CN106928994A - A kind of photochromic composite nano powder and preparation method thereof, application - Google Patents
A kind of photochromic composite nano powder and preparation method thereof, application Download PDFInfo
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- CN106928994A CN106928994A CN201511008674.7A CN201511008674A CN106928994A CN 106928994 A CN106928994 A CN 106928994A CN 201511008674 A CN201511008674 A CN 201511008674A CN 106928994 A CN106928994 A CN 106928994A
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Abstract
The present invention relates to a kind of photochromic composite nano powder and preparation method thereof, application, the photochromic composite nano powder particle is core shell structure, and shell is molybdenum trioxide, and kernel is titanium dioxide, wherein described titanium dioxide is anatase titanium dioxide nano particle, is shaped as graininess.The preparation of the powder employs simple and quick one step hydro thermal method, will molybdenum source and titanium source mixing, through hydro-thermal reaction obtain molybdenum oxide cladding Titanium dioxide nanoparticle；The photochromic composite nano powder can apply to energy-conservation pad pasting, energy-saving glass or energy-saving wall field.The photochromic composite nano powder of foregoing invention, has been capable of achieving the small-sized of molybdenum oxide, with excellent dispersiveness, stability, with efficient photochromic properties.
Description
Technical field
The present invention relates to field of inorganic nano material, more particularly to a kind of photochromic composite nano powder and its preparation side
Method.
Background technology
According to estimates, building energy consumption typically occupies 1/3rd of social total energy consumption.Meanwhile, energy for building is to world greenhouse
The contribution rate of gas discharge is up to 25%, so energy-saving and emission-reduction are the most important things of world's energy-conservation, and energy-saving and emission-reduction must be examined preferentially
Consider building energy conservation.Data display building energy consumption 50% is carried out by windowpane, and windowpane is building and ambient light heat exchange
Main thoroughfare, therefore building energy conservation is realized mainly by the Intelligent energy-saving window of development of new, reducing energy consumption reduces greenhouse gases
Discharge, is finally reached the purpose of energy-conserving and environment-protective.
The Energy Saving Windows or energy-conservation pad pasting (abbreviation Energy Saving Windows) for occurring at present are roughly divided into two classes, and a class is that optical property is consolidated
Fixed Energy Saving Windows, are representative with low-launch-rate (Low-E) glass in the market, and its advantage is cheap, thermal insulation
Can be superior, it is most widely used, but have the disadvantage can not be because seasonal variations realize summer in winter real-time regulation, it is difficult to adapt to most of China
The cold summer thermally area demand.It is another kind of, it is referred to as " intelligent type energy saving glass ", various cause off-color materials are used with to various
Physical stimulation produces corresponding optical change, is applicable to thermally area of warm summer in most of winter, energy-conservation and indoor environment is more relaxed
It is suitable.Intelligent power saving glass is divided into electrochromism, gas-discoloration, thermochromism and photochromic four kinds.Electrochromic material needs
Applied voltage, complex structure, preparation technology requires high, causes expensive；Gas-discoloration needs to be passed through hydrogen and could realize
Bidirectional modulation；Thermochromism glass colour is short of aesthetic feeling；And the light-induced variable that can be developed using the performance of molybdenum trioxide light color
Color Energy Saving Windows, automatically adjusting for illumination transmitance, simple structure, without artificial energy are realized due to that can comply with the change of four seasons light intensity
Source, is expected to turn into one of next energy-saving glass material of low-carbon environment-friendly.
So-called photochromic material refers to that can be tied by specific chemical reaction generation when compound A is subject to the illumination of wavelength h1
The structure product B different with spectrum property and in the presence of wavelength is for the illumination of h2 or heat the reversible compound that generates
Phenomenon.Photochromic material species is various, can typically divide organic photochromic and inorganic photochromic.Wherein the most popular nothing
One of machine photochromic material is molybdenum oxide.
Preparing photochromic intelligent glass has two ways, i.e., prepare molybdenum trioxide coated glass using extensive magnetron sputtering
Physics preparation method, and molybdenum trioxide nano powder with chemical means is prepared using nanometer technology in advance, then nano-powder is led to
Cross the modes such as chemicalpiston and prepare the chemical preparation mode as pad pasting energy-saving glass.Compared with former mode, the latter is due to setting
Standby simple, generality is strong, cheap, it is easy to which large area is produced, and wide application remarkable advantage, it is easier to for market connects
Receive.
