CN104817280A - Preparation method of red photonic crystal structure color thin film with photo-catalytic effect - Google Patents
Preparation method of red photonic crystal structure color thin film with photo-catalytic effect Download PDFInfo
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Abstract
The invention discloses a preparation method of a red photonic crystal structure color thin film with a photo-catalytic effect. The method comprises the following steps: firstly mixing SiO2 microsphere powder with particle diameter of 285+/-5 nm and polyvinylpyrrolidone and then adding water to prepare PVP (Polyvinyl Pyrrolidone)-modified SiO2 microspheres; then adding into absolute ethyl alcohol to perform ultrasonic treatment to obtain emulsion containing SiO2 microspheres; then preparing mixed solution of lithium hydroxide-ethanol and zinc acetate-ethanol; dropwise adding the emulsion containing SiO2 microspheres into the mixed solution, reacting and then filtering, washing, centrifuging, drying and thermally treating precipitate to prepare the SiO2@ZnO core-shell structure microspheres with the photo-catalytic effect; next adding ethanol into the SiO2@ZnO core-shell structure microspheres to perform ultrasonic dispersion to prepare emulsion; finally vertically inserting a glass substrate into the emulsion by using a vertical deposition method to generate the red photonic crystal structure color thin film with the photo-catalytic effect. The method is simple and easy, causes no pollution to environment, can realize large-scale industrial production and has broad application prospect.
Description
Technical field
The invention belongs to photonic crystal structure color film preparing technical field, be specifically related to a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect.
Background technology
The generation of photonic crystal structure color is because there is photon band gap in photon crystal material, when bandgap range drops in visible-range, the visible ray of CF will not continue to propagate by opal photonic crystal, these visible rays that can not continue to propagate can be reflected by photonic crystal, finally form coherent diffraction at the photon crystal surface with periodic structure, and produce bright and colourful schemochrome.Can find after the schemochrome research of occurring in nature and artificial preparation, this kind of material have bright-colored, will never fade, preparation cycle is short and advantages of environment protection, in display, decorate, there is good application in the field such as false proof.But, at present blank is still for the research of photonic crystal structure color film in photochemical catalysis.As Chinese invention patent application CN201310205537.7 discloses a kind of preparation method of red photon crystalline structure color glaze, obtain on ceramic body surface with the self-assembling technique of silicon dioxide microsphere, this red photon crystalline structure look has good colouring effect, but the photocatalysis performance of this red photon crystalline structure look material is not described.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect, the method is simple to operate, low for equipment requirements, environmentally safe, be applicable to industrialization scale operation, the red photon crystalline structure look film obtained through the method is bright-colored, will never fade, colouring effect and photocatalysis performance excellence.
The present invention is achieved through the following technical solutions:
There is a preparation method for the red photon crystalline structure look film of photocatalytic effect, comprise the following steps:
1) by 1:(1 ~ 3) mass ratio get the SiO that particle diameter is 285 ± 5nm
2microballoon powder and polyvinylpyrrolidone, add water after mixing, filters after abundant stirring reaction, will precipitate through washing, centrifugal and drying treatment, obtains the SiO that PVP modifies
2microballoon; By the solid-liquid ratio of (0.1 ~ 0.25) g:10mL, by the SiO that PVP modifies
2microballoon adds ultrasonic combination treatment in dehydrated alcohol, obtains containing SiO
2the emulsion of microballoon;
2) by 1:(1 ~ 3) mass ratio get lithium hydroxide and zinc acetate, lithium hydroxide and zinc acetate are used anhydrous alcohol solution respectively, are uniformly mixed, obtain lithium hydroxide-alcohol mixeding liquid and zinc acetate-alcohol mixeding liquid respectively; Zinc acetate-alcohol mixeding liquid is processed under 50 ~ 70 DEG C of waters bath with thermostatic control after stablizing to system temperature, by the volume ratio of 1:1, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid, stirs, obtained mixed solution;
3) by 1:(10 ~ 14) volume ratio, by step 1) in obtained containing SiO
2the emulsion of microballoon is added drop-wise to step 2) in obtained mixed solution, filter after abundant stirring reaction, to precipitate after washing, centrifugal, drying treatment, at 300 ~ 500 DEG C of thermal treatment 2 ~ 6h, obtain the SiO2@ZnO nucleocapsid structure microballoon with photo-catalysis function;
4) SiO2@ZnO core-shell particles is added dehydrated alcohol, be made into the mixed solution that mass percent is 0.25 ~ 0.45%, by mixed solution ultrasonic disperse, the obtained emulsion containing SiO2@ZnO nucleocapsid structure microballoon;
5) glass substrate of cleaning is vertically put into the emulsion containing SiO2@ZnO nucleocapsid structure microballoon, in 40 ~ 60 DEG C of vacuum-dryings to ethanol after volatilization completely, generate the red photon crystalline structure look film with photocatalytic effect at glass substrate surface.
