CN109422244A - Can ultraviolet blocking-up photochromic nano material and its preparation method and application - Google Patents

Can ultraviolet blocking-up photochromic nano material and its preparation method and application Download PDF

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CN109422244A
CN109422244A CN201710733741.4A CN201710733741A CN109422244A CN 109422244 A CN109422244 A CN 109422244A CN 201710733741 A CN201710733741 A CN 201710733741A CN 109422244 A CN109422244 A CN 109422244A
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solution
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nano material
photochromic
primitive
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CN109422244B (en
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吴长征
杨波
谢毅
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University of Science and Technology of China USTC
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Abstract

It is M that the present invention, which provides general formula,aObXcCan ultraviolet blocking-up photochromic nano material and its preparation method and application, wherein M, O and X and a, b and c are as defined herein.The nano material can be prepared by the following method: by containing M cation source compounds, polyalcohol, surfactant and the first solvent mixture heat obtain the first solution of heat under stiring；By containing X anion source compound and the second solvent be mixed to get the second solution；Second solution is injected into the first solution to react, obtains reaction mixture；The reaction mixture is post-processed.Nano material of the present invention can block 80% or more ultraviolet light, especially can be changed to transparent dead color in strong illumination, reduce transmitance；It can restore colorless and transparent state again in no strong illumination.In addition, the present invention has the characteristics that process flow is simple, low in cost, yield is big, is suitable for industrial production.

Description

Can ultraviolet blocking-up photochromic nano material and its preparation method and application
Technical field
The present invention relates to photochromic material fields, and in particular to can ultraviolet blocking-up photochromic nano material and its Preparation method and purposes.
Background technique
It is photochromic to refer to that under the light radiation of certain wavelength and intensity certain change occurs for certain compound-materials Reaction is learned, causes compound structure to change, compound colors is caused to change, remove illumination or again through another wavelength and intensity Light irradiation after, color is restored or occurs new variation.From the fifties in last century, Hirshberg et al. is reported about light Mutagens color was applied to after a possibility that optical recording stores, and the performance of various novel photochromic materials and its application are The research of system is widely used in building window glass, light-sensitive sunglasses eyeglass, vehicles glass pane, information storage material, decoration The fields such as material, photosensitive material.
The research of photochromic material focuses primarily upon two major classes, i.e. organic photochromic material and inorganic photochromic material Material.But organic photochromic material there are thermal stability it is poor, easy to aging, weatherability is weak the problems such as, limit its and practical answer With.Inorganic photochromic material is better than the good characteristic of organic photochromic material with its many and is concerned.So far, The research of inorganic photochromic material focuses primarily upon transition elements oxide of mutually (such as MoO3、TiO2、Nb2O5、WO3、Ta2Os、BeO Deng), metal halide (such as CuCl2、CdCl2, AgX etc.), polyoxometallate and rare earth compounding etc..Although some materials body System's relative maturity, but there is the problems such as such as higher cost of raw material and complicated processing technology, it is big to limit it Scale commercial application.Meanwhile existing many photochromic materials can only reduce the transmitance of light, and cannot block in sunlight To the maximum ultraviolet light of body effect.
CN1796321A discloses a kind of material Nd that can be used as glass additive2O30.05-1.00mol%, and added with this Agent is added to prepare photochromic glass.Document (Physical Chemistry Chemical Physics, 2002 (4): 1637- 1639.) it reports and prepares WO using spin-coating method3Film, and in WO3The surface of film deposits nanometer using the method being evaporated in vacuo Au particle prepares Au/WO3Composite photochromic film material.Document (Nature Materials, 2003 (2): 29-31.) report Road is by Ag particle deposition in TiO2Photochromic material is prepared on film.However, these technical matters are using expensive The expensive raw material such as Ag, Au, Nb are unable to satisfy requirement of the industrial production to production cost.
In addition, document (artificial lens journal, 2014,43 (12), 3113-3117.) reports photochromic WO3-TiO2- The preparation method of ZnO colloidal sol need to prepare WO respectively first3、TiO2With ZnO colloidal sol, three is then mixed in a certain ratio system ?；It needing with 500W Hg lamp irradiation ability changeable colour, while restoring the colourless time after no light to need 6h, discoloration efficiency is lower, And above-mentioned technical operation is cumbersome.Equally, document (Technical Physics Letters, 2009,35 (10): 909- 911.) it reports and utilizes WO on CuCl film3Vapor deposition is prepared for CuCl-WO3The composite film material of double-layer structure, benefit Use WO3Can the molecule of hydrogen atoms such as photodissociation hydrone property, release hydrogen atom, behind the surface hydrogen atoms contact CuCl, triggering Photochromic characteristic is presented in CuCl, and the reaction mechanism process is complicated, and discoloration efficiency is lower, and technology of preparing is more harsh.
It in summary it can be seen, that there are the costs of raw material is higher for existing embedded photoluminescent material, technology is complicated etc. can not The requirement for meeting industrial hinders development of the photochromic material in business application.Therefore, it is badly in need of exploitation tool Have that technology is simple, the cost of raw material is cheap, better heat stability, weatherability are relatively strong at the same can with ultraviolet blocking-up can The inorganic photochromic material of large-scale commercial applications application.
