungsten oxide quantum dot material provided by the invention has the advantages that tungstic acid or tungstate is used as a tungsten source, and the polyalcohol or the mixed solution of the polyalcohol and water is used as a solvent, so that the use of a template is omitted, the process steps are simplified, the high-loss filtering step is avoided, and the yield of the quantum dot is improved.
And separating the tungsten oxide quantum dot from the prepared tungsten oxide quantum dot polyalcohol solution to obtain the tungsten oxide quantum dot aqueous dispersion. And (3) placing the obtained tungsten oxide quantum dot polyalcohol solution into a dialysis bag, putting the dialysis bag into water for dialysis for 3-12 h, wherein the molecular interception amount of the dialysis bag is 1000-10000, preferably 8000, and thus obtaining the tungsten oxide quantum dot water dispersion.
The tungsten oxide quantum dot material obtained by the invention comprises tungsten oxide nanoparticles with the particle size of 1-3 nm and quantum size effect, the surface of the tungsten oxide nanoparticles is not coated by long-chain organic matters, and the tungsten oxide nanoparticles are highly dispersed in polar solvents, such as water and short-chain alcohol solutions. The tungsten oxide nano particles have uniform particle size, narrow particle size distribution and adjustable particle size, and can be stored for a long time.
The obtained tungsten oxide quantum dot polyalcohol solution has no obvious change after being placed for one year, and no precipitate is generated.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, adding 0.05mol of ammonium tungstate into 100mL of diethylene glycol, heating for 1.5h at 100 ℃ under continuous stirring at 400r/min, decomposing the ammonium tungstate in a diethylene glycol solvent to generate tungsten oxide crystal nuclei, forming bonding between tungsten oxygen bonds and hydroxyl groups on the diethylene glycol, and fully reacting and mixing to obtain a reaction precursor;
B. and D, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, reacting for 10 hours at 200 ℃ at 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot diethylene glycol solution.
Putting the obtained tungsten oxide quantum dot diethylene glycol solution into a dialysis bag (the molecular interception amount is 8000), putting the dialysis bag into water for dialysis for 4 hours, and obtaining the solution in the dialysis bag, namely the tungsten oxide quantum dot aqueous solution.
Fig. 1 shows the test performed by dropping an aqueous solution of tungsten oxide quantum dots on a silicon wafer, and fig. 2 shows the test performed by dropping an aqueous solution of tungsten oxide quantum dots on a carbon film copper mesh. FIG. 1 is an X-ray diffraction spectrum of the tungsten oxide quantum dot obtained in example 1, which is hexagonal phase tungsten oxide (JCPDF #85-2460), and the corresponding crystal planes are (100), (002) and (200), respectively, and the diffraction peaks obviously broadened indicate that extremely small particle sizes are generated. Fig. 2 is a transmission electron microscope picture of the tungsten oxide quantum dots obtained in example 1, and it can be clearly seen that the size distribution of the nano-scale tungsten oxide quantum dots is relatively uniform, and the size of the nano-scale tungsten oxide quantum dots is 1.2nm to 1.8 nm. FIG. 3 is a diagram of the ultraviolet absorption spectrum of the tungsten oxide quantum dot, and it can be seen that there is an absorption peak at 380 nm. The forbidden band width of the tungsten oxide quantum dot is 3.26ev and is far smaller than the forbidden band width of commercial tungsten oxide powder by 2.6ev (adv.mater.2014,26,4260.) through calculation, and the absorption spectrum generates obvious blue shift and generates quantum size effect. FIG. 4 is an X-ray photoelectron spectroscopy measurement of tungsten oxide quantum dots, both peaks correspond to + 6-valent tungsten, a peak of + 5-valent tungsten does not appear, and the element number ratio of tungsten to oxygen is 1: 3. Fig. 5 is an optical photograph of the tungsten oxide quantum dot diethylene glycol solution obtained in example 1, which is a light yellow clear transparent solution.
Example 2
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, 0.07mol of ammonium metatungstate is added into 100mLML glycerol, and the mixture is heated for 1h at 120 ℃ under the continuous stirring of 400r/min, and a reaction precursor is obtained after full reaction and mixing;
B. and D, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, reacting for 20h at 180 ℃ at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot glycerol solution.
Example 3
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, 0.06mol of ammonium paratungstate is added into 100mL of propylene glycol, and the mixture is heated for 3h at 130 ℃ under the continuous stirring of 500r/min, and a reaction precursor is obtained after full reaction and mixing;
B. and B, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, then stirring and reacting at 190 ℃ for 10h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot propylene glycol solution.
Example 4
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, adding 0.1mol of tungstic acid into 100mL of ethylene glycol, heating for 3h at 80 ℃ under continuous stirring at 400r/min, and fully reacting and mixing to obtain a reaction precursor;
B. and D, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring at 210 ℃ for reaction for 17 hours at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot ethylene glycol solution.
Example 5
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, 50g of xylitol is dissolved in 50mL of deionized water to form a mixed solution, then 0.15mol of tungstic acid is added into the mixed solution, the mixed solution is heated for 2 hours at 130 ℃ under continuous stirring at 800r/min, and a reaction precursor is obtained after full reaction and mixing;
B. and D, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring and reacting at 200 ℃ for 15h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot xylitol solution.
