CN110092591A - A kind of VO of 3-D ordered multiporous network-like structure2Film and its preparation method and application - Google Patents
A kind of VO of 3-D ordered multiporous network-like structure2Film and its preparation method and application Download PDFInfo
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- CN110092591A CN110092591A CN201910294999.8A CN201910294999A CN110092591A CN 110092591 A CN110092591 A CN 110092591A CN 201910294999 A CN201910294999 A CN 201910294999A CN 110092591 A CN110092591 A CN 110092591A
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- C01G31/00—Compounds of vanadium
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- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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- 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
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- 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
- C03C2218/00—Methods for coating glass
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- 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
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Abstract
The invention discloses a kind of VO of 3-D ordered multiporous network-like structure2Film and its preparation method and application, this method are first stacked polystyrene microsphere on a glass substrate by vertical infusion process, form preparation VO2The template is immersed in VO by the template of film2In precursor solution, so that V in precursor solution2O5The gap between polystyrene microsphere is adequately filled up, by subsequent drying, annealing process, so that V2O5It is converted into VO2, while polystyrene microsphere is by thermal evaporation, VO2It is formed 3-D ordered multiporous network-like；The film has complete 3-D ordered multiporous network-like structure.Because of hole in total, so that as the VO on some skeleton2When being produced fracture between particle, because hole is separated, so that the power of rupture is blocked out, so that transformation stress is diluted.
Description
[technical field]
The invention belongs to VO2Thermal induced phase transition intelligent glass field is related to a kind of VO of 3-D ordered multiporous network-like structure2
Film and its preparation method and application.
[background technique]
China is faced with huge energy consumption and energy crisis, and wherein building energy consumption accounts for about 38%, and air-conditioning accounts for about and builds
Build the 55% of energy consumption.Air-conditioning is mainly used for indoor cooling and warming, maintains preference temperature, but its brought energy consumption is not allowed
Ignore.How to find a kind of mode of energy-saving and environment-friendly regulation room temperature is a urgent problem to be solved.
VO2With excellent thermal induced phase transition performance, when temperature is lower than phase transition temperature, crystal is the insulation of monocline
Body phase (VO2(M)), when temperature is increased to phase transition temperature or more, just it is changed into the metal phase (VO of tetragonal2(R)).Its object
Rationality matter, e.g., resistivity, magnetic susceptibility and optical property etc. can also mutate, especially infrared and near infrared band transmission
Rate is changed significantly, and this process completely reversibility, in bolometer, light shutter device, light storage device and high-effect intelligence
The technical fields such as glass have huge potential application foreground.By VO2It can be changed applied to intelligent glass with sense ambient temperature
And it responds, principle are as follows: when environment temperature is lower than phase transition temperature, VO2Show as insulator phase and with high infrared
Light transmission, as light application time extends, room temperature is gradually risen, if room temperature is higher than phase transition temperature, VO2It will transformation
At metal phase, strong reflex is generated to infrared light, therefore ir transmissivity drastically reduces, passive feedback effect can be tieed up
It is constant to hold room temperature.Compared with air-conditioning, without consuming electric energy, mass energy will be saved.
How VO is increased substantially2Ability of regulation and control to infrared band and to adjust its phase transition temperature be the key that it applies skill
Art problem.Substantially, work as VO2When monocline-four directions phase transformation occurs with temperature, it is necessarily accompanied with volume change, is thus introduced repeatedly
Stress may cause film crack even from glass matrix peel off.Therefore, how to prepare light modulation ability it is strong, can
Release slow transformation stress and the uniform VO of structure2Film is it using urgent problem to be solved.
[summary of the invention]
It is an object of the invention to overcome the above-mentioned prior art, a kind of 3-D ordered multiporous network-like structure is provided
VO2Film and its preparation method and application.The film prepares VO by vertical infusion process2The template of film, by VO2Filling
Into template, the VO of 3-D ordered multiporous network-like structure is ultimately formed2Film.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of VO of 3-D ordered multiporous network-like structure2The preparation method of film, comprising the following steps:
(1) cleaning treatment glass substrate；
(2) polystyrene microsphere is adhered on a glass substrate by vertical infusion process, forms preparation VO2The mould of film
Plate；
(3) with V2O5For vanadium source, with CH3The mixed solution of OH and HCl is solvent, with N2H4For reducing agent, prepare mole dense
Degree is the VO of 10~100mmol/L2Precursor solution；
(4) by step (2) preparation VO obtained2The template of film is immersed in VO made from step (3)2In precursor solution,
Dry after pulling out, annealing, forms the VO of 3-D ordered multiporous network-like structure on a glass substrate2Film.