Summary of the invention
In order to solve the above problem, the present invention provides following technical schemes:
On the one hand, it is M that the present invention, which provides a kind of general formula,aObXcCan ultraviolet blocking-up photochromic nano material, Middle M indicate selected from one of tin, indium, antimony and bismuth it is a variety of or its with selected from one of titanium, barium, nickel, vanadium, zinc and copper or A variety of combinations；O indicates oxygen atom；X indicates to be selected from and the formula MaObXcIn (MaOb) primitive is capable of forming compound One of tungstate radicle primitive, molybdate primitive, vanadic acid foundation member, fluorine, chlorine, bromine and iodine or it is a variety of or its with selected from sulphur, carbon, One of phosphorus and boron or a variety of combinations, and in the formula MaObXcIn, each molar ratio a:b:c for forming primitive is (1 ~50): (1~50): 1.
In a preferred embodiment, in the formula MaObXcIn, each molar ratio a:b:c for forming primitive be (1~ 20): (1~30): 1.
It include one of quantum dot, nano wire, nanometer sheet, nanobelt and nano particle in the pattern of the nano material Or it is a variety of.
On the other hand, it is M that the present invention, which provides one kind and is used to prepare general formula,aObXcCan ultraviolet blocking-up it is photochromic The method of nano material, wherein M indicate selected from one of tin, indium, antimony and bismuth it is a variety of or its with selected from titanium, barium, nickel, vanadium, One of zinc and copper or a variety of combinations；O indicates oxygen atom；X indicates to be selected from and the formula MaObXcIn (MaOb) primitive It is capable of forming one of tungstate radicle primitive, molybdate primitive, vanadic acid foundation member, fluorine, chlorine, bromine and iodine of compound or a variety of, Or its with selected from one of sulphur, carbon, phosphorus and boron or a variety of combinations, and in the formula MaObXcIn, each composition primitive Molar ratio a:b:c is (1~50): (1~50): 1, it the described method comprises the following steps:
A) by containing M cation source compounds, polyalcohol, surfactant and the first solvent mixture add under stiring Heat obtains the first solution of heat；
B the anion source compound containing X is mixed with the second solvent), obtains the second solution；
C) the first solution that second solution is injected the heat obtains reaction mixture to react；
D) reaction mixture cool down, separate, wash and/or dry, obtain the photochromic nano material Material.
In a preferred embodiment, the polyalcohol is selected from oleyl alcohol, glycerine, pentaerythrite, xylitol, mannitol With one of sorbierite or a variety of；
In a preferred embodiment, the surfactant is selected from neopelex, cetyl front three Base ammonium bromide, disodium ethylene diamine tetraacetate, polyvinylpyrrolidone, lauroyl glutamate, sodium stearyl sulfate and fat One of alcohol polyethenoxy ether sodium sulfate is a variety of；
In a preferred embodiment, first solvent and second solvent are independently from each other C1-6Alkanol, One of deionized water, oleyl amine, hexamethylene and oleic acid are a variety of.
In a preferred embodiment, the mass ratio of the polyalcohol and the cation source compounds containing M is (1 ~1500): 15；
In a preferred embodiment, the mass ratio of the surfactant and the cation source compounds containing M For (1~2000): 20；
In a preferred embodiment, the mass ratio of first solvent and the cation source compounds containing M is (1~2000): 10；
In a preferred embodiment, the mass ratio of second solvent and the X yin source compound be (1~ 1500): 10.
In a preferred embodiment, the temperature of the first solution of the heat is 30~300 DEG C；
In a preferred embodiment, second solution injects the time of the first solution of the heat for 1s~12h.
In a preferred embodiment, described to be separated into centrifuge separation；
In a preferred embodiment, the drying be freeze-drying or heat drying, dry temperature be -50~ 150 DEG C and time are 1~72h.
On the other hand, the light-induced variable that the present invention provides above-mentioned photochromic nano material or prepared according to the above method Color nano material is used for building window glass, light-sensitive sunglasses eyeglass, vehicles glass pane, information storage material, ornament materials Or the purposes of photosensitive material.
The present invention provides can be with the photochromic nano material and its dopant material of the low cost of ultraviolet blocking-up.This hair Bright formula MaObXcNano material and its dopant material made of intelligence glass pane can block 80% or more ultraviolet light, especially It can be changed to transparent dead color in strong illumination, reduce transmitance；It can restore colourless again in dim light or without strong illumination when Bright state.In addition, photochromic nano material of the invention applies also for light-sensitive sunglasses eyeglass, vehicles glass pane, information The purposes of storage material, ornament materials, photosensitive material etc..
