CN108947242A - A kind of moisture environment intelligent response glass and its preparation method and application - Google Patents
A kind of moisture environment intelligent response glass and its preparation method and application Download PDFInfo
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- CN108947242A CN108947242A CN201810925723.0A CN201810925723A CN108947242A CN 108947242 A CN108947242 A CN 108947242A CN 201810925723 A CN201810925723 A CN 201810925723A CN 108947242 A CN108947242 A CN 108947242A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/005—Multi-cellular glass ; Porous or hollow glass or glass particles obtained by leaching after a phase separation step
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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Abstract
The invention discloses a kind of moisture environment intelligent response glass, are combined by halogen lead caesium perovskite quantum dot with cellular glass；The cellular glass is with SiO2、H3BO3、Na2CO3、CaCO3It is prepared as a raw material.The invention also discloses the preparation method and application of above-mentioned moisture environment intelligent response glass.Moisture environment intelligent response glass of the invention utilizes the principle of caesium halide different solubility and recrystallization in different solvents, realizes response of the photochromic switching realization to Environmental Water under ultraviolet.
Description
Technical field
The present invention relates to stimuli responsive material, in particular to a kind of moisture environment intelligent response glass and preparation method thereof and
Using.
Background technique
Stimuli responsive material is a kind of system with " intelligence " behavior, it can be to the stimulus signal of external environment, example
The variation of such as acid-base property, light, temperature, humidity and atmosphere makes itself to generate different variations, embodies corresponding function, greatly
The responsive materials of the existing research in part are usually organic molecule.And perovskite quantum dot can be lower to steady due to the formation of itself
It is qualitative poor, researchers done it is many by halogen lead caesium perovskite quantum dot and some matrixes it is compound come reach improve its stability
Purpose such as glass and organic glass cladding etc., still, the cladding of some dense substrates can make halogen lead caesium perovskite quantum
Point loses to extraneous response, and the halogen lead caesium perovskite quanta point material with excellent luminescent properties can not be used as to extraneous ring
The sensor of border variation.And cellular glass is a kind of inorganic porous material that can be easy to processing, it has aperture small and adjustable,
There is the features such as higher light transmission rate, good chemical stability in visible light wave range, is a kind of good luminous carrier material.
These advantages of cellular glass make load quantum dot improve its stability and have as environmental response material and intellectual material etc.
Application prospect.
Summary of the invention
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the purpose of the present invention is to provide a kind of moisture environment intelligence
Responsive glass, the stability of halogen lead caesium perovskite quantum dot therein in wet condition increases, and primary light is in water
In quench completely after have one can be with the appearance of prolonged blue light, so as to pass through observation glass color in the UV lamp
Variation determine moisture content.
Another object of the present invention is to provide the preparation methods of above-mentioned moisture environment intelligent response glass.
A further object of the present invention is to provide the applications of above-mentioned moisture environment intelligent response glass.
The purpose of the present invention is achieved through the following technical solutions:
A kind of moisture environment intelligent response glass is combined by halogen lead caesium perovskite quantum dot with cellular glass；
The cellular glass is with SiO2、H3BO3、Na2CO3、CaCO3It is prepared as a raw material.
A kind of preparation method of moisture environment intelligent response glass, comprising the following steps:
(1) preparation of cellular glass:
According to SiO2: B2O3: Na2O:CaO=(60~66): (25~30): (5~10): 1 ratio weighs SiO2、
H3BO3、Na2CO3、CaCO3Cellular glass is made with melt phase-separation in raw material；
(2) quantum dot halogen lead caesium perovskite solution is obtained with hot injection method；
(3) to obtain compound glass luminescent material after solution dipping method drying.