Step 1) described in abundant stirring reaction be adopt magnetic agitation reaction 2 ~ 4h.
Step 1) be according to every 1.5 ~ 2.0g SiO
2microballoon powder adds the consumption proportion of 100mL water to SiO
2deionized water is added in microballoon powder and the mixed system of polyvinylpyrrolidone.
Step 3) described in stir be adopt magnetic agitation reaction 2 ~ 6h.
Step 1) described in the ultrasonic combination treatment time be 10 ~ 20min.
Step 2) described in aluminium hydroxide-alcohol mixeding liquid be the lithium hydroxide of 0.08 ~ 0.12g to be dissolved in 100mL dehydrated alcohol obtained; Described zinc acetate-alcohol mixeding liquid is dissolved in by the zinc acetate of 0.08 ~ 0.36g in 100mL dehydrated alcohol obtaining.
Step 1) and 3) described in centrifugal be under 4000 ~ 8000r/min process 10 ~ 20min.
Step 1) and 3) described in washing be by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Described drying carries out at 60 ~ 80 DEG C.
Step 4) described in the ultrasonic disperse time be 10 ~ 30min.
Step 5) described in the glass substrate of cleaning be first soak 10h in the hydrogen peroxide solution of 30% in mass concentration by glass substrate, then to obtain after deionized water and washes of absolute alcohol 2 ~ 3 times
Compared with prior art, the present invention has following useful technique effect:
First particle diameter, is the SiO of 310 ± 5nm by the preparation method with the red photon crystalline structure look film of photocatalytic effect disclosed by the invention
2microballoon powder and polyvinylpyrrolidone mixing after add water, after filtration, washing, centrifugal drying series of processes, obtain PVP modify SiO
2microballoon; Then by the SiO of PVP modification
2microballoon adds in dehydrated alcohol obtained containing SiO
2the emulsion of microballoon.Secondly, the mixed solution of preparation lithium hydroxide-ethanol and zinc acetate-ethanol, will containing SiO
2the emulsion of microballoon is added drop-wise in this mixed solution, after filtration, washing, centrifugal drying series of processes, the obtained SiO with photo-catalysis function
2@ZnO nucleocapsid structure microballoon, the particle diameter of this nucleocapsid structure microballoon is 310 ± 5nm, due to SiO
2in@ZnO nucleocapsid structure, the existence at interface between kernel and shell, also makes catalytic degradation efficiency strengthen.At SiO
2the ZnO shell introduced in microballoon preparation process, not only increases the effective refractive index of core-shell particles, makes its red schemochrome more obvious, and achieves the photocatalytic degradation function of photonic crystal structure color film to tropeolin-D.Finally, adopt vertical deposition method, make SiO
2@ZnO nucleocapsid structure microballoon becomes red photon crystalline structure look film at glass basis surface self-organization, this schemochrome film presents periodically close-packed arrays, and this schemochrome red pigment color is beautiful, not fugitive color, solves the pigment such as Sudan red, red iron oxide, rhodamine b extra 500 that exists when orchil uses to the harm of human body and environment.Present invention process process is simple, environmentally safe, and energy large-scale commercial production, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the optical photograph that embodiment 1 gained has the red schemochrome film of photocatalytic effect;
Fig. 2 is the X-ray diffractogram that embodiment 1 gained has the red schemochrome film of photocatalytic effect;
Fig. 3 is the scanning electron microscope (SEM) photograph that embodiment 1 gained has the red schemochrome film of photocatalytic effect;
Fig. 4 is the reflected light spectrogram that embodiment 1 gained has the red schemochrome film of photocatalytic effect;
Fig. 5 is the Photocatalytic Degradation of Methyl Orange figure that embodiment 1 gained has the red photon crystalline structure look film of photocatalytic effect.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
The preparation method with the red photon crystalline structure look film of photocatalytic effect disclosed by the invention, the technical scheme of employing is:
First, by SiO
