CN110240902A - A kind of preparation method of tungsten oxide quanta point material - Google Patents
A kind of preparation method of tungsten oxide quanta point material Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of tungsten oxide quanta point material, comprising the following steps: A. prepares precursor: tungsten source is added in the solvent containing polyalcohol, in 60~140 DEG C heating stirring 1~4 hour, obtain precursors；B. then the obtained precursors of step A are placed in reaction kettle, are reacted 5~24 hours in 150~250 DEG C, it is cooling to obtain tungsten oxide quantum dot polyhydric alcohol solutions.The beneficial effects of the present invention are: synthetic method is simple and efficient, raw material sources are extensive, cheap and easy to get, the extremely complex removing template step of operating procedure is omitted, avoids residual template from having a negative impact the property of tungsten oxide quantum dot and use, is not necessarily to more steps of filtration, improve the yield of water-soluble quantum dot, preparing tungsten oxide quantum dot has water solubility, and the cladding of organic matter, high degree of dispersion is not present in surface, particle size narrowly distributing can store for a long time.
Description
Technical field
The present invention relates to a kind of preparation method of tungsten oxide quanta point material, in particular to a kind of high degree of dispersion, pattern are equal
One, the tungsten oxide quanta point material and its liquid phase preparation process of size adjustable, belongs to a nanometer new material technology field.
Background technique
Tungsten oxide has excellent electrical and optical properties, is widely used in as a kind of important semiconductor material
Intelligent color-changing smart window, photocatalysis, solar battery, sensor, photo-thermal therapy field.Semiconductor nanocrystal, i.e. quantum dot,
It is the aggregate of atom and molecule on nanoscale, the physical behavio(u)r such as light, electrical property of this zero dimension system is similar to atom,
It often thus is referred to as " artificial atom ", the discrete energy level structure of electronics in similar atom is presented in energy state wherein for electronics.
Semiconductor-quantum-point has unique physics and chemical property, in magnetics, electricity, optics, catalysis and chemical sensitisation and biology
Medicine etc. has broad application prospects.Tungsten oxide quanta point material is due to its unique physicochemical properties, in recent years
It gets more and more people's extensive concerning.Liu et al. (Appl.Surf.Sci.2019,480,404.) has been synthesized by the method for hydro-thermal to be contained
The tungsten oxide quantum dot of Lacking oxygen, it was demonstrated that it is with superior photochromic properties.Cong etc. (Adv.Mater.2014,
26,4260.) tungsten oxide quantum dot has been synthesized using two-step method, and has been connect conductive organic matter by the method that surface ligand is replaced
Branch arrives quantum dot surface, it is found that it has more excellent chemical property relative to block tungsten oxide material.Epifani etc.
(ACS Appl.Mater.Interfaces 2014,6,16808-16816.) has been synthesized as reaction dissolvent using oleic acid and has been contained
The tungsten oxide quantum dot of Lacking oxygen, and it is prepared into senser element, it was demonstrated that it has nitrogen dioxide and alcohol gas excellent
Detection accuracy.Although tungsten oxide quantum dot has been demonstrated there is good application prospect, tungsten oxide amount in numerous areas
The lag of son point synthetic method, results in the difficulty that the large-area applications of tungsten oxide quanta point material are promoted.