Step (1) is described to be made cellular glass with melt phase-separation, specifically:
Mixed raw material is placed in crucible, is heated to 1450~1580 DEG C, 60~300min of heat preservation is to melting, by fusant
It is poured on cooling iron plate and obtains glass, glass is put into annealing furnace the 2h that anneals at 450 DEG C~530 DEG C, subsequent sanding and polishing
Glass is put into Muffle furnace afterwards, split-phase is heat-treated 12~48h at 560~680 DEG C, separates alkali boron phase and silicon phase, is divided
Glass is put in distilled water 90~100 DEG C after second polishing after then split-phase glass sample is cut into small pieces by phase glass sample
12~48h is impregnated under water-bath；Be subsequently placed at 0.5~2mol/L that temperature is 90~100 DEG C and ratio is 1:1 HCl solution and
The NH of 0.5~3mol/L4The Na of Cl solution or saturation2B4O7In the buffer solution of solution, 12~60h of duration；By acidleach
Good glass is put in distilled water under 90~100 DEG C of water-baths after 12~48h of immersion again and wash with distilled water to neutral, baking
It is dry.
It is described to be heated to 1450~1580 DEG C, specifically:
1000 DEG C are warming up to 5~10 DEG C/min, then is warming up to 1450~1580 DEG C with 3~5 DEG C/min.
Step (2) is described to obtain quantum dot halogen lead caesium perovskite solution with hot injection method, specifically:
(2-1) by ratio be 1g:(30~50) ml:(5~10) and ml CsCO3, octadecylene, oleic acid is mixed is incorporated under vacuum
120~140 DEG C are heated to, until solute all dissolves, obtains Cs-OA solution；
Octadecylene, oleic acid, oleyl amine, lead halide are (4~8) by (2-2) by volume: (0.8~1.6): (0.8~1.6)
It mixes, the concentration of lead halide is 0.02~0.03mol/L in mixed liquor；
N is passed through after vacuumizing 10~15min at 25~100 DEG C2Gas is whole to lead halide after being heated to 100~150 DEG C
Dissolution, at 130~180 DEG C, the resulting Cs-OA solution of injection step (2-1), is put into ice-water bath after reaction and is cooled to room temperature,
And carried out centrifuge washing 3~5 times using the revolving speed of 2500~3500r/min, 5~10ml hexamethylene is dispersed by the sample after washing
In alkane, quantum dot solution is obtained.
Compound glass luminescent material is obtained after step (3) drying with solution dipping method, specifically:
By quantum dot solution prepared by step (2) and cellular glass prepared by step (1) impregnates in beaker or dropper
The quantum dot solution of aspiration step (2) preparation is added drop-wise on the cellular glass of step (1) preparation, is dried.
The application of the moisture environment intelligent response glass, for detecting ambient humidity, the moisture in environment enters ring
After the intelligent response glass of border, Color Conversion can occur under ultraviolet for moisture environment intelligent response glass.
The application of the moisture environment intelligent response glass, the moisture environment intelligent response glass after Color Conversion occurs
Restore green light using following methods:
After moisture environment intelligent response glass is dry, it is placed in toluene solution, the methanol solution of the CsBr of saturation is added dropwise, it is quiet
3~20min is set, i.e. recovery green light；
Or using following methods: the dry 0.5mol/L for being placed on 5~10ml of moisture environment intelligent response glass~
The HCl solution of 2mol/L is placed in the methanol solution of CsCl saturation, is waited 5~60min, that is, be can reach blue light, re-dry
It is placed in toluene solution, the methanol solution of the CsBr of saturation is added dropwise, stand 3~20min, restore to green light.
The present invention is reached using caesium halide the recrystallization principle of different solubility and principle of ion exchange in different solvents
The purpose for having arrived photochromic switching, obtained can the photochromic fluorescent glass of switching at runtime, and the response to water in environment may be implemented,
To can be used as environmental response material, intelligent material as ambient intelligence responsive glass using the color of achievable switching light
The application prospect of material etc..
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention is original in water using the ultraviolet 365nm cellular glass excited and halogen lead caesium perovskite composite material
It can continue to maintain a blue light after fluorescent quenching, be up to some months.