2add water after microballoon powder and polyvinylpyrrolidone mixing, after stirring reaction, filter, by throw out through washing, centrifugal and drying treatment, obtain the SiO that PVP modifies
2microballoon; By the SiO that PVP modifies
2microballoon adds ultrasonic combination treatment in dehydrated alcohol, obtains containing SiO
2the emulsion of microballoon;
Secondly, preparation lithium hydroxide-alcohol mixeding liquid and zinc acetate-alcohol mixeding liquid; Zinc acetate-alcohol mixeding liquid is processed under water bath with thermostatic control after stablizing to system temperature, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid, stirs, obtained mixed solution; Will containing SiO
2the emulsion of microballoon is added drop-wise in this mixed solution, and after abundant stirring reaction, filter, throw out after washing, centrifugal, drying treatment, then through thermal treatment, makes the SiO with photo-catalysis function
2@ZnO nucleocapsid structure microballoon;
Again, by SiO
2@ZnO nucleocapsid structure microballoon adds dehydrated alcohol, through ultrasonic disperse, and the obtained emulsion containing SiO2@ZnO nucleocapsid structure microballoon;
Finally, glass substrate is adopted vertical deposition method, generate the red photon crystalline structure look film with photocatalytic effect.
SiO of the present invention
2the particle diameter of microballoon powder is 285 ± 5nm, and this particle diameter is the SiO of 285 ± 5nm
2microballoon passes through
legal system is standby.Obtained SiO
2the particle diameter of@ZnO nucleocapsid structure microballoon is 310 ± 5nm.
Embodiment 1
There is a preparation method for the red photon crystalline structure look film of photocatalytic effect, comprise the following steps:
(1) in mass ratio for 1:3 takes the SiO that particle diameter is 285 ± 5nm
2microballoon powder and polyvinylpyrrolidone (PVP) some grams, be placed into after mixing in beaker, according to every 2.0g SiO
2the consumption proportion that microballoon powder adds 100mL water adds deionized water in beaker, magnetic agitation mix, reaction 4h after filter, throw out through washing, centrifugal, dry, can obtain PVP modify SiO
2microballoon;
Wherein, centrifugal is process 12min under 7000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 70 DEG C.
(2) precise step (1) obtains the SiO through PVP modification
2microballoon 0.25g, is added to ultrasonic mixing 20min in the dehydrated alcohol of 10mL, has obtained SiO
2the emulsion of microballoon.
(3) in mass ratio for 2.5:1 takes zinc acetate and lithium hydroxide, be dissolved in dehydrated alcohol respectively, be uniformly mixed; Subsequently zinc acetate-alcohol mixeding liquid is placed in 60 DEG C of waters bath with thermostatic control, after system temperature is stable, by the volume ratio of 1:1, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid and stirs, obtained mixed solution; Next emulsion obtained in step (2) is added drop-wise in mixed solution, filters after magnetic agitation reaction 4h, by throw out through washing, centrifugal, dry, and after 300 DEG C of thermal treatment 6h, the SiO with photo-catalysis function can be obtained
2@ZnO nucleocapsid structure microballoon;
Wherein, described aluminium hydroxide-alcohol mixeding liquid is dissolved in by the lithium hydroxide of 0.08g in 100mL dehydrated alcohol obtaining; Described zinc acetate-alcohol mixeding liquid is dissolved in by the zinc acetate of 0.2g in 100mL dehydrated alcohol obtaining.Centrifugal is process 20min under 4000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 80 DEG C.
(4) by the volume ratio of 1:10, by the SiO that step (3) obtains
2@ZnO nucleocapsid structure microballoon and dehydrated alcohol are made into mixed solution according to mass percent 0.4%, subsequently by mixed solution ultrasonic disperse 20min, obtain containing SiO
2the emulsion of@ZnO nucleocapsid structure microballoon;
(5) cleaned slide glass is vertically positioned in this emulsion, and whole system is placed in constant temperature (60 DEG C ± 1 DEG C) vacuum drying oven, approximately pass through 40h, after ethanol volatilization completely, a kind of red photon crystalline structure look film with photocatalytic effect will be generated at glass substrate surface.