A further improvement of the present invention is that:
Preferably, in step (1), clean glass substrate the step of are as follows: quartz glass is passed sequentially through into acetone and ethyl alcohol surpasses
After sonication, 5~30min is impregnated in Piranha solution, is ultrasonically treated 30~60min in deionized water.
Preferably, in step (2), vertical infusion process is ultrasound point after diluting polystyrene spheres lotion by deionized water
It dissipates, vertical dipping solution is made；Glass substrate is immersed in vertical dipping solution, the vertical dipping of glass substrate will be impregnated with
Solution induces 10~12h in 60~70 DEG C of evaporations, and VO is made after taking-up2The template of film.
Preferably, when diluting polystyrene spheres lotion by deionized water, the body of polystyrene spheres lotion and deionized water
Product is than being (1-2): (25-50).
Preferably, when diluting polystyrene spheres lotion by deionized water, the body of polystyrene spheres lotion and deionized water
Product is than being 1:25；Polystyrene spheres in polystyrene spheres lotion are having a size of 200-1500nm.
Preferably, in step (3), CH3In the mixed solution of OH and HCl, CH3The volume ratio of OH and HCl is 15:(1-3)；
The N of addition2H4And CH3OH volume ratio is (0.25-2): 60.
Preferably, in step (4), VO is prepared2The template of film is in VO2Soaking time in precursor solution is 3~10h.
Preferably, in step (4), VO will be prepared2The template of film is in VO2It is impregnated in precursor solution, dry 8 after pulling out
~12h, drying temperature are 60~100 DEG C；Annealing temperature is 450~500 DEG C, and annealing time is 1~2h.
A kind of VO for the 3-D ordered multiporous network-like structure prepared by above-mentioned any one preparation method2Film,
The VO2Film is honeycomb, is made of multiple holes, and the edge of each hole is VO2Particle side, the VO2Particle side by
Multiple VO2Particle is connected to form, and adjacent holes share a VO2Particle side；The size of each hole is 200-1500nm.
A kind of VO of above-mentioned 3-D ordered multiporous network-like structure2Film works as VO in the application in intelligent glass field2It is thin
Film is applied at intelligent glass field, VO2The infrared light modulation capability of film is 8.2%-10.8%, is at 2500nm in wavelength
Light modulation ability be 36.4%-59.5%.
Compared with prior art, the invention has the following advantages:
The invention discloses a kind of VO of 3-D ordered multiporous network-like structure2The preparation method of film, this method is first
Polystyrene microsphere is stacked on a glass substrate by vertical infusion process, forms preparation VO2The template of film soaks the template
Bubble is in VO2In precursor solution, so that VOCl in precursor solution2The Delta Region between polystyrene microsphere is adequately filled up, is led to
Subsequent drying, annealing process are crossed, so that VOCl2It is converted into VO2, while the heated decomposition gasification of polystyrene microsphere, form hole
Hole, VO2Form the skeleton of 3-D ordered multiporous network-like structure；The preparation process of this method is anti-without the hydro-thermal of high temperature and pressure
It answers, VO can be formed in 65 DEG C of water-baths, soaking at room temperature2Precursor solution；Whole preparation process experimental period is short, controllability is strong,
Experiment by common hydro-thermal method for 24 hours or 48h, shortening to 6h can be completed, and experimental procedure is simply clear, and repeatability greatly improves；
Because the film of preparation process is grown directly upon in quartz glass substrate, ingredient is uniform, film base binding performance is good, not easy-peel
It falls；The characteristics of decomposition gasification easy because of polystyrene microsphere high temperature, so that finally formed film has more complete three-dimensional order
Porous network shape structure greatly improves the light ability of regulation and control of infrared band.
Further, glass substrate is cleaned after acetone and EtOH Sonicate processing cleaning by Piranha solution, because
Piranha solution has very strong oxidisability, can thoroughly remove the organic matter in substrate, and with the sheet glass of treated with same
Surface highly-hydrophilic due to hydroxyl is prepared on a glass substrate for the attachment of subsequent polystyrene spheres.