(2) present invention can make composite material restore the green light after quenching in water using the method for solution, and utilization is water-soluble
The non-aqueous solution of liquid and caesium halide may be implemented in the dynamic translation of green light and blue light, be reached to can reach using the composite material
Detect the purpose of water in environment.
(3) present invention prepares composite material and realizes that the method for photochromic switching at runtime under ultraviolet 365nm excitation is simple, easily
In operation.
Detailed description of the invention
Fig. 1 is original cellular glass CsPbBr prepared by the embodiment of the present invention 13Perovskite quantum dot and cellular glass
The ultraviolet 365nm of composite luminescent material excites lower launching light spectrogram.
Fig. 2 is that the embodiment of the present invention 2 prepares original CsPb (Cl0.5Br0.5)3Perovskite quantum dot and cellular glass it is multiple
The ultraviolet 365nm for closing luminescent material excites lower launching light spectrogram.
Fig. 3 is CsPb (Br prepared by the embodiment of the present invention 30.5,I0.5)3Perovskite quantum dot and the compound hair of cellular glass
The ultraviolet 365nm of luminescent material excites lower launching light spectrogram.
Fig. 4 is original cellular glass CsPbBr prepared by the embodiment of the present invention 13Perovskite quantum dot and cellular glass
Composite luminescent material it is soaked after ultraviolet 365nm excite lower blue emission spectrum figure.
Fig. 5 is original cellular glass CsPbBr prepared by the embodiment of the present invention 13Perovskite quantum dot and cellular glass
The green emission spectrogram after Color Conversion under ultraviolet 365nm excitation of composite luminescent material.
Fig. 6 is original cellular glass CsPbBr prepared by the embodiment of the present invention 13Perovskite quantum dot and cellular glass
Launching light spectrogram after the Color Conversion of composite luminescent material under ultraviolet 365nm excitation.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
(1) 5.2917g SiO is accurately weighed2、4.8860g H3BO3、1.2110g Na2CO3、0.3333g CaCO3, mixing
Grinding uniformly, obtains precursor mixture in the agate mortar after above-mentioned raw materials.Precursor mixture is placed in crucible, then
Crucible is placed in temperature programming chamber type electric resistance furnace, is warming up to 1000 DEG C with the heating rate of 7 DEG C/min, then with 5 DEG C/
The heating rate of min is warming up to 1550 DEG C, is poured on cooling iron plate after heat preservation 2h and obtains glass, and it is transferred to rapidly annealing
In furnace, 450 DEG C of heat preservation 2h.Then glass is polished, polishing is placed in Muffle furnace to be kept the temperature for 24 hours at 580 DEG C.Glass is placed in
It is washed after 15min to neutrality in the NaOH solution of 1mol/L；Glass is put in distilled water and impregnates 12h under 95 DEG C of water-baths；And
Pretreated glass is placed in the NH of HCl solution l.5mol/L and 1.5mol/L that ratio is 1:14The mixed solution of Cl solution
In, and heating water bath 18h is carried out at 95 DEG C；The good glass of acidleach is put in again in distilled water and is impregnated under 95 DEG C of water-baths
After for 24 hours, wash with distilled water to neutral, drying.
(2) 6ml octadecylene (ODE), 0.5ml oleic acid (OA), 0.5ml oleyl amine (OAM) and 0.069g PbBr are taken2Mixing, and
N is passed through after vacuumizing 10min at 110 DEG C2After gas all dissolves after being heated to 120 DEG C to solute, Cs- is injected at 140 DEG C
OA solution is put into ice-water bath the revolving speed progress centrifuge washing 3~5 for being cooled to room temperature, and using 3000r/min after reacting 5s
It is secondary, it is scattered in 5ml hexamethylene.
(3) by the CsPbBr of gained 3ml3Quantum dot solution and cellular glass impregnate in 5ml beaker, dry after the completion.