In the present invention, the testing method of red photon crystalline structure look film color generation property is as follows:
The reflection spectrum of ultraviolet-visible-near-infrared spectrum instrument is adopted to analyze, INSTRUMENT MODEL: Lamda 950 type, Beckman company of the U.S., wavelength region 175 ~ 3300nm, bandwidth 0.5 ~ 5.0nm, stray light <0.00008%T, wavelength accuracy 0.08nm, scan three times, average.
In the present invention, the testing method of red photon crystalline structure look film light catalytic performance is as follows:
Photocatalytic Degradation On Methyl Orange Solution, the red photon crystalline structure look film with photocatalytic effect that methyl orange solution 80mL that concentration is 15mg/L and obtained film size are 1cm × 2cm is added in light-catalyzed reaction instrument, in unglazed darkroom, react 10min subsequently, make SiO
2@ZnO core-shell particles and tropeolin-D reaction solution fully mix, and reach absorption/desorption equilibrium.Open the mercury lamp of 500W after light-catalyzed reaction starts, and at the uniform velocity stirred by magnetic stirring apparatus, every 15min sampling, measure organic degradation effect by the absorbancy of reaction solution.Absorbancy adopts Lambda-950 type ultraviolet-visible spectrometer to measure.
Using the ratio of methyl orange solution starting point concentration in the concentration and its solution of t as the degradation rate of the solution that is degraded, characterize SiO respectively
2the Photocatalytic Degradation Property of@ZnO microsphere:
C/C
0＝A/A
0
In formula, C
0represent that reaction starts the concentration of solution when the concentration of front solution and photochemical catalysis start rear reaction t time respectively with C, A
0the absorbance at the absorbing wavelength place that solution is maximum when representing that reaction starts front and light-catalyzed reaction t time respectively with A.
Fig. 1, Fig. 4 are respectively the optical photograph with the red schemochrome film of photocatalytic effect and reflection spectrum that the present embodiment obtains, as can be seen from the figure, resulting structures look film color is gorgeous, and in red spectral band, have very strong reflection peak, and colorimetric purity is high.
Fig. 2 is the X-ray diffractogram with the red schemochrome film of photocatalytic effect that the present embodiment obtains, test result shows, in diffraction angle 2 θ=31.90 °, 34.39 °, 36.29 °, 47.60 °, 56.70 °, 62.89 °, 67.85 ° all there is diffraction peak wurtzite ZnO diffraction peak, there is no other dephasign diffraction peak to occur, this demonstrate that sample is pure wurtzite ZnO, and XRD diffraction peak has larger halfwidth, illustrate that ZnO nano grain diameter is less.
Fig. 3 is structural unit---the single dispersing SiO with the red schemochrome film of photocatalytic effect that the present embodiment obtains
2@ZnO scanning electron microscope (SEM) photograph, as can be seen from the figure, the surperficial roughen of silicon-dioxide otherwise smooth, illustrate that zinc oxide is successfully coated on silica sphere, as can be seen from the figure, zinc oxide is the surface that fine granularity is coated on silicon dioxide microsphere equably, and the microballoon after coated still keeps better sphericity, monodispersity is good, microspherulite diameter narrow distribution.
Fig. 5 is the Photocatalytic Degradation of Methyl Orange figure with the red photon crystalline structure look film of photocatalytic effect that the present embodiment obtains, can find the degradation efficiency of tropeolin-D by contrasting coated front and back microballoon, in 90min, 80% is reached to the degradation rate of tropeolin-D through coated complex microsphere, and same time does not almost have Degradation without coated silicon dioxide microsphere to tropeolin-D, demonstrate this function film and there is schemochrome effect and light-catalysed function simultaneously.
Embodiment 2
There is a preparation method for the red photon crystalline structure look film of photocatalytic effect, comprise the following steps:
(1) in mass ratio for 1:2.5 takes the SiO that particle diameter is 285 ± 5nm
2microballoon powder and polyvinylpyrrolidone (PVP) some grams, be placed into after mixing in beaker, according to every 1.5g SiO
2the consumption proportion that microballoon powder adds 100mL water adds deionized water in beaker, magnetic agitation mix, reaction 3h after through washing, centrifugal, dry, can obtain PVP modify SiO
2microballoon;
Wherein, centrifugal is process 20min under 4000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 80 DEG C.