Further, the concentration of PS lotion is adjusted by deionized water, the entire three-dimensional that can adjust subsequent formation has
The thickness of the network skeleton of sequence porous network shape structure is induced by evaporation, PS microballoon layer by layer is enabled to be attached to quartz
In glass substrate；By adjusting the size of PS ball in PS ball lotion, can adjust in the three-dimensional net structure finally prepared
Hole size.
Further, VO is filled with by dry and annealing2The VO of precursor liquid2The template of film, by 60~
It is dry at 100 DEG C, so that the VO around microballoon2Presoma adequately can solidify to form solid-state structure, while PS microballoon is at this
At a temperature of vitrifying so that being connected between ball and ball, ball and substrate of glass even closer；By annealing at 450~500 DEG C,
One side PS ball is heated decomposition gasification, has gradually formed the hole configurations in three-dimensional net structure, in another aspect precursor liquid
VOCl2It is changed into VO within this temperature range2, while solid VO2Heated gradually forming core grows up to form VO one by one2Nanometer
Particle, multiple VO2Nano particle is connected with each other, and forms the skeleton structure of three-dimensional net structure.
The invention also discloses a kind of VO of 3-D ordered multiporous network-like structure2Film, the film have complete three
Tie up ordered porous network-like structure.Because on the one hand total can be prevented effectively in film rich in hole, the presence of hole
The generation and extension of crackle, another aspect hole can also be stress caused by temperature change in phase transition process, provide certain
Slow space is released, so that transformation stress is weakened.
The invention also discloses a kind of VO of 3-D ordered multiporous network-like structure2Film answering in intelligent glass field
With because the film is orderly uniform three-dimensional net structure, and porosity is adjustable, so that the ability of regulation and control of infrared band mentions significantly
Height, infrared light modulation capability (the Δ T of the filmsol) it is 8.2%-10.8%, it is the light modulation ability at 2500nm in wavelength
(ΔT2500) it is 36.4%-59.5%.
[Detailed description of the invention]
Fig. 1 is VO of the invention2The distributed architecture figure of PS ball in the template of film；
Fig. 2 is VO of the invention2The scanning electron microscope (SEM) photograph of the surface topography of PS ball in the template of film；
Fig. 3 is the scanning electron microscope (SEM) photograph for the surface topography that the embodiment of the present invention 1 prepares film；
Fig. 4 is the X-ray diffraction spectrum that the embodiment of the present invention 1 prepares film；
Fig. 5 is the light transmittance test result that the embodiment of the present invention 1 prepares film；
Fig. 6 is the scanning electron microscope (SEM) photograph for the surface topography that the embodiment of the present invention 2 prepares film；
Fig. 7 is the X-ray diffraction spectrum that the embodiment of the present invention 2 prepares film；
Fig. 8 is the light transmittance test result that the embodiment of the present invention 2 prepares film；
Fig. 9 is the scanning electron microscope (SEM) photograph for the surface topography that the embodiment of the present invention 3 prepares film；
Figure 10 is the X-ray diffraction spectrum that the embodiment of the present invention 3 prepares film；
Figure 11 is the light transmittance test result that the embodiment of the present invention 3 prepares film；
[specific embodiment]
The invention will be described in further detail with attached drawing combined with specific embodiments below:
The invention discloses a kind of VO of 3-D ordered multiporous network-like structure2Film and its preparation method and application；It should
VO2Film is 3-D ordered multiporous network-like structure, which is honeycomb, is made of multiple holes, each
The edge of hole is by multiple VO2Nano particle composition, the edge of all adjacent holes, which shares, forms 3-D ordered multiporous net
Network shape structure.
The preparation process of the film the following steps are included:
(1) selecting high transparency quartz glass is substrate, is started the cleaning processing.Specifically includes the following steps: by high light transmission
After the quartz glass of rate is successively respectively ultrasonically treated 20~90min in acetone, ethyl alcohol, in Piranha solution (H2SO4: H2O2=
5~30min is impregnated in 7:3), is ultrasonically treated 30~60min in deionized water；High transparency quartz glass is cleaned as substrate
It is spare.