It is blue light compound glass material that obtained compound glass material is placed in the sample in distilled water after 10min, taken out, 80
It is taken out after dry 80min in DEG C drying box；It is put into 10ml toluene solution, the first of the CsBr of saturation is then added dropwise with rubber head dropper
After alcoholic solution 1ml, 3~20min is stood, sample is taken out and obtains green light material；After 60 DEG C of dryings, sample is placed in distilled water
The taking-up of blue light compound glass material is obtained after 10min；It is put into 5ml toluene solution, saturation then is added dropwise with rubber head dropper
After the methanol solution 1ml of CsBr, 3~20min is stood, sample is taken out and obtains green light material；After 60 DEG C of dryings, sample is placed in steaming
Blue light compound glass material is obtained in distilled water after 5min.Repeating the above steps can be obtained by green to blue again to green again to the movable of indigo plant
State switches photochromic glass material --- ambient intelligence responsive glass.
CsPbBr manufactured in the present embodiment3The original launching light spectrogram of quantum dot and cellular glass composite luminescent material is such as
Shown in Fig. 1, it is seen that material emission position is located near 516nm, is green light, glow peak is narrow, and monochromaticjty is good.
Compound glass material sample manufactured in the present embodiment impregnate in water after launching light spectrogram as shown in figure 4, shine
Position is near 440nm.
The hair for the green light that the process through converting is restored after compound glass material sample manufactured in the present embodiment impregnates in water
Spectrogram is penetrated as shown in figure 5, luminous position is near 508nm.
Compound glass material sample light conversion spectrum manufactured in the present embodiment is as shown in Figure 6.
Embodiment 2
(1) 5.2065g SiO is accurately weighed2、5.0916g H3BO3、0.9879g Na2CO3、0.3333g CaCO3, mixing
Grinding uniformly, obtains precursor mixture in the agate mortar after above-mentioned raw materials.By precursor mixture be placed in crucible and in
In temperature programming chamber type electric resistance furnace, 1000 DEG C are warming up to the speed of 7.5 DEG C/min, is then warming up to 1500 DEG C with 5 DEG C/min
It is poured on cooling iron plate after heat preservation 2h and obtains glass, and it is transferred in annealing furnace rapidly, 450 DEG C of heat preservation 2h.Then by glass
Glass polishing, polishing is placed in Muffle furnace to be kept the temperature for 24 hours at 590 DEG C.Glass is placed in the NaOH solution of 1mol/L after 15min
And it washs to neutrality；Glass is put in distilled water under 90 DEG C of water-baths and impregnates 12h；And it is 1 that pretreated glass, which is placed in ratio:
1 HCl solution l.5mol/L and the NH of 1.5mol/L4In the mixed solution of Cl solution, and heating water bath is carried out at 90 DEG C,
Duration 36h；The good glass of acidleach is put in again after being impregnated for 24 hours under 90 DEG C of water-baths in distilled water, wash with distilled water extremely
Neutrality, drying
(2) 5ml octadecylene (ODE), 1ml oleic acid (OA), 1ml oleyl amine (OAM) and 0.026g PbCl are taken2With 0.0345g
PbBr2Mixing, and N is passed through after vacuumizing 10min at 100 DEG C2After gas all dissolves after being heated to 130 DEG C to solute, 140
DEG C when inject Cs-OA solution, be put into ice-water bath and be cooled to room temperature after reacting 5s, and using the revolving speed of 3000r/min carry out from
The heart washs 3~5 times, by more sample dispersions in 5ml hexamethylene.
(3) by the CsPb (Cl of gained 3ml0.5Br0.5)3Quantum dot solution and cellular glass impregnate in 5ml beaker, or
Dropper is selected to draw the CsPb (Cl of 3ml0.5Br0.5)3Quantum dot solution is added drop-wise on glass, is dried after the completion.By compound glass
It is blue light compound glass material that material, which is placed in the sample in distilled water after 5min, obtained, the dry 60min in 80 DEG C of drying boxes
After take out；It is put into 5ml toluene solution, after the methanol solution 1ml of the CsBr of saturation is added dropwise with rubber head dropper, standing 3~
20min takes out sample and obtains green light material；After 60 DEG C of dryings, sample is placed in distilled water after 5min and obtains blue light compound glass
Glass material takes out；It is then placed in 5ml toluene solution, after the methanol solution 1ml of the CsBr of saturation is then added dropwise with rubber head dropper,
3~20min is stood, sample is taken out and obtains green light material；After 60 DEG C of dryings, sample is placed in distilled water and obtains blue light after 5min
Compound glass material.Repeat the above steps it is available by indigo plant to it is blue to it is green again again can the photochromic glass of switching at runtime to green to indigo plant
Material --- ambient intelligence responsive glass.