Method prepared by molybdenum oxide is a lot, and pattern is also a lot, but there is a problem of one it is common：The particle size of preparation compared with
Greatly.Particle is big to hundreds of nanometers in Chinese patent (CN103288138A, CN102603005A, CN102153142A),
Minimum is also greater than 50 nanometers.And this patent depend on titan oxide particles it is tiny the characteristics of, coat one layer of molybdenum oxide, integrally reduce
The size of particle.
Simultaneously because molybdenum trioxide semiconductor itself can the limitation with (in ultraviolet light range), material dimming scope and discoloration
Efficiency is much worse than ideal application.In order to solve this problem, unbodied molybdenum trioxide can be coated on what is matched with molybdenum trioxide
Metal oxide semiconductor, its basic reason is two kinds can form a kind of heterojunction structure with the semiconductor of matching, reduce energy
Bandwidth, expands dimming scope, it is to avoid light induced electron and hole in conjunction with improving photochromic efficiency.
The conductor oxidate matched with molybdenum oxide energy band has compared with more options, and titanium dioxide performance is protruded, and 1) main cause is
Because titanium oxide is used as photochemical catalyst, its excellent performance shows light induced electron that it produces under light conditions and hole than general
Material is more, and this has critical help to improving molybdenum trioxide photochromic efficiency；2) titanium dioxide stable performance, repeats
Property is good；3) molybdenum trioxide and coated by titanium dioxide, the new optical texture unit of configuration, it is anti-that similar designs multilayer film obtains reflection
Only effect is the same.Bigger optical effect can be obtained out using the complicated optical effect of this core shell structure.
Prepare the difficult point that above-mentioned core shell structure is also this patent.Existing certain methods cladding has synthesized titanium oxide molybdenum oxide
Composite (Sensors and Actuators B (2011) 270, J.Am.Chem.Soc. (2000) 5138).But the above method is operated
Complexity, takes, power consumption.And the compound coating of these patterns does not all study photochromic properties.
In sum, now to molybdenum oxide research shortcoming main reason is that, 1) comparing organic and inorganic light-induced variable
Under color material, more researcher has been transferred to organic photochromic material, and have ignored improves molybdenum trioxide performance with chemical means
Research.2) the simple mature technology for being combined molybdenum oxide and titanium oxide is lacked.3) lack and this cladding is applied as energy-saving film
Technology.Due to above reason, currently without one kind on photochromic performance and structure all preferably nano particle and energy-conservation
Film.
The content of the invention
The technical problems to be solved by the invention are, there is provided a kind of photochromic composite nano powder and preparation method thereof, should
Photochromic composite nano powder has efficient photochromic properties.
In the present invention, the photochromic composite nano powder is core shell structure, and shell is molybdenum trioxide, and kernel is dioxy
Change titanium.Wherein described titanium dioxide is anatase titanium dioxide nano particle, is shaped as little particle, and particle size is not
One, distribution is 4-20nm, and preferable particle size is 5-10nm, and the molybdenum trioxide is unbodied molybdenum trioxide nano
Grain, cladding thickness 2-10nm.
The invention provides a kind of photochromic composite nano powder preparation, including choose molybdenum acid solution or by other molybdenums
Hydrochlorate obtains molybdenum acid solution as molybdenum source in being dissolved in acid solution, and adds titanium source in the molybdenum acid solution, obtains precursor solution；
Alkali and reductant-oxidant are added in the precursor solution, answering for the molybdenum trioxide cladding titanium dioxide is obtained through hydro-thermal reaction
Close nano particle.
Preferably, the amount of the titanium ion in addition molybdenum acid solution is relative to its mol ratio 19 of the amount of molybdenum ion:1-1:1.
Preferably, the molybdate is ammonium molybdate, sodium molybdate.The titanium source is preferably titanium tetrachloride or titanium sulfate.
Preferably, the acid solution is identical with the acid group of the titanium source.The preferred 2-3ml/L of acid solutions.The acid solution
Preferably hydrochloric acid solution or sulfuric acid solution.The molybdenum acid solution concentration is preferably 0.0083-1.588g/ml.
It is preferred that titanium ion and the hydrionic mol ratio 6 of the acid solution:(15-20).
Preferably, the aqueous slkali is ammoniacal liquor, NaOH or potassium hydroxide, more preferably ammoniacal liquor.
Preferably, the reductant-oxidant is 35% hydrogen peroxide, and the amount of the hydrogen peroxide of addition is to be added per 1mL titanium sources relatively
0.1~1g.