(2) vertical infusion process is utilized, polystyrene (PS) microballoon is subjected to self assembly ordered arrangement, shape on a glass substrate
At preparation VO2The template of film.The detailed process of the step is commercially available or self-control PS ball lotion, the PS in general PS ball lotion
The size of ball is 200-1500nm, and the size of PS ball directly affects the size of the three-dimensional net structure Hole；Pass through deionization
Water dilutes PS ball lotion, and in dilution, the volume ratio of PS lotion and deionized water is (1-2): (25-50), the ratio are preferred
For 1:25；By adjusting the concentration (i.e. dilute strength) of the PS ball lotion, the entire three-dimensional net structure prepared can be adjusted
The number of plies of skeleton；After diluted PS ball lotion ultrasonic disperse 1-2h, vertical dipping solution is prepared, will be cleaned in step (1)
Quartz glass substrate suspension be immersed in vertical dipping solution, whole system is placed in air dry oven, 60~70 DEG C steam
Hair 10~12h of induction, is made VO after taking-up2The template of film；Referring to Fig. 1, this step adjusts PS cream by deionized water first
The concentration of liquid adjusts the thickness of three-dimensional network skeleton, that is, the thickness of entire template, is induced by evaporation and dry, so that
PS microballoon layer by layer can be attached on quartz glass substrate, and Fig. 2 is the VO as made from this method2PS is micro- in the template of film
The microcosmic scanning electron microscope (SEM) photograph of ball, as can be seen from the figure PS microballoon is because of its good sphericity, large specific surface area, uniform in size controllable
Feature, can on glass backing plate uniform stacked in multi-layers, form the formwork structure at initial stage.
(3) with V2O5For vanadium source (solute), with CH3OH and HCl is solvent, with N2H4For reducing agent, V is prepared2O5It is mole dense
Degree is the CH of 10~100mmol/L3OH, HCl solution, wherein CH3The mixed solution of OH and HCl is solvent, the volume proportion of the two
For 15:(1-3), CH3OH and N2H4Volume ratio be 60:(0.25-2), mixed process are as follows: in 60~70 DEG C of water-bath magnetic agitations
Under, CH is added in vanadium source3In OH solution, HCl and N is then successively added dropwise2H4, sufficiently after reaction, taken out from water-bath,
It is cooled to room temperature, prepares VO2Precursor solution, the V in the precursor solution is with VOCl2Compound form exist.
(4) VO will be made made from step (2) at room temperature2The template of film is immersed in VO23~10h is fished out in precursor solution
Out, in air dry oven, in 60~100 DEG C of dry 8~12h；450~500 DEG C of 1~2h of annealing in argon atmosphere are formed
VO23-D ordered multiporous network-like structure film.In the step, first by VO2The template of film is immersed in VO23 in presoma~
10h, so that VO2VOCl in precursor solution2It can adequately be filled full of the gap between PS microballoon, soaking time to it
Time dries the VO so that around microballoon in air dry oven after pulling out2Precursor solution can adequately solidify to be formed admittedly
State structure, while the vitrifying at such a temperature of PS microballoon so that connected between ball and ball, ball and substrate of glass it is even closer,
VO around PS microballoon2After precursor solution sufficiently solidifies, whole system is annealed at 450~500 DEG C, one side PS ball by
Thermal decomposition gasification, has gradually formed the hole configurations in three-dimensional net structure, the VOCl in another aspect precursor liquid2In the temperature
It is changed into VO in degree range2, while solid VO2Heated gradually forming core grows up to form VO one by one2Nano particle, multiple VO2It receives
Rice grain is connected with each other, and forms the skeleton structure of three-dimensional net structure, the structure of formation is referring to Fig. 3.