Detailed description of the invention
Fig. 1 is the Bi prepared according to the embodiment of the present invention 15O7The X ray diffracting spectrum of I nano material；
Fig. 2 is the Bi prepared according to the embodiment of the present invention 15O7The transmission electron microscope photo of I nano material；
Fig. 3 is the Bi prepared according to the embodiment of the present invention 15O7I nano material is after reset condition, light color and unglazed The UV-visible-near infrared absorption of recovery state after irradiation；
Light transmittance curve when Fig. 4 is the photochromic glass different conditions prepared using embodiment according to the present invention 10 Figure；
Fig. 5 is the photochromic glass that is prepared using embodiment according to the present invention 10 in sensitive area and non-sensitive area boundary The optical microscope photograph at place.
Specific embodiment
It is M the present invention provides a kind of general formulaaObXcCan ultraviolet blocking-up photochromic nano material, wherein M indicate Selected from one of tin, indium, antimony and bismuth it is a variety of or its with selected from one of titanium, barium, nickel, vanadium, zinc and copper or a variety of groups It closes；O indicates oxygen atom；X indicates to be selected from and the formula MaObXcIn (MaOb) primitive is capable of forming the wolframic acid foundation of compound One of member, molybdate primitive, vanadic acid foundation member, fluorine, chlorine, bromine and iodine or it is a variety of or its in sulphur, carbon, phosphorus and boron One or more combinations, and in the formula MaObXcIn, each molar ratio a:b:c for forming primitive is (1~50): (1 ~50): 1.
Being used to prepare general formula the present invention also provides one kind is MaObXcCan ultraviolet blocking-up photochromic nano material Method, wherein M indicate selected from one of tin, indium, antimony and bismuth it is a variety of or its in titanium, barium, nickel, vanadium, zinc and copper One or more combinations；O indicates oxygen atom；X indicates to be selected from and the formula MaObXcIn (MaOb) primitive is capable of forming One of tungstate radicle primitive, molybdate primitive, vanadic acid foundation member, fluorine, chlorine, bromine and iodine of compound or a variety of or itself and choosing One of bin cure, carbon, phosphorus and boron or a variety of combinations, and in the formula MaObXcIn, each molar ratio a for forming primitive: B:c is (1~50): (1~50): 1, it the described method comprises the following steps:
A) by containing M cation source compounds, polyalcohol, surfactant and the first solvent mixture add under stiring Heat obtains the first solution of heat；
B the anion source compound containing X is mixed with the second solvent), obtains the second solution；
C) the first solution that second solution is injected the heat obtains reaction mixture to react；
D) reaction mixture cool down, separate, wash and/or dry, obtain the photochromic nano Material.
As used in this article, statement " M indicate selected from one of tin, indium, antimony and bismuth it is a variety of or its with selected from titanium, One of barium, nickel, vanadium, zinc and copper or a variety of combinations " means that M can be only one of tin, indium, antimony and bismuth or a variety of, Simultaneously M may be one of tin, indium, antimony and bismuth or it is a variety of be selected from one of titanium, barium, nickel, vanadium, zinc and copper or a variety of Cationic source combination.In the case where M is that the cationic source combines, mole coefficient a is to own in cationic source combination The sum of molal quantity of atom.
As used in this article, " X indicates to be selected from and the formula M for statementaObXcIn (MaOb) primitive is capable of forming chemical combination One of tungstate radicle primitive, molybdate primitive, vanadic acid foundation member, fluorine, chlorine, bromine and iodine of object or it is a variety of or its with selected from sulphur, One of carbon, phosphorus and boron or a variety of combinations " mean X can be only tungstate radicle primitive, molybdate primitive, vanadic acid foundation member, One of fluorine, chlorine, bromine and iodine are a variety of, at the same X may be tungstate radicle primitive, molybdate primitive, vanadic acid foundation member, fluorine, One of chlorine, bromine and iodine a variety of are combined with selected from one of sulphur, carbon, phosphorus and boron or a variety of anion sources.Here, Shen It asks someone it is noted that these primitives are separate single in the case where X is tungstate radicle primitive, molybdate primitive, vanadic acid foundation member Member or atomic group, and the metallic atom and O atom for including in these primitives all belong to the X in general formula, and cannot return respectively Belong to the formula MaObXcIn M and O.In the case where X is that the anion source combines, mole coefficient c is the anion source The sum of the molal quantity of all primitives in combination.
The cation source compounds containing M are preferably stannide, bismuthide, antimonide and indium compound, more preferably on State the trivalent compound, 4 valence compounds or 5 valence compounds of metal, the soluble trivalent compound of more preferably above-mentioned metal, 4 Valence compound or 5 valence compounds, specifically can be, for example, tin/bismuth/antimony/indium chloride, tin/bismuth/antimony/indium acetate, tin/bismuth/ Antimony/indium nitrate, tin/bismuth/antimony/indium citrate etc..
The polyalcohol is not particularly limited in the present invention, with conventional polyol well known to those skilled in the art, Those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement, the present invention The polyalcohol is preferably pentaerythrite, neopentyl glycol, cinnamyl alcohol, trimethylolethane, glycerine, xylitol, oleyl alcohol, sweet dew One of pure and mild sorbierite is a variety of, more preferably oleyl alcohol, glycerine, pentaerythrite, xylitol, mannitol and sorbierite One or more, most preferably oleyl alcohol, glycerine, xylitol and mannitol is one or more.