The photochromic composite nano powder of the present invention is made up of molybdenum oxide cladding Titanium dioxide nanoparticle；The preparation of the powder
Employ simple and quick one step hydro thermal method, will molybdenum source and titanium source mixing, through hydro-thermal reaction obtain molybdenum oxide cladding titanium oxide receive
Rice grain；The photochromic composite nano powder can apply to energy-conservation pad pasting, energy-saving glass or energy-saving wall field.Above-mentioned hair
Bright photochromic composite nano powder, has been capable of achieving the small-sized of molybdenum oxide, with excellent dispersiveness, stability, tool
There are efficient photochromic properties.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of the molybdenum trioxide cladding titanium dioxide nano particle prepared by embodiment 1
Spectrum；
Fig. 2 is the XRD of pure zirconia titanium in the present invention；
Fig. 3 is transmission electron microscope (TEM) photo of molybdenum trioxide cladding titanium dioxide nano particle of the present invention, X-ray energy spectrogram
(EDS) and choose electron diffraction diagram；
Fig. 4 is XRD and the SEM figure of pure zirconia molybdenum in the present invention；
Fig. 5 is the photochromic properties comparison diagram of molybdenum trioxide cladding titanium dioxide nano particle of the present invention and pure phase molybdenum oxide；
Fig. 6 is the TEM comparison diagrams of different molybdenum source/titanium sources；
Fig. 7 is the light modulation efficiency chart of different molybdenum source/titanium sources.
Specific embodiment
In the present invention, the photochromic composite nano powder is made up of molybdenum oxide cladding Titanium dioxide nanoparticle.It is described
Molybdenum oxide cladding Titanium dioxide nanoparticle is core shell structure, with anatase titanium dioxide nano particle as core, with unbodied three
Molybdenum oxide nanoparticles are shell.The titania nanoparticles are spherical, and described molybdenum trioxide nano particle uniformly coats institute
Titania nanoparticles are stated, the coated particle size distribution that different ratio is prepared is uneven, and scope is 4-20nm.It is described
The cladding thickness 2-10nm of molybdenum trioxide.Efficiency is dimmed according to it, it is preferable that the coated particle particle diameter is 5-10nm.
The photochromic composite nano powder of the present invention is made up of molybdenum oxide cladding Titanium dioxide nanoparticle；The preparation of the powder
Simple and quick one step hydro thermal method is employed, specially adds acid solution to prepare precursor solution molybdenum source and titanium source, then added again
Enter alkali and reductant-oxidant, the nano particle that the molybdenum oxide coats titanium oxide is obtained through hydro-thermal reaction.The molybdenum salt can be molybdenum
Sour ammonium, sodium molybdate.The titanium source can be titanium tetrachloride or titanium sulfate.
Preparation on precursor solution, specifically can be dissolved in molybdates such as ammonium molybdate or sodium molybdates concentration and be more than
Concentration is obtained in 2mol/L acid solutions for 0.0083~1.588g/ml molybdenum acid solutions, at room temperature, stirring gained molybdenum acid solution is simultaneously
Titanium source of the addition with acid group identical with acid solution, such as titanium tetrachloride or titanium sulfate, obtain precursor solution.Can also be direct
Choose concentration be 0.0083~1.588g/ml molybdenum acid solutions as molybdenum source, at room temperature, stirring gained molybdenum acid solution simultaneously adds tool
There is a titanium source of acid group identical with acid solution, such as titanium tetrachloride or titanium sulfate, obtain precursor solution.On the dense of acid solution
Degree, is preferably greater than 2mol/L simultaneously less than 3mol/L, so sufficiently dissolves titanium source, reduces its volatilization.
Aqueous slkali is added in the precursor solution, through alkalization, molybdenum titanium colloidal sol is obtained, now colloidal sol is in neutral or alkali
Property.Then reductant-oxidant is added in the molybdenum titanium colloidal sol, is put into reactor, then dispersion liquid is obtained by hydro-thermal reaction.Plus
The aqueous slkali for entering can be ammoniacal liquor, NaOH or potassium hydroxide, preferably ammoniacal liquor.In order to neutralize acid solution generation metatitanic acid structure,
It is unlikely to neutralize the generation of too fast influence clad structure again, the mass fraction of the aqueous slkali of addition is preferably 28%.And the alkali for adding
The amount of solution is monitored in terms of PH, untill neutral or meta-alkalescence is dissolved as, metatitanic acid is complexed into reach whole titanium sources, is adsorbed
Molybdenum source.Reductant-oxidant selection is hydrogen peroxide that concentration is 35%, the amount of addition be add 0.1 per 1mL titanium sources relatively~
1g, the hydroxyl in being precipitated for desorption reaction.The reaction temperature of hydro-thermal reaction should be controlled at 150 degrees Celsius, during the reaction time
Between 6 hours.The dispersion liquid is cooled to room temperature, filtering, deionized water washing and absolute ethanol washing is sequentially passed through, dried
Molybdenum oxide cladding Titanium dioxide nanoparticle is obtained afterwards.Drying temperature is 70-90 degrees Celsius.