Chinese patent (CN104789218A) first reacts inorganic tungsten compound with organic ligand in certain temperature
Organic tungsten presoma is generated, then organic no tungsten presoma is reacted at high temperature with organic solvent, is divided after reaction
From obtaining tungsten oxide quantum dot.Although the method can obtain tungsten oxide quantum dot, tungsten oxide quantum dot surface coats one layer
It is not easy the long-chain organic matter not soluble in water removed, this greatly reduces the electric conductivity and biocompatibility of tungsten oxide quantum dot,
To limit the range of its practical application.Chinese patent (CN104861971A) is prepared for tungsten oxide amount by raw material of tungsten sulfide
Son point material, detailed process include first tungsten sulfide solid being formed suspension by the method for ultrasound in distilled water, being hanged
Filter cake is obtained by filtration in supernatant liquid, then filter cake is resuspended in distilled water to be placed in high temperature water heating kettle and is reacted, finally by hydro-thermal
Product after reaction is filtered, and obtained filtrate is tungsten oxide quantum dot aqueous solution.The method has obtained water-soluble oxygen
Change tungsten quantum dot, and surface does not include the cladding of long-chain organic matter, the application for tungsten oxide quantum dot is beneficial.However,
The waste of the method raw material is extremely serious, just obtains tungsten oxide quantum dot aqueous solution after filtering twice, raw material availability,
High production cost is unfavorable for producing on a large scale.Chinese patent (CN107416906A) is first body with tungsten disulfide, using double
The strong oxidizing property of oxygen water aoxidizes tungsten disulfide by solvent-thermal method in alcohols dispersion liquid to obtain fluorescence tungsten oxide quantum dot.
But this method uses hydrogen peroxide as oxidant, is not only easy to cause to corrode to equipment, but also make the post-processing of reaction solution
At trouble, certain harm can be generated to environment.Watanabe etc. (Chem.Commun., 2013,49,8477.) utilizes nanometer
Porous silicon successfully synthesizes the controllable tungsten oxide quantum dot of size as reaction template.Such method tungsten oxide quantum dot yield
Low, template is difficult to remove, and very big difficulty is brought to subsequent application.Wang etc. (J.Mater.Chem.C, 2015,3,
3280.) using tungsten chloride as tungsten source, ethylene glycol has synthesized tungsten oxide amount as reaction dissolvent, by the method for microwave solvothermal
Sub- point.This process is relatively simple, but the concentration of reactant is extremely low, and tungsten chloride is costly and with very strong corrosivity, easily
It reacts with the vapor in air, reaction process is difficult to control, this can all increase production cost, it is made to be not easy to industrialize
Production.In conclusion there is problems for the synthetic method of tungsten oxide quantum dot at present, tungsten oxide quantum is greatly limited
The large scale application of point, so the tungsten oxide quantum dot synthetic method important in inhibiting that exploitation is simple and efficient.
Summary of the invention
Present invention aims to overcome that existing technological deficiency, provides a kind of tungsten oxide quantum of efficiently simple low cost
Point preparation method.
To achieve the above object, the present invention provides a kind of preparation method of tungsten oxide quanta point material, comprising the following steps:
A. prepare precursor: tungsten source be added in the solvent containing polyalcohol, in 60~140 DEG C heating stirring 1~4 hour,
Obtain precursors；
B. then the obtained precursors of step A are placed in reaction kettle, are reacted 5~24 hours in 150~250 DEG C, it is cooling
Obtain tungsten oxide quantum dot polyhydric alcohol solutions.
The use of template is omitted in method of the invention, avoids the template not removed that tungsten oxide quantum dot performance is caused to drop
Low, without can be obtained tungsten oxide quanta point material by consuming the separating steps such as serious filtering, yield is high, to environmental hazard
It is small.And obtained tungsten oxide quantum dot has water solubility, and the cladding of long-chain organic matter, high degree of dispersion, grain is not present in surface
Diameter narrowly distributing, particle size is adjustable, can store for a long time.
In the preparation method of the tungsten oxide quanta point material, the tungsten source is wolframic acid, ammonium tungstate, ammonium metatungstate, secondary tungsten
At least one of sour ammonia.
In the preparation method of the tungsten oxide quanta point material, the polyalcohol be pentaerythrite, propylene glycol, xylitol,
Sorbierite, ethylene glycol, glycerine, 2- methyl-1,3-propanediol, diethylene glycol, trihydroxy ethane, butanediol, Glycerin
At least one of.
In the preparation method of the tungsten oxide quanta point material, in step A, the tungsten source is in the polyol solvent
Amount of substance concentration range is 0.1~2mol/L, preferably 0.5~1mol/L.
In the preparation method of the tungsten oxide quanta point material, heating temperature is preferably 100 DEG C in the step A, heating
Time is preferably 4h.
In the preparation method of the tungsten oxide quanta point material, reaction temperature is preferably 200 DEG C in the step B, reaction
Time is preferably 16h.