Surfactant of the present invention is not particularly limited, and is with conventional surfactants well known to those skilled in the art Can, those skilled in the art can select and adjust, this hair according to practical condition, raw material condition and product requirement The bright surfactant is preferably lignosulfonates, neopelex, cetyl trimethylammonium bromide, weight alkane Base benzene sulfonate, alkylsulfonate, disodium ethylene diamine tetraacetate, polyvinylpyrrolidone, lauroyl glutamate, octadecyl Sodium sulphate and sodium sulfate of polyethenoxy ether of fatty alcohol, more preferably neopelex, cetyl trimethylammonium bromide, Disodium ethylene diamine tetraacetate, polyvinylpyrrolidone, lauroyl glutamate, sodium stearyl sulfate and aliphatic alcohol polyethenoxy One or more, most preferably cetyl trimethylammonium bromide, disodium ethylene diamine tetraacetate, the polyvinyl pyrrole of ether sodium sulfate Alkanone and neopelex it is one or more.
The additional amount of Surfactant of the present invention is not particularly limited, with surface-active well known to those skilled in the art The amount of being routinely added to of agent, those skilled in the art can according to practical condition, raw material condition and product requirement into Row selection and adjustment.The mass ratio of the surfactant and the M cation source compounds is preferably (1~2000): 20, more Preferably (1~1000): 20, more preferably (1~500): 20, most preferably (1~150): 20.
First and second organic solvent can be independently selected from alcohols, pentane, deionized water, acetone, oleyl amine, ten One of eight alkene, hexamethylene and oleic acid are a variety of, more preferably alcohols, deionized water, oleyl amine, oleic acid, hexamethylene and 18 One of alkene is a variety of, most preferably one of alcohols, deionized water, oleyl amine, oleic acid and octadecylene or a variety of.
The mass ratio of first solvent and the M cation source compounds is preferably (1~2000): 10, more preferably (1~1800): 10, most preferably (1~1200): 10；
The yin source compound preferably includes the tungstates, molybdate or potassium vanadate of sodium, potassium and ammonium；Chlorination tricresyl phosphate Sodium；Vanadium chloride；Sodium, potassium, manganese, barium, copper, magnesium and ammonium one of halide such as potassium fluoride, potassium chloride etc. or a variety of, more preferably For potassium tungstate, potassium molybdate, potassium vanadate, sodium tungstate, sodium molybdate, sodium vanadate, ammonium tungstate, ammonium molybdate, ammonium vanadate, chlorination tricresyl phosphate Sodium, vanadium chloride, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, ammonium fluoride, chlorination One of ammonium, ammonium bromide and ammonium iodide are a variety of, most preferably potassium tungstate, potassium molybdate, potassium vanadate, sodium tungstate, sodium molybdate, vanadium Sour sodium, sodium tungstate, sodium molybdate, ammonium vanadate, Efficacious Disinfeitant, vanadium chloride, potassium chloride, potassium bromide, potassium iodide, sodium chloride, bromine Change one of sodium, sodium iodide, ammonium chloride, ammonium bromide and ammonium iodide or a variety of.
The mass ratio of second solvent and the negative source compound is preferably (1~1500): 10, more preferably (1~ 1300): 10, most preferably (1~1000): 10.
For the progress for guaranteeing reaction, the heating temperature of first solution is preferably 30~500 DEG C, more preferably 30~ 300 DEG C, most preferably 80~200 DEG C.
The time of first solution of the second solution injection heat is preferably 1s~12h, more preferably 1s~6h, most preferably For 1s~2h.The time of the cooling is preferably 1~180min, more preferably 1~60min, most preferably 1~30min.
The temperature of the cooling is preferably -50~50 DEG C, more preferably -20~20 DEG C, most preferably -10~10 DEG C.
Dry temperature is not particularly limited in the present invention, with the temperature of drying well known to those skilled in the art, Those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement.It is described dry Dry for example can be freeze-drying or heat drying, and dry temperature is preferably -50~150 DEG C, more preferably -50~ 120 DEG C, most preferably -50~60 DEG C.
The dry time is not particularly limited in the present invention, is with the conventional drying time well known to those skilled in the art Can, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement.It is described The dry time is preferably 1~72h, more preferably 1~60h, most preferably 8~for 24 hours.
In the present invention, formula MaObXcMiddle each element ratio is preferably (1~20) a:b:c=: (1~30): 1.
Above-mentioned photochromic nano material of the invention can be used for building window glass, light-sensitive sunglasses eyeglass, traffic work Have the fields such as glass pane, information storage material, ornament materials, photosensitive material.
Embodiment
In order to further illustrate the present invention, with reference to embodiments to a kind of inorganic photochromic material provided by the invention And preparation method thereof be described in detail, but it is to be understood that these embodiments are under the premise of the technical scheme of the present invention Implemented, the detailed implementation method and specific operation process are given, only for further illustrate feature of the invention and Advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.Meanwhile In the case where no in addition explanation, various source chemicals involved in present specification and equipment are purchased from market simultaneously Directly use.