(2) precise step (1) obtains the SiO through PVP modification
2microballoon 0.2g, is added to ultrasonic mixing 20min in 10mL dehydrated alcohol, has obtained SiO
2the emulsion of microballoon.
(3) in mass ratio for 3:1 takes zinc acetate and lithium hydroxide some grams, be dissolved into respectively in dehydrated alcohol, be uniformly mixed; Subsequently zinc acetate-alcohol mixeding liquid is placed in 60 DEG C of waters bath with thermostatic control, after system temperature is stable, by the volume ratio of 1:1, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid and stirs, obtained mixed solution; Next emulsion obtained in step (2) is added drop-wise in mixed solution, filters after magnetic agitation reaction 6h, by throw out through washing, centrifugal, dry, and after 400 DEG C of thermal treatment 5h, the SiO with photo-catalysis function can be obtained
2@ZnO nucleocapsid structure microballoon;
Wherein, described aluminium hydroxide-alcohol mixeding liquid is dissolved in by the lithium hydroxide of 0.1g in 100mL dehydrated alcohol obtaining; Described zinc acetate-alcohol mixeding liquid is dissolved in by the zinc acetate of 0.3g in 100mL dehydrated alcohol obtaining; Centrifugal is process 10min under 8000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 70 DEG C.
(4) by the volume ratio of 1:12, by the SiO that step (3) obtains
2@ZnO nucleocapsid structure microballoon and dehydrated alcohol are made into mixed solution according to mass percent 0.35%, subsequently by mixed solution ultrasonic disperse 30min, obtain containing SiO
2the emulsion of@ZnO nucleocapsid structure microballoon.Cleaned slide glass is vertically positioned in emulsion, and whole system is placed in constant temperature (55 DEG C ± 1 DEG C) vacuum drying oven, approximately pass through 40h, after ethanol volatilization completely, a kind of red photon crystalline structure look film with photocatalytic effect will be generated at glass substrate surface.
In the present invention, the testing method of red photon crystalline structure look film color generation property is as follows:
The reflection spectrum of ultraviolet-visible-near-infrared spectrum instrument is adopted to analyze, INSTRUMENT MODEL: Lamda 950 type, Beckman company of the U.S., wavelength region 175 ~ 3300nm, bandwidth 0.5 ~ 5.0nm, stray light <0.00008%T, wavelength accuracy 0.08nm, scan three times, average.
In the present invention, the testing method of red photon crystalline structure look film light catalytic performance is as follows:
Photocatalytic Degradation On Methyl Orange Solution, the red photon crystalline structure look film with photocatalytic effect that methyl orange solution 70mL that concentration is 15mg/L and the film size that obtains are 1cm × 2cm is added in light-catalyzed reaction instrument, in unglazed darkroom, react 10min subsequently, make SiO
2@ZnO core-shell particles and tropeolin-D reaction solution fully mix, and reach absorption/desorption equilibrium.Open the mercury lamp of 500W after light-catalyzed reaction starts, and at the uniform velocity stirred by magnetic stirring apparatus, every 15min sampling, measure organic degradation effect by the absorbancy of reaction solution.Absorbancy adopts Lambda-950 type ultraviolet-visible spectrometer to measure.
Embodiment 3
There is a preparation method for the red photon crystalline structure look film of photocatalytic effect, comprise the following steps:
(1) in mass ratio for 1:2 takes the SiO that particle diameter is 285 ± 5nm
2microballoon powder and polyvinylpyrrolidone (PVP) some grams, be placed into after mixing in beaker, according to every 2.0g SiO
2the consumption proportion that microballoon powder adds 100mL water adds deionized water in beaker, magnetic agitation mix, reaction 3h after filter, throw out through washing, centrifugal, dry, can obtain PVP modify SiO
2microballoon;
Wherein, centrifugal is process 15min under 5000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 70 DEG C.