CsPb (Cl manufactured in the present embodiment0.5Br0.5)3The original luminous light of quantum dot and cellular glass composite luminescent material
Spectrogram is as shown in Figure 2.Visible material luminous position is located near 466nm, is blue light.It can be sent out after implementing the operation of switching at runtime
It is existing, it is soaked after spectrum it is similar with the soaked spectrum of embodiment 1, recovery green spectrum is also similar to Example 1 after repeating.
Embodiment 3
(1) 5.2637g SiO is accurately weighed2、5.0961g H3BO3、1.0567g Na2CO3、0.25g CaCO3, in mixing
It is ground uniformly in the agate mortar after stating raw material, obtains precursor mixture.Precursor mixture is placed in crucible and is placed
In temperature programming chamber type electric resistance furnace, 1000 DEG C are warming up to the speed of 8 DEG C/min, is then warming up to 1500 DEG C with 5 DEG C/min
It is poured on cooling iron plate after heat preservation 2h and obtains glass, and it is transferred in annealing furnace rapidly, 450 DEG C of heat preservation 2h.Then by glass
Glass polishing, polishing is placed in Muffle furnace to be kept the temperature for 24 hours at 620 DEG C.Glass is placed in the NaOH solution of 1mol/L after 15min
And it washs to neutrality；Glass is put in distilled water under 98 DEG C of water-baths and impregnates 12h；And it is 1 that pretreated glass, which is placed in ratio:
The HCl solution of 1 0.5mol/L and the NH of 0.5mol/L4In the mixed solution of Cl solution, and heating water bath is carried out at 98 DEG C,
Duration 36h；The good glass of acidleach is put in again after being impregnated for 24 hours under 98 DEG C of water-baths in distilled water, wash with distilled water extremely
Neutrality, drying.
(2) 7ml octadecylene (ODE), 1ml oleic acid (OA), 1ml oleyl amine (OAM) and 0.0276g PbBr are taken2With 0.0522g
PbI2Mixing, and N is passed through after vacuumizing 10min at 25 DEG C2After gas all dissolves after being heated to 130 DEG C to solute, at 140 DEG C
When inject Cs-OA solution, be put into ice-water bath and be cooled to room temperature after reacting 5s, and be centrifuged using the revolving speed of 3000r/min
Washing 3~5 times, by gained sample dispersion in 5ml hexamethylene.
(3) by the CsPb (Br of gained 3ml0.4I0.6)3Quantum dot solution and cellular glass impregnate in 5ml beaker, complete
After dry.It is blue light compound glass material that compound glass luminescent material, which is placed in the sample in distilled water after 60min, taken out,
Material takes out after dry 120min in 80 DEG C of drying boxes；It is put into 8ml toluene solution, the CsBr of saturation is added dropwise with rubber head dropper
Methanol solution 5ml after, stand 20min, take out sample obtain green light material；After 60 DEG C of dryings, sample is placed in distilled water
The taking-up of blue light compound glass material is obtained after 30min；It is then placed in 8ml toluene solution, saturation then is added dropwise with rubber head dropper
CsBr methanol solution 3ml after, stand 3~20min, take out sample obtain green light material；After 60 DEG C of dryings, sample is placed in
Blue light compound glass material is obtained in distilled water after 30min.Repeating the above steps can be obtained by red to blue again to green again to indigo plant
It can the photochromic glass material of switching at runtime --- ambient intelligence responsive glass.