Embodiment 1:Bi5O7The preparation of I nano material
Weighing the addition of 0.5g bismuth nitrate and filling the volume of 30mL deionized water is to use magnetic stirring apparatus in the three-necked bottle of 50mL Stirring 5 minutes；It weighs 0.6g mannitol and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 100 DEG C；Weigh 1g polyethylene pyrrole Lip river Alkanone is added to above-mentioned mixed liquor, continues heating stirring 30 minutes, until transparence is presented in solution, obtains the first solution；
Weighing the addition of 0.1g sodium iodide and filling the volume of 10mL deionized water is in the beaker of 25mL, with equipped with electric heating cover Magnetic stirrer 15 minutes, until solution present transparence, obtain the second solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 100s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and deionized water circular centrifugal after the reaction was completed, (supercentrifuge is purchased from middle section Good Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the constant temperature by sample at 60 DEG C is done It is dried in dry case.
Obtained sample is examined using X-ray diffractometer (instrument model: Philips X ' Pert PRO SUPER) It surveys, obtains the X ray diffracting spectrum of Fig. 1, determine that the sample is Bi5O7I.As can be seen from Figure 1: prepared by the present embodiment 1 Bi5O7I nano material purity is higher, and no other impurities diffraction maximum occurs.
Obtained sample is detected using transmission electron microscope (instrument model: JEM-2100F), obtains Fig. 2's Transmission electron microscope photo.As can be seen from Figure 2: Bi prepared by the present embodiment 15O7The pattern of I material is 10 nanometers or less Quantum dot and size uniformity；
Using deep ultraviolet-it is visible-near infrared spectrometer (model: DUV -3700) detects sample, obtain The UV-visible-near infrared absorption figure of Fig. 3.As can be seen from Figure 3: Bi prepared by the present embodiment 15O7I material, in original 80% or more ultraviolet light can be blocked under beginning state, photochromic state and recovery state；Meanwhile in photochromic state Under, it can be with blocking part visible light to reduce luminous intensity.
The preparation of embodiment 2:InOI nano material
Weighing the addition of 0.65g inidum chloride and filling the volume of 30mL deionized water is to use magnetic agitation in the three-necked bottle of 50mL Device stirs 5 minutes；It weighs 1g xylitol and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 100 DEG C；Weigh 1g ethylenediamine tetrem Acid disodium is added to above-mentioned mixed liquor, continues heating stirring 30 minutes, until transparence is presented in solution, obtains the first solution；
Weighing the addition of 0.5g sodium iodide and filling the volume of 15mL deionized water is in the beaker of 25mL, with equipped with electric heating cover Magnetic stirrer 15 minutes, until solution present transparence, obtain the second solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 150s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and deionized water circular centrifugal after the reaction was completed, (supercentrifuge is purchased from middle section Good Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the constant temperature by sample at 60 DEG C is done It is dried in dry case.
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform InOI nano particle, can block 80% or more under reset condition, photochromic state and recovery state Ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
Embodiment 3:Bi9V2O18The preparation of Cl nano material
Weighing the addition of 0.85g bismuth nitrate and filling the volume of 30mL octadecylene is to use magnetic stirring apparatus in the three-necked bottle of 50mL Stirring 5 minutes；It weighs 0.5g oleyl alcohol and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 100 DEG C；Weigh 0.5g cetyl three Methyl bromide ammonium is added to above-mentioned mixed liquor, continues heating stirring 30 minutes, until transparence is presented in solution, obtains the first solution；
Weighing the addition of 0.1g vanadium chloride and filling the volume of 5mL oleyl amine is in the beaker of 10mL, with the magnetic for being furnished with electric heating cover Power blender stirs 25 minutes, until transparence is presented in solution, obtains the second solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 60s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and deionized water circular centrifugal after the reaction was completed, (supercentrifuge is purchased from middle section Good Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the freezing by sample at -50 DEG C is done It is dry in dry case (purchased from Shanghai than bright instrument manufacturing Co., Ltd).
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform Bi9V2O18Cl nano wire can block 80% or more under reset condition, photochromic state and recovery state Ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
Embodiment 4:BiBaO2The preparation of Br nano material
Weighing the addition of 0.5g bismuth nitrate and filling the volume of 30mL deionized water is to use magnetic stirring apparatus in the three-necked bottle of 50mL Stirring 5 minutes；It weighs 1g mannitol and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 100 DEG C；Weigh the addition of 0.6g barium acetate Above-mentioned mixed liquor continues heating stirring 10 minutes；It weighs 1g disodium ethylene diamine tetraacetate and is added to above-mentioned mixed liquor, continue to heat Stirring 30 minutes obtains the first solution until transparence is presented in solution；
Weighing the addition of 0.45g sodium bromide and filling the volume of 10mL deionized water is in the beaker of 25mL, with equipped with electric heating The magnetic stirrer of set 15 minutes obtains the second solution until transparence is presented in solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 240s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and deionized water circular centrifugal after the reaction was completed, (supercentrifuge is purchased from middle section Good Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the freezing by sample at -50 DEG C is done It is dry in dry case (purchased from Shanghai than bright instrument manufacturing Co., Ltd).