The beneficial effects of the present invention are: synthetic method is simple and efficient, and raw material sources are extensive, cheap and easy to get, omits operation
The extremely complex removing template step of technique avoids residual template from having a negative impact the property of tungsten oxide quantum dot and use,
Without more steps of filtration, the yield of water-soluble quantum dot is improved, preparing tungsten oxide quantum dot has water solubility, and there is no have on surface
The cladding of machine object, high degree of dispersion, particle size narrowly distributing can store for a long time.
Detailed description of the invention
Fig. 1 is embodiment 1 gained target product tungsten oxide quantum dot X-ray diffraction (XRD) map；
Fig. 2 is that transmission electron microscope (TEM) of the 1 gained target product tungsten oxide quantum dot of embodiment under different scales shines
Piece；
Fig. 3 is 1 gained target product tungsten oxide quantum dot ultraviolet-visible absorption spectroscopy figure of embodiment；
Fig. 4 is 1 gained target product tungsten oxide quantum dot x-ray photoelectron spectroscopy figure (XPS) of embodiment；
Fig. 5 is optical photograph of the 1 gained target product tungsten oxide quantum dot of embodiment in polyalcohol；
Fig. 6 is embodiment 2 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Fig. 7 is embodiment 3 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Fig. 8 is embodiment 4 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Fig. 9 is embodiment 5 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Figure 10 is embodiment 6 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Figure 11 is embodiment 7 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Figure 12 is embodiment 8 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Figure 13 is embodiment 9 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Figure 14 is embodiment 10 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo；
Figure 15 is embodiment 11 gained target product tungsten oxide quantum dot transmission electron microscope (TEM) photo.
Specific embodiment
In order to further deepen the understanding of the present invention, the preferred embodiments of the invention are carried out below with reference to example
Description, but it is to be understood that the description of these examples is intended merely to further illustrate the features and advantages of the present invention, rather than right
The limitation of invention claim.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.All raw materials of the present invention, are not particularly limited its purity, present invention preferably employs
It analyzes pure.
Property illustrated below illustrates preparation method of the invention.
Firstly, being added in tungsten source in the solvent containing polyalcohol.The tungsten source used can be wolframic acid, ammonium tungstate, metatungstic acid
At least one of ammonium, para-tungstic acid ammonia.The polyalcohol can be pentaerythrite, propylene glycol, xylitol, sorbierite, ethylene glycol, third
Triol, 2- methyl-1,3-propanediol, trihydroxy ethane, butanediol, in Glycerin are at least one at diethylene glycol.Contain
The solvent for having polyalcohol can also include water, wherein the volume ratio of polynary alcohol and water can be 1:(2~4).Pentaerythrite, xylose
It is solid under alcohol, sorbierite, trihydroxy ethane, Glycerin room temperature, needs first to be dissolved in water, it is water-soluble forms polyalcohol
Then liquid tungsten source is added.
In the above preparation method, the tungsten oxygen key in step A tungsten source is bonded with the formation of the hydroxyl of polyalcohol, obtains tungsten oxide
The precursors of quantum dot；Polyalcohol is coated on tungsten oxide nucleating surface during the reaction, limits the length of tungsten oxide nucleus
Greatly, the reunion of tungsten oxide nanoparticles is prevented, it is hereby achieved that the tungsten oxide quantum dot polyalcohol that monodispersed size is minimum
Solution.Step B is not in the case where needing additionally to add high pressure, self-generated pressure of the solvent under high-temperature closed environment, promotes anti-
Should carry out.
Tungsten source containing the amount of substance concentration range in polyol solvent be 0.1~2mol/L, preferably 0.5~1mol/L,
More preferably 1mol/L.Under the same reaction conditions, tungsten source concentration is higher, and the required reaction time is shorter, the grain diameter of generation
It is bigger.
Then in 60~140 DEG C of 1~4h of stirring, the revolving speed of stirring can be 200~800r/min, make tungsten source and polyalcohol into
Row sufficiently reaction mixing, obtains precursors.