The preparation process can adjust the big of three-dimensional net structure Hole by adjusting the size of PS ball in PS ball lotion
It is small, by adjusting the degree that PS lotion is diluted, the thickness of entire film can be adjusted；Simultaneously as film is initially formed is exactly
It is formed on a glass substrate, so that film base binding performance is good, is not easy to peel off；Referring to Fig. 3, it is somebody's turn to do by what this method was prepared
VO2Film is 3-D ordered multiporous network-like structure, which is honeycomb, is made of multiple holes, each
The edge of hole is by multiple VO2Particle composition, the edge of all adjacent holes share formed it is 3-D ordered multiporous network-like
Structure；This three-dimensional net structure is orderly uniform, and porosity is adjustable, so that the ability of regulation and control of infrared band greatly improves, entirely
For structure rich in hole, on the one hand the presence of hole can effectively prevent the generation and extension of crackle in film, another aspect hole
It can also be stress caused by temperature change in phase transition process, provide and centainly release slow space, so that transformation stress is weakened.It is logical
Cross the VO that this method is prepared2Film, infrared light modulation capability (the Δ T of the filmsol) it is 8.2%-10.8%, be in wavelength
Light modulation ability (Δ T at 2500nm2500) it is 36.4%-59.5%.
Embodiment 1
(1) quartz plate is successively respectively ultrasonically treated 30min in acetone, ethyl alcohol, 30min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 30min in deionized water；
(2) the PS ball lotion of 2mL is added to ultrasonic disperse 2h in the deionized water of 50mL, PS ball dilution is prepared, will walk
Suddenly the quartz glass vertical hanging that (1) cleans up is immersed in PS ball dilution, is placed in air dry oven, is lured in 60 DEG C of evaporations
10h is led, PS ball template is formed.
(3) in 60mLCH3In OH solution, vanadium source, 4mLHCl and 0.25mLN are sequentially added2H4, prepare V2O5Concentration is
22.6mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:1, CH3OH and N2H4Volume ratio be 60:
0.25。
(4) the good PS ball template of self assembly is immersed in VO by room temperature23h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 100 DEG C of dry 10h.Then, by sample in argon atmosphere 500 DEG C of annealing 1h.
It is the VO of this example preparation referring to Fig. 32Film shows as 3-D ordered multiporous network-like structure, can be with from Fig. 3
Find out, the embodiment surface uniformly, structural integrity；Fig. 4 is the X-ray diffraction spectrum of the embodiment, is as can be seen from the figure prepared
Film out is the VO of M crystal form2, from figure 5 it can be seen that the infrared light ability of regulation and control Δ Tsol=10.8% of the film,
Wavelength is the light modulation ability Δ T at 2500nm2500=52%.
Embodiment 2
(1) quartz plate is successively respectively ultrasonically treated 30min in acetone, ethyl alcohol, 30min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 30min in deionized water；
(2) ultrasonic disperse 2h in 50mL deionized water is added in 2mL PS ball lotion, PS ball dilution is prepared, by step
(1) the quartz glass suspension cleaned up is immersed in PS ball dilution, is placed in air dry oven, induces 12h in 60 DEG C of evaporations,
Form PS ball template.
(3) in 60mLCH3In OH solution, vanadium source, 8mLHCl and 0.5mLN are sequentially added2H4, prepare V2O5Concentration is
33.9mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:2, CH3OH and N2H4Volume ratio be 60:
0.5。
(4) the good PS ball template of self assembly is immersed in VO by room temperature25h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 100 DEG C of dry 10h.Then, by sample in argon atmosphere 500 DEG C of annealing 1h.
It is the VO of this example preparation referring to Fig. 62Film shows as 3-D ordered multiporous network-like structure, can be with from Fig. 6
Find out, the embodiment surface uniformly, structural integrity；Fig. 7 is the X-ray diffraction spectrum of the embodiment, is as can be seen from the figure prepared
Film out is the VO of M crystal form2, as can be seen from Figure 8, the infrared light ability of regulation and control Δ T of the filmsol=9.9%, in wave
Light modulation ability Δ T at a length of 2500nm2500=59.5%
Embodiment 3
(1) quartz plate is successively respectively ultrasonically treated 30min in acetone, ethyl alcohol, 30min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 30min in deionized water；
(2) ultrasonic disperse 2h in 50mL deionized water is added in 2mLPS ball lotion, PS ball dilution is prepared, by step (1)
The quartz glass suspension cleaned up is immersed in PS ball dilution, is placed in air dry oven, induces 10h, shape in 60 DEG C of evaporations
At PS ball template.
(3) in 60mLCH3In OH solution, vanadium source, 8mLHCl and 0.5mLN are sequentially added2H4, prepare V2O5Concentration is
45.2mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:2, CH3OH and N2H4Volume ratio be 60:
0.5。
(4) the good PS ball template of self assembly is immersed in VO by room temperature23h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 100 DEG C of dry 10h.Then, by sample in argon atmosphere 500 DEG C of annealing 1h.