(2) precise step (1) obtains the SiO through PVP modification
2microballoon 0.15g, is added to ultrasonic mixing 15min in 10mL dehydrated alcohol, has obtained SiO
2the emulsion of microballoon.
(3) in mass ratio for 2:1 takes zinc acetate and lithium hydroxide some grams, be dissolved into respectively in dehydrated alcohol, be uniformly mixed; Subsequently zinc acetate-alcohol mixeding liquid is placed in 55 DEG C of waters bath with thermostatic control, after system temperature is stable, by the volume ratio of 1:1, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid and stirs, obtained mixed solution; Next be added drop-wise in mixed solution by emulsion obtained in step (2), filter after magnetic agitation reaction 4h, throw out through washing, centrifugal, dry, and after 400 DEG C of thermal treatment 2h, can obtain the SiO with photo-catalysis function
2@ZnO nucleocapsid structure microballoon;
Wherein, described aluminium hydroxide-alcohol mixeding liquid is dissolved in by the lithium hydroxide of 0.12g in 100mL dehydrated alcohol obtaining; Described zinc acetate-alcohol mixeding liquid is dissolved in by the zinc acetate of 0.36g in 100mL dehydrated alcohol obtaining.Centrifugal is process 12min under 7000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 65 DEG C.
(4) by the volume ratio of 1:14, by the SiO that step (3) obtains
2@ZnO nucleocapsid structure microballoon and dehydrated alcohol are made into mixed solution according to mass percent 0.45%, subsequently by mixed solution ultrasonic disperse 15min, obtain containing SiO
2the emulsion of@ZnO nucleocapsid structure microballoon.Cleaned slide glass is vertically positioned in emulsion, and whole system is placed in constant temperature (50 DEG C ± 1 DEG C) vacuum drying oven, approximately pass through 40h, after ethanol volatilization completely, a kind of red photon crystalline structure look film with photocatalytic effect will be generated at glass substrate surface.
Embodiment 4
There is a preparation method for the red photon crystalline structure look film of photocatalytic effect, comprise the following steps:
(1) in mass ratio for 1:1.5 takes the SiO that particle diameter is 285 ± 5nm
2microballoon powder and polyvinylpyrrolidone (PVP) some grams, be placed into after mixing in beaker, according to every 1.8g SiO
2the consumption proportion that microballoon powder adds 100mL water adds deionized water in beaker, magnetic agitation mix, reaction 2h after filter, throw out through washing, centrifugal, dry, can obtain PVP modify SiO
2microballoon;
Wherein, centrifugal is process 16min under 5000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 80 DEG C.
(2) precise step (1) obtains the SiO through PVP modification
2microballoon 0.15g, is added to ultrasonic mixing 10min in 10mL dehydrated alcohol, has obtained SiO
2the emulsion of microballoon.
(3) in mass ratio for 2:1 takes zinc acetate and lithium hydroxide some grams, be dissolved into respectively in dehydrated alcohol, be uniformly mixed; Subsequently zinc acetate-alcohol mixeding liquid is placed in 60 DEG C of waters bath with thermostatic control, after system temperature is stable, by the volume ratio of 1:1, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid and stirs, obtained mixed solution; Next be added drop-wise in mixed solution by emulsion obtained in step (2), filter after magnetic agitation reaction 3h, throw out through washing, centrifugal, dry, and after 400 DEG C of thermal treatment 2h, can obtain the SiO with photo-catalysis function
2@ZnO nucleocapsid structure microballoon.
Wherein, described aluminium hydroxide-alcohol mixeding liquid is dissolved in by the lithium hydroxide of 0.08g in 100mL dehydrated alcohol obtaining; Described zinc acetate-alcohol mixeding liquid is dissolved in by the zinc acetate of 0.16g in 100mL dehydrated alcohol obtaining.Centrifugal is process 10min under 8000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 75 DEG C.
(4) by the volume ratio of 1:10, by the SiO that step (3) obtains
2@ZnO nucleocapsid structure microballoon and dehydrated alcohol are made into mixed solution according to mass percent 0.3%, subsequently by mixed solution ultrasonic disperse 15min, obtain containing SiO
2the emulsion of@ZnO nucleocapsid structure microballoon.Cleaned slide glass is vertically positioned in emulsion, and whole system is placed in constant temperature (45 DEG C ± 1 DEG C) vacuum drying oven, approximately pass through 40h, after ethanol volatilization completely, a kind of red photon crystalline structure look film with photocatalytic effect will be generated at glass substrate surface.