As an example, being further specifically described photochromic composite nano powder preparation of the invention, it is included such as
Lower step：1) molybdenum source is dissolved in acid solution, obtains molybdenum acid solution, the molybdenum acid solution of stirring；2) at room temperature, stir
Mix the molybdenum acid solution and add titanium source, obtain precursor solution；3) aqueous slkali is added in the precursor solution, through alkali
Change, obtain molybdenum titanium colloidal sol；4) reductant-oxidant is added in the molybdenum titanium colloidal sol, dispersion liquid is obtained by hydro-thermal reaction；5)
The dispersion liquid is cooled to room temperature, by filtering, washing, molybdenum oxide cladding Titanium dioxide nanoparticle is obtained.Alternatively, institute
Molybdenum source is stated for ammonium molybdate, sodium molybdate or molybdic acid, the titanium source is titanium tetrachloride or titanium sulfate, the acid group of the acid solution with it is described
The acid group of titanium source is identical；The acid solutions are more than 2ml/L, and the molybdenum acid solution concentration is 0.0083-1.588g/ml.It is preferred that
Ground, the acid solution is hydrochloric acid or sulfuric acid, and the titanium source is titanium tetrachloride, and the titanium source is 6 with the volume ratio of the acid solution:
(15-20).Alternatively, the aqueous slkali is ammoniacal liquor, NaOH or potassium hydroxide, it is preferable that the aqueous slkali is ammonia
Water, the colloidal sol is in neutral or alkalescence.Alternatively, the reductant-oxidant is hydrogen peroxide, it is preferable that the hydrogen peroxide concentration
It is 35%, the amount of addition is to add 0.1~1g per 1mL titanium sources relatively.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground description, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
Embodiment in invention, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
Embodiment 1
This embodiment describes a kind of preparation method of molybdenum trioxide cladding titanium dioxide nano particle, including：
S1：Soluble molybdenum acid solution is obtained in the hydrochloric acid solution that 0.1576g ammonium paramolybdates are added 10ml, 2mol/L；
S2：Soluble molybdenum acid solution adds 1ml titanium tetrachlorides under stirring at room temperature, obtains precursor solution；
S3：Appropriate ammoniacal liquor is added dropwise in the precursor solution makes solution PH>7, through alkalization, obtain molybdenum titanium colloidal sol；
S4：In the molybdenum titanium colloidal sol, 0.5g hydrogen peroxide is added per 1mL titanium sources relatively, be put into reactor, in 150 DEG C of temperature
Lower reaction 6 hours, reaction terminates to obtain dispersion liquid；
S5：Dispersion liquid is cooled to room temperature, is washed through deionized water successively, absolute ethanol washing, through drying, obtains molybdenum trioxide bag
Cover titanium dioxide (TiO2-MoO3Cladding) core-shell structure nanopowder body, it is named as TM-10.
Embodiment 2
The preparation of pure zirconia titanium：Refering to the preparation process of the molybdenum trioxide cladding titanium dioxide nano particle described in embodiment 1,
Step S1 hydrochloric acid solutions are added without ammonium paramolybdate in embodiment 1, and remaining step is with embodiment 1, you can prepare pure zirconia
Titanium.
Fig. 1 is X-ray diffraction (XRD) figure of the molybdenum trioxide cladding titanium dioxide nano particle prepared by embodiment 1
Spectrum, Fig. 2 is the XRD of the pure zirconia titanium prepared by embodiment 2.Comparison diagram 1 and Fig. 2 are visible, prepared by embodiment 1
The characteristic peak of molybdenum trioxide cladding titanium dioxide nano particle is TiO2, do not have other impurities peak in Fig. 1 and occur, illustrate three
TiO in molybdenum oxide cladding titanium dioxide nano particle2It is crystalline state, MoO3It is amorphous state.