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform BiBaO2Br nanometer sheet can block 80% or more under reset condition, photochromic state and recovery state Ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
Embodiment 5:Sb4O5Cl2The preparation of nano material
Weighing the addition of 0.8g antimony chloride and filling the volume of 30mL deionized water is to use magnetic stirring apparatus in the three-necked bottle of 50mL Stirring 5 minutes；It weighs 0.5g xylitol and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 150 DEG C；Weigh 1g polyethylene pyrrole Lip river Alkanone is added to above-mentioned mixed liquor, continues heating stirring 15 minutes, until transparence is presented in solution, obtains the first solution；
Weighing the addition of 0.2g sodium chloride and filling the volume of 3mL oleic acid is in the beaker of 10mL, with the magnetic for being furnished with electric heating cover Power blender stirs 25 minutes, until transparence is presented in solution, obtains the second solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 80s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and hexamethylene circular centrifugal after the reaction was completed, (supercentrifuge is purchased from good in middle section Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the freeze-drying by sample at -50 DEG C It is dry in case (purchased from Shanghai than bright instrument manufacturing Co., Ltd).
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform Sb4O5Cl2CdS quantum dots can block under reset condition, photochromic state and recovery state 80% or more ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
Embodiment 6:Bi9O18P2The preparation of Cl nano material
Weighing the addition of 0.5g bismuth nitrate and filling the volume of 30mL octadecylene is to be stirred in the three-necked bottle of 50mL with magnetic stirring apparatus It mixes 5 minutes；It weighs 0.5g oleyl alcohol and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 150 DEG C；Weigh 0.4g polyethylene pyrrole Lip river alkane Ketone is added to above-mentioned mixed liquor, continues heating stirring 15 minutes, until transparence is presented in solution, obtains the first solution；
Weighing the addition of 0.15g Efficacious Disinfeitant and filling the volume of 3mL oleyl amine is in the beaker of 10mL, with equipped with electric heating The magnetic stirrer of set 20 minutes obtains the second solution until transparence is presented in solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 180s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and hexamethylene circular centrifugal after the reaction was completed, (supercentrifuge is purchased from good in middle section Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the freeze-day with constant temperature by sample at 60 DEG C It is dry in case.
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform Bi9O18P2Cl nanometer sheet can block 80% or more under reset condition, photochromic state and recovery state Ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
Embodiment 7:Sb8O11Br2The preparation of nano material
Weighing the addition of 0.5g antimony acetate and filling the volume of 30mL ethylene glycol is to be stirred in the three-necked bottle of 50mL with magnetic stirring apparatus It mixes 5 minutes；It weighs 0.5g glycerine and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 150 DEG C；Weigh 0.8g cetyl three Above-mentioned mixed liquor is added in methyl bromide ammonium, continues heating stirring 15 minutes, until transparence is presented in solution, obtains the first solution；
It weighs 0.2g sodium bromide and is added and fill the volume of 5mL ethylene glycol and be in the beaker of 10mL, with equipped with electric heating cover Magnetic stirrer 15 minutes, until transparence is presented in solution, obtain the second solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 200s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and deionized water circular centrifugal after the reaction was completed, (supercentrifuge is purchased from middle section Good Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the constant temperature by sample at 60 DEG C is done It is dry in dry case.
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform Sb8O11Br2Nanobelt can block 80% or more under reset condition, photochromic state and recovery state Ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
Embodiment 8:Bi2O3WO3The preparation of nano material
Weighing the addition of 0.5g bismuth nitrate and filling the volume of 30mL deionized water is to use magnetic stirring apparatus in the three-necked bottle of 50mL Stirring 5 minutes；It weighs 0.5g mannitol and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 90 DEG C；Weigh 0.8g cetyl Trimethylammonium bromide is added to above-mentioned mixed liquor, continues heating stirring 30 minutes, until transparence is presented in solution, it is molten to obtain first Liquid；
Weighing the addition of 0.2g sodium tungstate and filling the volume of 5mL deionized water is in the beaker of 10mL, with equipped with electric heating cover Magnetic stirrer 15 minutes, until solution present transparence, obtain the second solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 240s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and deionized water circular centrifugal after the reaction was completed, (supercentrifuge is purchased from middle section Good Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the constant temperature by sample at 60 DEG C is done It is dry in dry case.
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform Bi2O3WO3Nano particle can block 80% or more under reset condition, photochromic state and recovery state Ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
Embodiment 9:SnO2MoO3The preparation of nano material
Weighing the addition of 0.75g tin tetrachloride and filling the volume of 30mL deionized water is to be stirred in the three-necked bottle of 100mL with magnetic force Device is mixed to stir 5 minutes；It weighs 0.5g glycerine and above-mentioned mixed liquor is added, electricity consumption heating mantle heats are to 100 DEG C；Weigh 1.0g 12 Sodium alkyl benzene sulfonate is added to above-mentioned mixed liquor, continues heating stirring 30 minutes, until transparence is presented in solution, it is molten to obtain first Liquid；
Weighing the addition of 1.5g ammonium molybdate and filling the volume of 20mL deionized water is in the beaker of 25mL, with equipped with electric heating cover Magnetic stirrer 15 minutes, until solution present transparence, obtain the second solution；
Second solution syringe is injected into the first solution, three heated in above-mentioned magnetic stirrer, electric heating cover After reacting 300s in neck bottle, reaction system is cooled to room temperature in ice bath；
Washing 3~5 times with dehydrated alcohol and deionized water circular centrifugal after the reaction was completed, (supercentrifuge is purchased from middle section Good Scientific Instruments Corporation, centrifugal speed 14000rpm, centrifugation time 5 minutes every time)；Finally, the constant temperature by sample at 60 DEG C is done It is dry in dry case.