It is the VO of this example preparation referring to Fig. 92Film shows as 3-D ordered multiporous network-like structure, from Fig. 1,6,9
As can be seen that the embodiment surface is uniform, structural integrity, the aperture for the hole prepared is 200-300nm；Figure 10 is the implementation
The X-ray diffraction spectrum of example, the film as can be seen from the figure prepared are the VO of M crystal form2, it can be seen from fig. 11 that this is thin
The infrared light ability of regulation and control Δ T of filmsol=8.2%, it is the light modulation ability Δ T at 2500nm in wavelength2500=44.1%.
Embodiment 4
(1) quartz plate is successively respectively ultrasonically treated 20min in acetone, ethyl alcohol, 30min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 60min in deionized water；
(2) ultrasonic disperse 1h in 50mL deionized water is added in 1mLPS ball lotion, PS ball dilution is prepared, by step (1)
The quartz glass vertical hanging cleaned up is immersed in PS ball dilution, is placed in air dry oven, is induced in 70 DEG C of evaporations
10h forms PS ball template.
(3) in 60mLCH3In OH solution, vanadium source, 6mLHCl and 0.35mLN are sequentially added2H4, prepare V2O5Concentration is
50.6mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:1.5, CH3OH and N2H4Volume ratio be 60:
0.35。
(4) the good PS ball template of self assembly is immersed in VO by room temperature210h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 60 DEG C of dry 12h.Then, by sample in argon atmosphere 450 DEG C of annealing 2h.
Embodiment 5
(1) quartz plate is successively respectively ultrasonically treated 90min in acetone, ethyl alcohol, 5min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 40min in deionized water；
(2) ultrasonic disperse 1h in 25mL deionized water is added in 2mLPS ball lotion, PS ball dilution is prepared, by step (1)
The quartz glass vertical hanging cleaned up is immersed in PS ball dilution, is placed in air dry oven, is induced in 65 DEG C of evaporations
11h forms PS ball template.
(3) in 75mLCH3In OH solution, vanadium source, 10mLHCl and 0.7mLN are sequentially added2H4, prepare V2O5Concentration is
58.2mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:2, CH3OH and N2H4Volume ratio be 60:
0.6。
(4) the good PS ball template of self assembly is immersed in VO by room temperature28h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 70 DEG C of dry 11h.Then, by sample in argon atmosphere 450 DEG C of annealing 2h.
Embodiment 6
(1) quartz plate is successively respectively ultrasonically treated 40min in acetone, ethyl alcohol, 10min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 50min in deionized water；
(2) ultrasonic disperse 1.5h in 40mL deionized water is added in 1mLPS ball lotion, PS ball dilution is prepared, by step
(1) the quartz glass suspension cleaned up is immersed in PS ball dilution, is placed in air dry oven, induces 12h in 62 DEG C of evaporations,
Form PS ball template.
(3) in 80mLCH3In OH solution, vanadium source, 12mLHCl and 1.0mLN are sequentially added2H4, prepare V2O5Concentration is
68.7mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:2.25, CH3OH and N2H4Volume ratio be
60:0.77。
(4) the good PS ball template of self assembly is immersed in VO by room temperature27h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 80 DEG C of dry 10h.Then, by sample in argon atmosphere 480 DEG C of annealing 1.5h.
Embodiment 7
(1) quartz plate is successively respectively ultrasonically treated 50min in acetone, ethyl alcohol, 15min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 45min in deionized water；
(2) ultrasonic disperse 1.5h in 35mL deionized water is added in 2mLPS ball lotion, PS ball dilution is prepared, by step
(1) the quartz glass suspension cleaned up is immersed in PS ball dilution, is placed in air dry oven, induces 10h in 68 DEG C of evaporations,
Form PS ball template.
(3) in 85mLCH3In OH solution, vanadium source, 15mLHCl and 1.5mLN are sequentially added2H4, prepare V2O5Concentration is
82.4mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:2.64, CH3OH and N2H4Volume ratio be
60:1.01。
(4) the good PS ball template of self assembly is immersed in VO by room temperature26h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 90 DEG C of dry 8h.Then, by sample in argon atmosphere 470 DEG C of annealing 1.5h.