Refer to Fig. 3：Fig. 3 is the transmission electron microscope of the molybdenum trioxide cladding titanium dioxide nano particle prepared by embodiment 1
(TEM) photo, X-ray energy spectrogram (EDS) and selection electron diffraction diagram.TEM schemes and the combination of EDS figures can be seen
Go out, be crystalline particulate state TiO in the middle of the sample prepared by embodiment 12, around it is coated with amorphous state MoO3, in addition,
Choosing electronic diffraction photo has diffraction ring, further illustrates the TiO of crystallization2It is polycrystalline state, thus, prepared by embodiment 1
Molybdenum oxide cladding titanium oxide nano particle in TiO2It is polycrystalline state, MoO3It is amorphous state.
Embodiment 3
In order to study TiO2-MoO3Improvement of the cladding nanosphere to photochromic properties, prepares comparative sample.On pure phase molybdenum oxide
Prepare：The preparation process of the molybdenum trioxide cladding titanium dioxide nano particle described in embodiment 1 is see, in embodiment 1
Cast out step S2, remaining step is with embodiment 1, you can prepare pure zirconia titanium.
Fig. 4 is XRD and the SEM figure of pure zirconia molybdenum in the present invention, and the pure phase molybdenum oxide prepared by the present embodiment is oxygen
Change molybdenum nanometer rods.XRD in analysis chart 4, it is known that oxidation molybdenum structure is α-MoO3。
Embodiment 4
The pure phase molybdenum oxide powder point with prepared by embodiment 3 that molybdenum trioxide prepared by embodiment 1 is titanium dioxide nano powder coated
Do not evenly spread in ethanol solution, obtain 0.3wt% sample solutions and test their photochromic properties.
Fig. 5 is referred to, Fig. 5 is the light-induced variable of molybdenum trioxide cladding titanium dioxide nano particle of the present invention and pure phase molybdenum oxide
Color performance comparison figure.As seen from Figure 5, the molybdenum trioxide cladding titanium dioxide nano particle prepared by embodiment 1 is photochromic
Efficiency is 20 times of the photochromic efficiency of prepared pure phase molybdenum oxide in embodiment 3, it can be seen that, molybdenum trioxide cladding
There is titania nanoparticles high light to cause discoloration.
Embodiment 5,6,7 and 8 is unitary variant comparative example, and with reference to the preparation process of embodiment 1, unique change is molybdenum
The mol ratio of ion and titanium ion.The mol ratio of molybdenum ion and titanium ion is once corresponded to：5:95,15:85,25:75,
50:50.And TM-5 is named as according to this, its dependent variable of TM-15, TM-25, TM-50. is no longer detailed in the patent to be explained, but
The interest field of the present invention can not be limited with this.
Fig. 6 is referred to, Fig. 6 is the TEM comparison diagrams of different molybdenum source/titanium sources.With the increase of molybdenum source, particle mean size is got over
Come smaller, particle dispersion is become better and better, and particle distribution range is less and less.TM-5 is distributed as 4-20nm, TM-25
Narrow down to 5-8nm. molybdenum sources it is excessive when, particle is grown up again, and different types of particle occurs.Therefore TM-25 is minimum chi
Very little cladding.
Fig. 7 is referred to, Fig. 7 is the light modulation efficiency chart of different molybdenum source/titanium sources, and solution prepares exemplary embodiment 4, sample solution
Concentration is prepared into 0.05wt%.It is therefrom visible, the light modulation efficiency highest of optimum size TM-25.This previous claims exactly
The reason for particle size optimizes in book.
Above disclosed is only a kind of preferred embodiment of the invention, can not limit the right of the present invention with this certainly
Scope, one of ordinary skill in the art will appreciate that all or part of flow of above-described embodiment is realized, and will according to right of the present invention
Made equivalent variations are sought, the covered scope of invention is still fallen within.
Claims (8)
1. a kind of photochromic composite nano powder, it is characterized in that, the photochromic composite nano powder particle is core shell structure, and shell is molybdenum trioxide, and kernel is titanium dioxide, wherein described titanium dioxide is anatase titanium dioxide nano particle, graininess is shaped as, clad structure particle diameter of nanometer powder is distributed as 4-20nm, and the molybdenum trioxide is unbodied molybdenum trioxide nano particle, cladding thickness distribution is uneven, and distribution is 2-10nm.