CsPb (Br manufactured in the present embodiment0.4I0.6)3The launching light spectrogram of quantum dot and cellular glass composite luminescent material
As shown in figure 3, visible material luminous position is located near 622nm, it is orange light, glow peak is narrow, and monochromaticjty is good.Implement dynamic to cut
It can be found that the blue spectrum after soaked is similar with the soaked spectrum of embodiment 1 after the operation changed, the green light light that restores after repeating
It composes also similar to Example 1.
Embodiment 4
(1) 5.2917g SiO is accurately weighed2、4.8860g H3BO3、1.2110g Na2CO3、0.3333g CaCO3, mixing
Grinding uniformly, obtains precursor mixture in the agate mortar after above-mentioned raw materials.Precursor mixture is placed in crucible, then
Crucible is placed in temperature programming chamber type electric resistance furnace, is warming up to 1000 DEG C with the heating rate of 8 DEG C/min, then with 5 DEG C/
The heating rate of min is warming up to 1550 DEG C, is poured on cooling iron plate after heat preservation 2h and obtains glass, and it is transferred to rapidly annealing
In furnace, 450 DEG C of heat preservation 2h.Then glass is polished, polishing is placed in Muffle furnace to be kept the temperature for 24 hours at 580 DEG C.Glass is placed in
It is washed after 15min to neutrality in the NaOH solution of 1mol/L；Glass is put in distilled water and impregnates 12h under 95 DEG C of water-baths；And
Pretreated glass is placed in the NH of HCl solution l.5mol/L and 1.5mol/L that ratio is 1:14The mixed solution of Cl solution
In, and heating water bath 18h is carried out at 95 DEG C；The good glass of acidleach is put in again in distilled water and is impregnated under 95 DEG C of water-baths
After for 24 hours, wash with distilled water to neutral, drying.
(2) 6ml octadecylene (ODE), 0.5ml oleic acid (OA), 0.5ml oleyl amine (OAM) and 0.069g PbBr are taken2Mixing, and
N is passed through after vacuumizing 10min at 110 DEG C2After gas all dissolves after being heated to 120 DEG C to solute, Cs- is injected at 140 DEG C
OA solution is put into ice-water bath the revolving speed progress centrifuge washing 3~5 for being cooled to room temperature, and using 3000r/min after reacting 5s
It is secondary, it is scattered in 5ml hexamethylene.
(3) by the CsPbBr of gained 3ml3Quantum dot solution and cellular glass impregnate in 5ml beaker, dry after the completion.
It is blue light compound glass material that obtained compound glass material is placed in the sample in distilled water after 10min, taken out, 80
It is taken out after dry 80min in DEG C drying box；It is put into 5ml toluene solution, the first of the CsBr of saturation is then added dropwise with rubber head dropper
After alcoholic solution 2ml, 20min is stood, sample is taken out and obtains green light material；After 60 DEG C of dryings, it is by the concentration that sample is placed in 10ml
The taking-up of blue light compound glass material is obtained in the HCl solution of 1mol/L after 10min；It is put into after drying in 5ml toluene solution, then
After the methanol solution 1ml of the CsBr of saturation is added dropwise with rubber head dropper, 3~20min is stood, sample is taken out and obtains green light material；60
It is to obtain blue light compound glass material after 10min in the HCl solution of 1mol/L by the concentration that sample is placed in 10ml after DEG C dry.
Repeat the above steps it is available by it is green to it is blue again to it is green again to indigo plant can the photochromic glass material of switching at runtime --- ambient intelligence
Responsive glass.
CsPbBr manufactured in the present embodiment3The original launching light spectrogram of quantum dot and cellular glass composite luminescent material with
And it is soaked after spectrum and restore spectrum it is similar to Example 1.