Embodiment 8
(1) quartz plate is successively respectively ultrasonically treated 60min in acetone, ethyl alcohol, 20min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 55min in deionized water；
(2) ultrasonic disperse 2h in 30mL deionized water is added in 1mLPS ball lotion, PS ball dilution is prepared, by step (1)
The quartz glass suspension cleaned up is immersed in PS ball dilution, is placed in air dry oven, induces 11h, shape in 65 DEG C of evaporations
At PS ball template.
(3) in 85mLCH3In OH solution, vanadium source, 15mLHCl and 2.0mLN are sequentially added2H4, prepare V2O5Concentration is
The precursor solution of 100mmol/L；Wherein CH3The volume ratio of OH and HCl is 15:2.64, CH3OH and N2H4Volume ratio be 60:
1.41。
(4) the good PS ball template of self assembly is immersed in VO by room temperature24h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 90 DEG C of dry 9h.Then, by sample in argon atmosphere 460 DEG C of annealing 2h.
Embodiment 9
(1) quartz plate is successively respectively ultrasonically treated 70min in acetone, ethyl alcohol, 25min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 35min in deionized water；
(2) ultrasonic disperse 1h in 45mL deionized water is added in 1mLPS ball lotion, PS ball dilution is prepared, by step (1)
The quartz glass suspension cleaned up is immersed in PS ball dilution, is placed in air dry oven, induces 12h, shape in 70 DEG C of evaporations
At PS ball template.
(3) in 90mLCH3In OH solution, vanadium source, 18mLHCl and 3.0mLN are sequentially added2H4, prepare V2O5Concentration is
98.7mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:3, CH3OH and N2H4Volume ratio be 60:2.
(4) the good PS ball template of self assembly is immersed in VO by room temperature29h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 80 DEG C of dry 10h.Then, by sample in argon atmosphere 500 DEG C of annealing 1h.
Embodiment 10
(1) quartz plate is successively respectively ultrasonically treated 80min in acetone, ethyl alcohol, 25min is impregnated in Piranha solution
Afterwards, spare after ultrasonic treatment 40min in deionized water；
(2) ultrasonic disperse 2h in 45mL deionized water is added in 2mLPS ball lotion, PS ball dilution is prepared, by step (1)
The quartz glass suspension cleaned up is immersed in PS ball dilution, is placed in air dry oven, induces 12h, shape in 65 DEG C of evaporations
At PS ball template.
(3) in 80mLCH3In OH solution, vanadium source, 10mLHCl and 1.7mLN are sequentially added2H4, prepare V2O5Concentration is
91.6mmol/L precursor solution；Wherein CH3The volume ratio of OH and HCl is 15:1.875, CH3OH and N2H4Volume ratio be
60:1.275。
(4) the good PS ball template of self assembly is immersed in VO by room temperature210h in blue precursor solution, is pulled out.It is placed in air blast
In drying box, in 70 DEG C of dry 11h.Then, by sample in argon atmosphere 500 DEG C of annealing 1h.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of VO of 3-D ordered multiporous network-like structure2The preparation method of film, which comprises the following steps:
(1) cleaning treatment glass substrate；
(2) polystyrene microsphere is adhered on a glass substrate by vertical infusion process, forms preparation VO2The template of film；
(3) with V2O5For vanadium source, with CH3The mixed solution of OH and HCl is solvent, with N2H4For reducing agent, preparing molar concentration is
The VO of 10~100mmol/L2Precursor solution；
(4) by step (2) preparation VO obtained2The template of film is immersed in VO made from step (3)2In precursor solution, pull out
Dry afterwards, annealing, forms the VO of 3-D ordered multiporous network-like structure on a glass substrate2Film.
2. a kind of VO of 3-D ordered multiporous network-like structure according to claim 12The preparation method of film, feature
Be, in step (1), clean glass substrate the step of are as follows: by quartz glass pass sequentially through acetone and EtOH Sonicate processing after,
5~30min is impregnated in Piranha solution, is ultrasonically treated 30~60min in deionized water.