Then gained precursors are placed in the reaction kettle with agitating function, are stirred to react 5 in 150~250 DEG C
~for 24 hours, after reaction, cools to room temperature and obtain polyalcohol tungsten oxide quantum dot solution.The revolving speed of stirring can be 300
~600r/min.
Chinese patent CN104861971A obtains method by ultrasound filtration hydro-thermal reaction and is prepared for using tungsten disulfide as raw material
Tungsten oxide quantum dot aqueous solution, but the concentration of precursors tungsten disulfide is only 0.15mg/ml, and is needed by mistake twice
Filter can just obtain tungsten oxide quantum dot aqueous solution, and most reaction raw materials are filtered out, obtained tungsten oxide quantum dot concentration pole
Low, wastage of material is serious.Raw material availability of the present invention is high, and the concentration in presoma tungsten source is preferably 1mol/L, directly by tungsten source with
Reaction dissolvent mixing, obtains tungsten oxide quantum dot polyhydric alcohol solutions by solvent thermal reaction, raw material availability is close to 100%, greatly
Big reduces production cost.Therefore, the preparation method of tungsten oxide quanta point material of the present invention, with wolframic acid or tungstates
As tungsten source, using the mixed solution of polyalcohol or polyalcohol and water as solvent, the use of template is omitted, simplifies technique step
Suddenly, it and avoids improving the yield of quantum dot using the filtration step of high loss.
It can also be separated from tungsten oxide quantum dot polyhydric alcohol solutions obtained and obtain tungsten oxide quantum dot aqueous dispersions.It will
The tungsten oxide quantum dot polyhydric alcohol solutions obtained are placed in bag filter, the molecule interception 1000~10000 of bag filter, preferably
8000, dialyse 3~12h into the water, can be obtained tungsten oxide quantum dot aqueous dispersions.
It is 1~3nm and the tungsten oxide with quantum size effect that gained tungsten oxide quanta point material of the invention, which includes partial size,
Nanoparticle, the cladding of long-chain organic matter is not present in surface, in polar solvent, as highly divided in the alcoholic solution of water and short chain
It dissipates.The tungsten oxide nanometer particle diameter is uniform, particle diameter distribution is narrow, and particle size is adjustable, can store for a long time.
Gained tungsten oxide quantum dot polyhydric alcohol solutions place one-year age without significant change, and no precipitating generates.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 0.05mol ammonium tungstate is added in 100mL diethylene glycol first, in 100 DEG C under continuous 400r/min stirring
1.5h is heated, ammonium tungstate is decomposed in diethylene glycol solvent, generates tungsten oxide nucleus, the hydroxyl in tungsten oxygen key and diethylene glycol
Base forms bonding, sufficiently obtains precursors after reaction mixing；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, reacts 10h at 200 DEG C, with 400r/min, and it is molten to obtain tungsten oxide quantum dot diethylene glycol after cooling down to room temperature
Liquid.
Gained tungsten oxide quantum dot diethylene glycol solution is placed in bag filter (molecule interception is 8000), into the water thoroughly
4h is analysed, acquired solution is tungsten oxide quantum dot aqueous solution in bag filter.
Fig. 1 is tested on silicon wafer by the water-soluble drop-coated of tungsten oxide quantum dot, and Fig. 2 is by tungsten oxide quantum dot water
What solution drop coating was tested on carbon film copper mesh.The X-ray diffraction spectrogram of 1 gained tungsten oxide quantum dot of Fig. 1 embodiment is six
Square phase oxidation tungsten (JCPDF#85-2460), corresponding crystal face are respectively (100), (002) and (200), hence it is evident that the diffraction of wideization
Peak shows to generate minimum partial size.Fig. 2 is the transmission electron microscope picture of tungsten oxide quantum dot that embodiment 1 obtains, in figure
Size distribution is relatively uniform with can clearly be seen that nanoscale tungsten quantum dot, the size of nanometer tungsten oxide be 1.2nm~
1.8nm.Fig. 3 is the uv absorption spectra of tungsten oxide quantum dot, it can be seen that has absorption peak in 380nm.It can be with by calculating
The forbidden bandwidth for obtaining tungsten oxide quantum dot is 3.26ev, far smaller than the forbidden bandwidth 2.6ev of commercial oxidation tungsten powder body
Obvious blue shift occurs for (Adv.Mater.2014,26,4260.), absorption spectrum, and quantum size effect occurs.Fig. 4 is tungsten oxide amount
The x-ray photoelectron spectroscopy measurement of son point, all corresponding+6 valence tungsten in two peaks, does not occur the peak of+5 valence tungsten, and obtains tungsten and oxygen
Element number ratio is 1:3.Fig. 5 is the optical photograph of 1 gained tungsten oxide quantum dot diethylene glycol Solutions Solution of embodiment, the solution
For flaxen clear transparent solutions.