Embodiment 5
(1) 5.2917g SiO is accurately weighed2、4.8860g H3BO3、1.2110g Na2CO3、0.3333g CaCO3, mixing
Grinding uniformly, obtains precursor mixture in the agate mortar after above-mentioned raw materials.Precursor mixture is placed in crucible, then
Crucible is placed in temperature programming chamber type electric resistance furnace, is warming up to 1000 DEG C with the heating rate of 8 DEG C/min, then with 5 DEG C/
The heating rate of min is warming up to 1550 DEG C, is poured on cooling iron plate after heat preservation 2h and obtains glass, and it is transferred to rapidly annealing
In furnace, 450 DEG C of heat preservation 2h.Then glass is polished, polishing is placed in Muffle furnace to be kept the temperature for 24 hours at 580 DEG C.Glass is placed in
It is washed after 15min to neutrality in the NaOH solution of 1mol/L；Glass is put in distilled water and impregnates 12h under 95 DEG C of water-baths；And
Pretreated glass is placed in the NH of HCl solution l.5mol/L and 1.5mol/L that ratio is 1:14The mixed solution of Cl solution
In, and heating water bath 18h is carried out at 95 DEG C；The good glass of acidleach is put in again in distilled water and is impregnated under 95 DEG C of water-baths
After for 24 hours, wash with distilled water to neutral, drying.
(2) 6ml octadecylene (ODE), 0.5ml oleic acid (OA), 0.5ml oleyl amine (OAM) and 0.069g PbBr are taken2Mixing, and
N is passed through after vacuumizing 10min at 110 DEG C2After gas all dissolves after being heated to 120 DEG C to solute, Cs- is injected at 140 DEG C
OA solution is put into ice-water bath the revolving speed progress centrifuge washing 3~5 for being cooled to room temperature, and using 3000r/min after reacting 5s
It is secondary, it is scattered in 5ml hexamethylene.
(3) by the CsPbBr of gained 3ml3Quantum dot solution and cellular glass impregnate in 5ml beaker, dry after the completion.
It is blue light compound glass material that obtained compound glass material is placed in the sample in distilled water after 10min, taken out, 80
It is taken out after dry 80min in DEG C drying box；It is put into 4ml toluene solution, the first of the CsBr of saturation is then added dropwise with rubber head dropper
After alcoholic solution 3ml, 20min is stood, sample is taken out and obtains green light material；After 60 DEG C of dryings, sample is placed in 5ml toluene solution
In, and be added dropwise in the methanol solution for the CsCl that 3ml is saturated and obtain the taking-up of blue light compound glass material after 10min；It is put into after drying
In 5ml toluene solution, after the methanol solution 3ml of the CsBr of saturation is then added dropwise with rubber head dropper, 3~20min is stood, takes out sample
Product obtain green light material；After 60 DEG C of dryings, sample is placed in 5ml toluene solution after 10min to and is added dropwise the CsCl's of 3ml saturation
Blue light compound glass material is obtained in methanol solution after 10min.Repeating the above steps can be obtained by green to blue again to green again to indigo plant
Can the photochromic glass material of switching at runtime --- ambient intelligence responsive glass.
CsPbBr manufactured in the present embodiment3The original launching light spectrogram of quantum dot and cellular glass composite luminescent material with
And it is soaked after spectrum and restore spectrum it is similar to Example 1.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of moisture environment intelligent response glass, which is characterized in that compound by halogen lead caesium perovskite quantum dot and cellular glass
It forms；
The cellular glass is with SiO2、H3BO3、Na2CO3、CaCO3It is prepared as a raw material.
2. a kind of preparation method of moisture environment intelligent response glass, which comprises the following steps:
(1) preparation of cellular glass:
According to SiO2: B2O3: Na2O:CaO=(60~66): (25~30): (5~10): 1 ratio weighs SiO2、H3BO3、
Na2CO3、CaCO3Cellular glass is made with melt phase-separation in raw material；
(2) quantum dot halogen lead caesium perovskite solution is obtained with hot injection method；
(3) compound glass luminescent material is obtained with solution dipping method.