Identification identical with above-described embodiment 1 and detection and analysis are carried out to resulting sample, determine that resulting sample is ruler Very little uniform SnO2MoO3Nanometer sheet can block 80% or more under reset condition, photochromic state and recovery state Ultraviolet light；It, can be with blocking part visible light to reduce luminous intensity meanwhile under photochromic state.
In order to further illustrate the present invention, below in conjunction with a kind of nothing of the embodiment preparation of above-mentioned photochromic material preparation Machine photochromic material is applied to be described in detail, but it is to be understood that these Application Examples are with skill of the present invention Implemented under premised on art scheme, the detailed implementation method and specific operation process are given, is only further explanation The features and advantages of the present invention, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following Embodiment.Meanwhile various raw materials and equipment involved in specification are purchased from market.
Embodiment 10: can ultraviolet blocking-up skin covering of the surface laminar photochromic translucent glass preparation
With glass cutter by general window glass-cutting at the rectangle glass piece having a size of 2.2 × 3.8cm, with acetone and nothing Water-ethanol wash cycles are clean to glass sheet surface；By the sheet glass cleaned up, drying is standby in 60 DEG C of thermostatic drying chamber With；
Weigh the BiBaO of 1g prepared in example 42The volume for filling 10mL dehydrated alcohol is added in Br nano material It is ultrasonic at 25 DEG C with the thermostatic ultrasonic machine (instrument model: PS-40A10L) of the 240W of power in the screw socket bottle of 25mL 30min obtains finely dispersed lotion；
It takes the above-mentioned evenly dispersed emulsion droplets of 1mL to be added on the sheet glass of above-mentioned clean dried, is paved with glass bar Entire sheet glass, when room temperature is 20 DEG C, one layer of uniform film can be formed on the surface of sheet glass by spontaneously drying 30min, Obtain skin covering of the surface laminar photochromic translucent glass.
Using deep ultraviolet-it is visible-near infrared spectrometer (model: DUV -3700) is to obtained superficial film Formula photochromic translucent glass carries out light transmission rate detection, obtains the optical transmission spectra figure of Fig. 4.As can be seen from Figure 4: utilizing The skin covering of the surface laminar photochromic translucent glass of inorganic photochromic nano material preparation of the invention is in reset condition, light-induced variable The light of ultraviolet band can be filtered out under color state and recovery state；It, can with filtration fraction meanwhile under photochromic state The light-exposed transmitance for reducing light, weakens luminous intensity；
Fig. 5 is the photochromic glass that is prepared using embodiment according to the present invention 8 in sensitive area and non-sensitive area boundary The optical microscope photograph at place.As can be seen from Figure 5: sensitive area presents apparent dark-coloured, and non-sensitive area is colourless, and boundary Locate distinct.
Embodiment 11: can ultraviolet blocking-up incorporation formula photochromic translucent glass preparation
Weigh the Sb prepared in 0.25g above-described embodiment 54O5Cl2Nano material and 50g polycarbonate, are added to ball mill In (instrument model: DECO-PBM-V-0.4L), ball milling 1h obtains uniformly mixed mixed powder；By above-mentioned mixed uniformly powder Body is squeezed into fine and close transparent film with film hot-pressing machine (instrument model: TH-XC601-HC100), obtains incorporation formula light-induced variable Color transparent glass film.
To the progress of resulting incorporation formula photochromic translucent glass-film and the same detection in above-described embodiment 10, class is obtained As a result, the incorporation formula photochromic translucent glass-film prepared using inorganic photochromic nano material of the invention in original The light of ultraviolet band can be filtered out under beginning state, photochromic state and recovery state；Meanwhile under photochromic state, The transmitance that light can be reduced with filtration fraction visible light, weakens luminous intensity.
Embodiment 12: can ultraviolet blocking-up self-support type photochromic translucent film preparation
It will be having a size of the rectangular general window sheet glass of 10 × 10cm, with acetone and dehydrated alcohol wash cycles to sheet glass Clean surface；By the sheet glass cleaned up in 60 DEG C of thermostatic drying chamber drying for standby；
Weigh the SnO prepared in 0.1g above-described embodiment 92MoO3Nano material and 5g polyvinyl butyral (PVB), add Enter to fill the volume of 20mL isopropanol in the screw socket bottle of 25mL, the thermostatic ultrasonic machine with the 240W of power is ultrasonic at 25 DEG C 30min obtains finely dispersed glue；
The above-mentioned evenly dispersed glue of 5mL is taken to be added dropwise on the sheet glass of above-mentioned clean dried, with spin coating instrument (instrument type Number: KW-4A type sol evenning machine) the spin coating 30s in the case where revolving speed is 800 revs/min of revolving speed, then the good sheet glass of spin coating is transferred to Dry 60min in the thermostatic drying chamber that temperature is 60 DEG C can form one layer of uniform transparent membrane on the surface of sheet glass, use Small blade scrapes institute's made membrane de- from glass, obtains self-support type photochromic translucent film.