Embodiment 2
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 0.07mol ammonium metatungstate is added in 100mLmL glycerine first, in 120 under continuous 400r/min stirring
DEG C heating 1h, sufficiently reaction mixing after obtain precursors；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL reacts 20h at 180 DEG C, with 400r/min, tungsten oxide quantum dot glycerin solution is obtained after cooling down to room temperature.
Embodiment 3
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 0.06mol para-tungstic acid ammonia is added in 100mL propylene glycol first, in 130 DEG C under continuous 500r/min stirring
3h is heated, sufficiently obtains precursors after reaction mixing；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, then 190 DEG C, be stirred to react 10h with 400r/min, tungsten oxide quantum dot third is obtained after cooling down to room temperature
Glycol solution.
Embodiment 4
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 0.1mol wolframic acid is added in 100mL ethylene glycol first, in 80 DEG C of heating 3h under continuous 400r/min stirring,
Sufficiently precursors are obtained after reaction mixing；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 210 DEG C, reaction 17h is stirred to react with 400r/min, tungsten oxide quantum dot second is obtained after cooling down to room temperature
Glycol solution.
Embodiment 5
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 50g xylitol is dissolved in 50mL deionized water first and forms mixed solution, be then added to 0.15mol wolframic acid mixed
It closes in solution, in 130 DEG C of heating 2h under continuous 800r/min stirring, sufficiently obtains precursors after reaction mixing；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 200 DEG C, reaction 15h is stirred to react with 400r/min, tungsten oxide quantum dot wood is obtained after cooling down to room temperature
Sugar alcohol solution.
Embodiment 6
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 50g sorbierite is dissolved in 50mL deionized water first and forms mixed solution, be then added to 0.08mol ammonium tungstate
In mixed solution, in 110 DEG C of heating 2.5h under continuous 500r/min stirring, reaction precursor sufficiently is obtained after reaction mixing
Body；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 240 DEG C, reaction 15h is stirred to react with 400r/min, tungsten oxide quantum dot mountain is obtained after cooling down to room temperature
Pears alcoholic solution.
Embodiment 7
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 50g trihydroxy ethane is dissolved in 50mL deionized water first and forms mixed solution, then by 0.1mol ammonium metatungstate
It is added in mixed solution, in 60 DEG C of heating 3h under continuous 600r/min stirring, before sufficiently obtaining reaction after reaction mixing
Drive body；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 220 DEG C, reaction 18h is stirred to react with 400r/min, tungsten oxide quantum dot three is obtained after cooling down to room temperature
Hydroxyl ethane solution.
Embodiment 8
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 50g Glycerin is dissolved in 50mL deionized water first and forms mixed solution, then by 0.07mol para-tungstic acid ammonia
It is added in mixed solution, in 90 DEG C of heating 2h under continuous 700r/min stirring, before sufficiently obtaining reaction after reaction mixing
Drive body；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 240 DEG C, reaction 16h is stirred to react with 400r/min, tungsten oxide quantum dot three is obtained after cooling down to room temperature
Hydroxy propane solution.
Embodiment 9
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 50g xylitol is dissolved in 50mL deionized water first and forms mixed solution, then 0.07mol para-tungstic acid ammonia is added
Into mixed solution, in 90 DEG C of heating 2h under continuous 700r/min stirring, precursors sufficiently are obtained after reaction mixing；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 240 DEG C, reaction 16h is stirred to react with 400r/min, tungsten oxide quantum dot wood is obtained after cooling down to room temperature
Sugar alcohol solution.