Example 6
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, 50g of sorbitol is dissolved in 50mL of deionized water to form a mixed solution, then 0.08mol of ammonium tungstate is added into the mixed solution, the mixed solution is heated for 2.5 hours at 110 ℃ under the condition of continuous stirring at 500r/min, and a reaction precursor is obtained after full reaction and mixing;
B. and D, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring and reacting at 240 ℃ for 15h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot sorbitol solution.
Example 7
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, dissolving 50g of trihydroxyethane in 50mL of deionized water to form a mixed solution, then adding 0.1mol of ammonium metatungstate into the mixed solution, heating for 3h at 60 ℃ under continuous stirring at 600r/min, and fully reacting and mixing to obtain a reaction precursor;
B. and B, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring and reacting at 220 ℃ for 18h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot trihydroxy ethane solution.
Example 8
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, 50g of trihydroxypropane is dissolved in 50mL of deionized water to form a mixed solution, then 0.07mol of ammonium paratungstate is added into the mixed solution, the mixed solution is heated for 2 hours at 90 ℃ under continuous stirring at 700r/min, and a reaction precursor is obtained after full reaction and mixing;
B. and B, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring and reacting at 240 ℃ for 16h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot trihydroxypropane solution.
Example 9
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, 50g of xylitol is dissolved in 50mL of deionized water to form a mixed solution, then 0.07mol of ammonium paratungstate is added into the mixed solution, the mixed solution is heated for 2 hours at 90 ℃ under continuous stirring at 700r/min, and a reaction precursor is obtained after full reaction and mixing;
B. and D, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring and reacting at 240 ℃ for 16h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot xylitol solution.
Example 10
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, 50g of sorbitol is dissolved in 50mL of deionized water to form a mixed solution, then 0.08mol of ammonium tungstate is added into the mixed solution, the mixed solution is heated for 2 hours at 85 ℃ under the continuous stirring of 600r/min, and a reaction precursor is obtained after full reaction and mixing;
B. and D, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring and reacting at 240 ℃ for 16h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot sorbitan solution.
Example 11
A tungsten oxide quantum dot material and a preparation method thereof comprise the following steps:
A. firstly, dissolving 50g of trihydroxyethane in 50mL of deionized water to form a mixed solution, then adding 0.07mol of tungstic acid into the mixed solution, heating for 2h at 90 ℃ under continuous stirring at 700r/min, and fully reacting and mixing to obtain a reaction precursor;
B. and B, then placing the reaction precursor obtained in the step A into a reaction kettle with a stirring function, wherein the total volume of the reaction kettle is 200mL, stirring and reacting at 240 ℃ for 16h at a speed of 400r/min, and cooling to room temperature to obtain the tungsten oxide quantum dot trihydroxy ethane solution.
The above-described embodiments are merely illustrative of several embodiments of the invention and do not represent a limitation on the scope of the invention, which may in fact be embodied in many different forms. Several variations and modifications are within the scope of the invention without departing from the spirit thereof, which is to be determined from the appended claims.
Claims (5)
1. A preparation method of a tungsten oxide quantum dot material is characterized by comprising the following steps:
A. preparing a precursor: adding a tungsten source into a solvent containing polyol, heating and stirring at 60-140 ℃ for 1-4 hours to obtain a reaction precursor; the tungsten source is at least one of tungstic acid, ammonium tungstate, ammonium metatungstate and ammonium paratungstate;
B. and B, placing the reaction precursor obtained in the step A into a reaction kettle, reacting for 5-24 hours at the temperature of 150-250 ℃, and cooling to obtain the tungsten oxide quantum dot polyalcohol solution.
2. The method according to claim 1, wherein the polyhydric alcohol is at least one of pentaerythritol, propylene glycol, xylitol, sorbitol, ethylene glycol, glycerol, 2-methyl-1, 3-propanediol, diethylene glycol, trihydroxyethane, butanediol, and trihydroxypropane.
3. The preparation method according to claim 1, wherein in the step A, the concentration of the tungsten source in the solvent is in the range of 0.1-2 mol/L.
4. The preparation method according to claim 3, wherein in the step A, the concentration of the tungsten source in the solvent is 0.5-1 mol/L.
5. The method according to claim 1, wherein in the step a, the solvent containing the polyhydric alcohol further contains water, and the volume ratio of the polyhydric alcohol to the water is 1: (2-4).
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| CN107055618A (en) * | 2016-12-23 | 2017-08-18 | 青岛大学 | Method for simultaneously preparing tungsten oxide quantum dots and tungsten oxide nanowires |
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| CN104789218A (en) * | 2014-01-21 | 2015-07-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Tungsten oxide quantum dot material and preparation method thereof |
| CN107055618A (en) * | 2016-12-23 | 2017-08-18 | 青岛大学 | Method for simultaneously preparing tungsten oxide quantum dots and tungsten oxide nanowires |
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| Hydrothermal synthesis of oxygen-deficiency tungsten oxide quantum dots with excellent photochromic reversibility;Liu Qingqing;《Applied Surface Science》;20190302;第480卷;全文 * |
| Oxygen defect-induced localized surface plasmon resonance at the WO3−x quantum dot/silver nanowire interface:SERS and photocatalysis;Wei Wei;《Nanoscale》;20190225;第11卷(第12期);第5544页左栏第2段 * |
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