3. the preparation method of moisture environment intelligent response glass according to claim 2, which is characterized in that step (1) institute
It states and cellular glass is made with melt phase-separation, specifically:
Mixed raw material is placed in crucible, is heated to 1450~1580 DEG C, fusant is poured on by 60~300min of heat preservation to melting
Glass is obtained on cooling iron plate, glass is put into annealing furnace the 2h that anneals at 450 DEG C~530 DEG C, it will after subsequent sanding and polishing
Glass is put into Muffle furnace, and split-phase is heat-treated 12~48h at 560~680 DEG C, is separated alkali boron phase and silicon phase, is obtained split-phase glass
Glass is put in 90~100 DEG C of water-baths in distilled water after second polishing after then split-phase glass sample is cut into small pieces by glass sample
12~48h of lower immersion；Be subsequently placed at the HCl for 0.5~2mol/L that temperature is 90~100 DEG C and ratio is 1:1 acid solution and
The NH of 0.5~3mol/L4The Na of Cl solution or saturation2B4O7In the buffer solution of solution, 12~60h of duration；By acidleach
Good glass is put in distilled water under 90~100 DEG C of water-baths after 12~48h of immersion again and wash with distilled water to neutral, baking
It is dry.
4. the preparation method of moisture environment intelligent response glass according to claim 3, which is characterized in that described to be heated to
1450~1580 DEG C, specifically:
1000 DEG C are warming up to 5~10 DEG C/min, then is warming up to 1450~1580 DEG C with 3~5 DEG C/min.
5. the preparation method of moisture environment intelligent response glass according to claim 2, which is characterized in that step (2) institute
It states and quantum dot halogen lead caesium perovskite solution is obtained with hot injection method, specifically:
(2-1) by ratio be 1g:(30~50) ml:(5~10) and ml CsCO3, octadecylene, oleic acid is mixed is incorporated in heating under vacuum
To 120~140 DEG C, until solute all dissolves, Cs-OA solution is obtained；
Octadecylene, oleic acid, oleyl amine, lead halide are (4~8) by (2-2) by volume: (0.8~1.6): (0.8~1.6) mixing,
The concentration of lead halide is 0.02~0.03mol/L in mixed liquor；
N is passed through after vacuumizing 10~15min at 25~100 DEG C2Gas all dissolves after being heated to 100~150 DEG C to lead halide,
At 130~180 DEG C, the resulting Cs-OA solution of injection step (2-1), is put into ice-water bath after reaction and is cooled to room temperature, and make
It is carried out centrifuge washing 3~5 times with the revolving speed of 2500~3500r/min, by the sample dispersion after washing in 5~10ml hexamethylene
In, obtain quantum dot solution.
6. the preparation method of moisture environment intelligent response glass according to claim 2, which is characterized in that step (3) institute
It states to obtain compound glass luminescent material after solution dipping method drying, specifically:
The cellular glass of the quantum dot solution of step (2) preparation and step (1) preparation is impregnated in beaker or dropper is drawn
The quantum dot solution of step (2) preparation is added drop-wise on the cellular glass of step (1) preparation, is dried.
7. the application of moisture environment intelligent response glass described in claim 1, which is characterized in that for detecting ambient humidity,
After moisture in environment enters ambient intelligence responsive glass, moisture environment intelligent response glass issues raw Color Conversion ultraviolet.
8. the application of moisture environment intelligent response glass according to claim 7, which is characterized in that after Color Conversion occurs
Moisture environment intelligent response glass restore green light under ultraviolet using following methods:
It after moisture environment intelligent response glass is dry, is placed in toluene solution, the methanol solution of the CsBr of saturation is added dropwise, stand 3
~20min, i.e. recovery green light；
Or use following methods: the dry 0.5mol/L~2mol/L for being placed on 5~10ml of moisture environment intelligent response glass
HCl solution or be placed in CsCl saturation methanol solution in, wait 5~60min, that is, can reach blue light, re-dry is placed on
In toluene solution, the methanol solution of the CsBr of saturation is added dropwise, stands 3~20min, restores to green light.
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