Embodiment 10
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 50g sorbierite is dissolved in 50mL deionized water first and forms mixed solution, be then added to 0.08mol wolframic acid ammonia
In mixed solution, in 85 DEG C of heating 2h under continuous 600r/min stirring, precursors sufficiently are obtained after reaction mixing；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 240 DEG C, reaction 16h is stirred to react with 400r/min, tungsten oxide quantum dot mountain is obtained after cooling down to room temperature
Pears alcohol alkane solution.
Embodiment 11
A kind of tungsten oxide quanta point material and preparation method thereof, comprising the following steps:
A. 50g trihydroxy ethane is dissolved in 50mL deionized water first and forms mixed solution, then 0.07mol wolframic acid is added
Into mixed solution, in 90 DEG C of heating 2h under continuous 700r/min stirring, precursors sufficiently are obtained after reaction mixing；
B. then the obtained precursors of step A are placed in the reaction kettle with agitating function, the total volume of reaction kettle is
200mL, 240 DEG C, reaction 16h is stirred to react with 400r/min, tungsten oxide quantum dot three is obtained after cooling down to room temperature
Hydroxyl ethane solution.
Embodiment described above only illustrates several embodiments of the invention, does not represent the range to the invention patent
Limitation, actually the invention can be realized in many different forms.Several modification and improvement are not departing from this design
In the case of belong to protection scope of the present invention, scope of patent protection of the invention should with subject to appended claims.
Claims (6)
1. a kind of preparation method of tungsten oxide quanta point material, which comprises the following steps:
A. prepare precursor: tungsten source be added in the solvent containing polyalcohol, in 60~140 DEG C heating stirring 1~4 hour,
Obtain precursors；
B. then the obtained precursors of step A are placed in reaction kettle, are reacted 5~24 hours in 150~250 DEG C, it is cooling
Obtain tungsten oxide quantum dot polyhydric alcohol solutions.
2. preparation method according to claim 1, which is characterized in that the tungsten source be wolframic acid, ammonium tungstate, ammonium metatungstate,
At least one of para-tungstic acid ammonia.
3. preparation method according to claim 1 or 2, which is characterized in that the polyalcohol be pentaerythrite, propylene glycol,
Xylitol, sorbierite, ethylene glycol, glycerine, 2- methyl-1,3-propanediol, diethylene glycol, trihydroxy ethane, butanediol and three
At least one of hydroxy propane.
4. preparation method described in any one of claim 1 to 3, which is characterized in that in step A, the tungsten source is in institute
Stating the amount of substance concentration range in solvent is 0.1~2 mol/L, preferably 0.5~1mol/L.
5. preparation method according to any one of claims 1 to 4, which is characterized in that in step A, the tungsten source is in institute
Stating the amount of substance concentration range in solvent is 0.5~1mol/L.
6. preparation method according to any one of claims 1 to 5, which is characterized in that described containing polynary in step A
The solvent of alcohol also contains water, wherein the volume ratio of polynary alcohol and water is 1:(2~4).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | Preparation method while a kind of tungsten oxide quantum dot and tungsten oxide nano |
-
2019
- 2019-07-11 CN CN201910624874.7A patent/CN110240902B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | Preparation method while a kind of tungsten oxide quantum dot and tungsten oxide nano |
Non-Patent Citations (2)
| Title |
|---|
| LIU QINGQING: "Hydrothermal synthesis of oxygen-deficiency tungsten oxide quantum dots with excellent photochromic reversibility", 《APPLIED SURFACE SCIENCE》 * |
| WEI WEI: "Oxygen defect-induced localized surface plasmon resonance at the WO3−x quantum dot/silver nanowire interface:SERS and photocatalysis", 《NANOSCALE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355030A (en) * | 2021-06-03 | 2021-09-07 | 中稀产业发展(天津)集团有限公司 | Preparation method of intelligent dimming glass color-changing heat insulation adhesive film based on quantum dots |
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