3. a kind of VO of 3-D ordered multiporous network-like structure according to claim 12The preparation method of film, feature
It is, in step (2), vertical infusion process is after diluting polystyrene spheres lotion by deionized water, and ultrasonic disperse is made vertical
Dipping solution；Glass substrate is immersed in vertical dipping solution, will be impregnated with the vertical dipping solution of glass substrate 60~
70 DEG C of evaporations induce 10~12h, and VO is made after taking-up2The template of film.
4. a kind of VO of 3-D ordered multiporous network-like structure according to claim 32The preparation method of film, feature
It is, when diluting polystyrene spheres lotion by deionized water, the volume ratio of polystyrene spheres lotion and deionized water is (1-
2): (25-50)；Polystyrene spheres in polystyrene spheres lotion are having a size of 200-1500nm.
5. a kind of VO of 3-D ordered multiporous network-like structure according to claim 42The preparation method of film, feature
It is, when diluting polystyrene spheres lotion by deionized water, the volume ratio of polystyrene spheres lotion and deionized water is 1:25.
6. a kind of VO of 3-D ordered multiporous network-like structure according to claim 12The preparation method of film, feature
It is, in step (3), CH3In the mixed solution of OH and HCl, CH3The volume ratio of OH and HCl is 15:(1-3)；The N of addition2H4
And CH3OH volume ratio is (0.25-2): 60.
7. a kind of VO of 3-D ordered multiporous network-like structure according to claim 12The preparation method of film, feature
It is, in step (4), prepares VO2The template of film is in VO2Soaking time in precursor solution is 3~10h.
8. a kind of VO of 3-D ordered multiporous network-like structure according to claim 12The preparation method of film, feature
It is, in step (4), VO will be prepared2The template of film is in VO2It is impregnated in precursor solution, dry 8~12h, dry after pulling out
Temperature is 60~100 DEG C；Annealing temperature is 450~500 DEG C, and annealing time is 1~2h.
9. a kind of VO for the 3-D ordered multiporous network-like structure prepared by claim 1-8 any one preparation method2It is thin
Film, which is characterized in that the VO2Film is honeycomb, is made of multiple holes, and the edge of each hole is VO2Particle side,
The VO2Particle side is by multiple VO2Particle is connected to form, and adjacent holes share a VO2Particle side；The size of each hole
For 200-1500nm.
10. a kind of VO of 3-D ordered multiporous network-like structure as claimed in claim 92Film intelligent glass field application,
It is characterized in that, working as VO2Film is applied at intelligent glass field, VO2The infrared light modulation capability of film is 8.2%-
10.8%, it be light modulation ability at 2500nm in wavelength is 36.4%-59.5%.
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| CN112624214A (en) * | 2020-12-28 | 2021-04-09 | 苏州大学张家港工业技术研究院 | Magnetic nickel oxide film and preparation method thereof |
| CN112811826A (en) * | 2020-12-30 | 2021-05-18 | 西安交通大学 | SnS2Two-dimensional ordered nano-pore film, preparation method and application thereof |
| ES2955079A1 (en) * | 2022-04-20 | 2023-11-28 | Univ Cadiz | PROCEDURE FOR PREPARING THIN VO2 FILMS WITH THERMOCHROMIC EFFECT AT LOW TEMPERATURE AND IMPROVED LIGHT TRANSMITANCE (Machine-translation by Google Translate, not legally binding) |
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| CN105254185A (en) * | 2015-09-15 | 2016-01-20 | 中国建材国际工程集团有限公司 | Method for preparing porous-structure VO2 film with polystyrene bead as soft template |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624214A (en) * | 2020-12-28 | 2021-04-09 | 苏州大学张家港工业技术研究院 | Magnetic nickel oxide film and preparation method thereof |
| CN112624214B (en) * | 2020-12-28 | 2023-06-23 | 苏州大学张家港工业技术研究院 | Magnetic nickel oxide film and preparation method thereof |
| CN112811826A (en) * | 2020-12-30 | 2021-05-18 | 西安交通大学 | SnS2Two-dimensional ordered nano-pore film, preparation method and application thereof |
| ES2955079A1 (en) * | 2022-04-20 | 2023-11-28 | Univ Cadiz | PROCEDURE FOR PREPARING THIN VO2 FILMS WITH THERMOCHROMIC EFFECT AT LOW TEMPERATURE AND IMPROVED LIGHT TRANSMITANCE (Machine-translation by Google Translate, not legally binding) |
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