To the progress of resulting self-support type photochromic translucent film and the same detection in above-described embodiment 10, class is obtained As a result, the self-support type photochromic translucent film prepared using inorganic photochromic nano material of the invention in original The light of ultraviolet band can be filtered out under beginning state, photochromic state and recovery state；Meanwhile under photochromic state, The transmitance that light can be reduced with filtration fraction visible light, weakens luminous intensity.
As can be seen from the above embodiments, photochromic nano material prepared by the present invention can block 80% or more ultraviolet light, It especially can be changed to transparent dead color in strong illumination, reduce light transmission rate；It can restore again in no strong illumination colorless and transparent State.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims (10)

1. a kind of general formula is MaObXcCan ultraviolet blocking-up photochromic nano material, wherein M indicate selected from tin, indium, antimony and One of bismuth or it is a variety of or its with selected from one of titanium, barium, nickel, vanadium, zinc and copper or a variety of combinations；O indicates that oxygen is former Son；X indicates to be selected from and the formula MaObXcIn (MaOb) primitive is capable of forming the tungstate radicle primitive of compound, molybdic acid foundation One of member, vanadic acid foundation member, fluorine, chlorine, bromine and iodine or it is a variety of or its with selected from one of sulphur, carbon, phosphorus and boron or a variety of Combination, and in the formula MaObXcIn, each molar ratio a:b:c for forming primitive is (1~50): (1~50): 1.
2. photochromic nano material according to claim 1, which is characterized in that in the formula MaObXcIn, it is each to form The molar ratio a:b:c of primitive is (1~20): (1~30): 1.
3. photochromic nano material according to claim 1, which is characterized in that the pattern of the nano material be selected from One of quantum dot, nano wire, nanometer sheet, nanobelt and nano particle are a variety of.
4. it is M that one kind, which is used to prepare general formula,aObXcCan ultraviolet blocking-up photochromic nano material method, wherein M indicate Selected from one of tin, indium, antimony and bismuth it is a variety of or its with selected from one of titanium, barium, nickel, vanadium, zinc and copper or a variety of groups It closes；O indicates oxygen atom；X indicates to be selected from and the formula MaObXcIn (MaOb) primitive is capable of forming the wolframic acid foundation of compound One of member, molybdate primitive, vanadic acid foundation member, fluorine, chlorine, bromine and iodine or it is a variety of or its in sulphur, carbon, phosphorus and boron One or more combinations, and in the formula MaObXcIn, each molar ratio a:b:c for forming primitive is (1~50): (1 ~50): 1, it the described method comprises the following steps:
A) by containing M cation source compounds, polyalcohol, surfactant and the first solvent mixture heat under stiring, Obtain the first solution of heat；
B the anion source compound containing X is mixed with the second solvent), obtains the second solution；
C) the first solution that second solution is injected the heat obtains reaction mixture to react；
D) reaction mixture cool down, separate, wash and/or dry, obtain the photochromic nano material.
5. according to the method described in claim 4, it is characterized in that,
The polyalcohol is selected from one of oleyl alcohol, glycerine, pentaerythrite, xylitol, mannitol and sorbierite or a variety of；
The surfactant be selected from neopelex, cetyl trimethylammonium bromide, disodium ethylene diamine tetraacetate, One of polyvinylpyrrolidone, lauroyl glutamate, sodium stearyl sulfate and sodium sulfate of polyethenoxy ether of fatty alcohol Or it is a variety of；
First solvent and second solvent are independently from each other C1-6Alkanol, deionized water, oleyl amine, hexamethylene and oil One of acid is a variety of.
6. according to the method described in claim 4, it is characterized in that,
The mass ratio of the polyalcohol and the cation source compounds containing M is (1~1500): 15；
The mass ratio of the surfactant and the cation source compounds containing M is (1~2000): 20；
The mass ratio of first solvent and the cation source compounds containing M is (1~2000): 10；
The mass ratio of second solvent and the X yin source compound is (1~1500): 10.
7. according to the method described in claim 4, it is characterized in that, the temperature of the first solution of the heat is 30~300 DEG C.
8. according to the method described in claim 4, it is characterized in that, second solution inject the first solution of the heat when Between be 1s~12h.
9. according to the method described in claim 4, it is characterized in that, described be separated into centrifuge separation；The temperature of the drying be- 50~150 DEG C and time are 1~72h.
10. photochromic nano material according to any one of claim 1-3 or according to any one of claim 4-9 The photochromic nano material of the described method preparation for building window glass, light-sensitive sunglasses eyeglass, vehicles glass pane, The purposes of information storage material, ornament materials or photosensitive material.
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