2. it is a kind of as claimed in claim 1 photochromic composite nano powder preparation method, it is characterised in that including：Choose molybdenum acid solution or be dissolved in other molybdates and molybdenum acid solution as molybdenum source is obtained in acid solution, and titanium source is added in the molybdenum acid solution, obtain precursor solution；Alkali and reductant-oxidant are added in the precursor solution, the composite nanometer particle of the molybdenum trioxide cladding titanium dioxide is obtained through hydro-thermal reaction.
3. photochromic composite nano powder preparation according to claim 2, it is characterised in that the molybdenum salt is ammonium molybdate, sodium molybdate, the titanium source is titanium tetrachloride or titanium sulfate.
4. the photochromic composite nano powder preparation according to Claims 2 or 3, it is characterised in that the acid solutions 2-3ml/L.
5., according to one of any described photochromic composite nano powder preparations of claim 2-4, it is characterised in that the molybdenum acid solution concentration is 0.0083-1.588g/ml, titanium ion and the mol ratio of molybdenum ion are 19 in reaction solution:1-1:1.
6. according to one of any described photochromic composite nano powder preparations of claim 2-5, it is characterised in that titanium ion is 6 with the hydrionic mol ratio of the acid solution:（15-20）.
7. according to one of any described photochromic composite nano powder preparations of claim 2-6, it is characterised in that the aqueous slkali is the alkaline solutions such as ammoniacal liquor, NaOH, potassium hydroxide.
8., according to one of any described photochromic composite nano powder preparations of claim 2-7, it is characterised in that the reductant-oxidant is the hydrogen peroxide of concentration 35%, the amount of addition is to add 0.1~1g hydrogen peroxide per 1mL titanium sources relatively.
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| CN107722027A (en) * | 2017-11-10 | 2018-02-23 | 江苏视客新材料股份有限公司 | The preparation method of spiro-pyrans class photochromic nano complex microsphere |
| CN107722027B (en) * | 2017-11-10 | 2020-04-14 | 江苏视科新材料股份有限公司 | Preparation method of spiropyran photochromic nano composite microspheres |
| CN107722028B (en) * | 2017-11-10 | 2020-04-21 | 江苏视科新材料股份有限公司 | Photochromic optical material |
| CN107722028A (en) * | 2017-11-10 | 2018-02-23 | 江苏视客新材料股份有限公司 | A kind of photochromic optical material |
| CN111356734A (en) * | 2017-12-29 | 2020-06-30 | 依视路国际公司 | Method for manufacturing a light-absorbing polymer matrix |
| JP2021527028A (en) * | 2018-11-19 | 2021-10-11 | チョーチアン チンイー ニュー マテリアル テクノロジー カンパニー リミテッドＺｈｅｊｉａｎｇ Ｊｉｎｇｙｉ Ｎｅｗ Ｍａｔｅｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．Ｌｔｄ | Inorganic-organic hybrid core shell type nanorod and light bulb with the nanorod |
| JP7026847B2 (en) | 2018-11-19 | 2022-02-28 | チョーチアン チンイー ニュー マテリアル テクノロジー カンパニー リミテッド | Inorganic-organic hybrid core shell type nanorods and light bulbs with the nanorods |
| US11248168B2 (en) | 2018-11-19 | 2022-02-15 | Zhejiang Jingyi New Material Technology Co. Ltd | Inorganic-organic hybrid core-shell nanorod and light valve having the nanorod |
| CN109592909A (en) * | 2019-01-31 | 2019-04-09 | 山西普思盈创科技有限公司 | A kind of preparation method of antiultraviolet energy-saving glass |
| CN112694120A (en) * | 2019-10-23 | 2021-04-23 | 中国科学院宁波工业技术研究院慈溪生物医学工程研究所 | Semiconductor nano particle with composite structure, preparation method and application thereof |
| CN111944512A (en) * | 2020-08-17 | 2020-11-17 | 山东大学 | Ultra-small inorganic nano heterojunction photochromic material, erasable and rewritable medium prepared by adopting material and preparation method of erasable and rewritable medium |
| CN111944512B (en) * | 2020-08-17 | 2021-07-16 | 山东大学 | Ultra-small inorganic nano heterojunction photochromic material, erasable and rewritable medium prepared by adopting material and preparation method of erasable and rewritable medium |
| CN113337270A (en) * | 2021-04-13 | 2021-09-03 | 中国石油大学(北京) | Inorganic photochromic powder and preparation method and application thereof |
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