Embodiment 5
There is a preparation method for the red photon crystalline structure look film of photocatalytic effect, comprise the following steps:
(1) in mass ratio for 1:1 takes the SiO that particle diameter is 285 ± 5nm
2microballoon powder and polyvinylpyrrolidone (PVP) some grams, be placed into after mixing in beaker, according to every 1.6g SiO
2the consumption proportion that microballoon powder adds 100mL water adds deionized water in beaker, magnetic agitation mix, reaction 2h after filter, throw out through washing, centrifugal, dry, can obtain PVP modify SiO
2microballoon;
Wherein, centrifugal is process 13min under 7000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 60 DEG C.
(2) precise step (1) obtains the SiO through PVP modification
2microballoon 0.15g, is added to ultrasonic mixing 10min in 10mL dehydrated alcohol, has obtained SiO
2the emulsion of microballoon.
(3) in mass ratio for 1.5:1 takes zinc acetate and lithium hydroxide some grams, be dissolved into respectively in dehydrated alcohol, be uniformly mixed; Subsequently zinc acetate-alcohol mixeding liquid is placed in 50 DEG C of waters bath with thermostatic control, after system temperature is stable, by the volume ratio of 1:1, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid and stirs, obtained mixed solution; Next emulsion obtained in step (2) is added drop-wise in mixed solution, filters after magnetic agitation reaction 4h, by throw out through washing, centrifugal, dry, and after 300 DEG C of thermal treatment 5h, the SiO with photo-catalysis function can be obtained
2@ZnO nucleocapsid structure microballoon;
Wherein, described aluminium hydroxide-alcohol mixeding liquid is dissolved in by the lithium hydroxide of 0.1g in 100mL dehydrated alcohol obtaining; Described zinc acetate-alcohol mixeding liquid is dissolved in by the zinc acetate of 0.15g in 100mL dehydrated alcohol obtaining.Centrifugal is process 16min under 6000r/min, and washing is by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Drying carries out at 80 DEG C.
(4) by the volume ratio of 1:12, by the SiO that step (3) obtains
2@ZnO nucleocapsid structure microballoon and dehydrated alcohol are made into mixed solution according to mass percent 0.25%, subsequently by mixed solution ultrasonic disperse 10min, obtain containing SiO
2the emulsion of@ZnO nucleocapsid structure microballoon.Cleaned slide glass is vertically positioned in emulsion, and whole system is placed in constant temperature (45 DEG C ± 1 DEG C) vacuum drying oven, approximately pass through 40h, after ethanol volatilization completely, a kind of red photon crystalline structure look film with photocatalytic effect will be generated at glass substrate surface.
In sum, the invention provides a kind of bright-colored, will never fade, and there is the preparation method of the red photon crystalline structure look film of photocatalytic effect, by nano-ZnO particle encapsulation to SiO
2photonic crystal structure color film is prepared on the surface of microballoon, thus obtains a kind of red photon crystalline structure look film with photocatalytic effect.Under the irradiation of UV-light, electron-hole pair can be produced after ZnO is stimulated, electronic energy makes the Viability ion-oxygen of hydrogen reduction existed around it, and high performance hole can decomposition catalyst surface attachment water and generate hydroxyl radical free radical, and then the contaminant degradation of catalyst surface is become free of contamination carbonic acid gas and water etc.SiO
2in@ZnO nucleocapsid structure, the existence at interface between kernel and shell, also makes catalytic degradation efficiency strengthen.Further, can also, by heat-treating this red photon crystalline structure look material, be used for strengthening its adhesion strength; After high-temperature heat treatment, colouring effect and the photocatalysis performance of schemochrome film all get a promotion.
Claims (10)
1. there is a preparation method for the red photon crystalline structure look film of photocatalytic effect, it is characterized in that, comprise the following steps:
1) by 1:(1 ~ 3) mass ratio get the SiO that particle diameter is 285 ± 5nm
2microballoon powder and polyvinylpyrrolidone, add water after mixing, filters after abundant stirring reaction, will precipitate through washing, centrifugal and drying treatment, obtains the SiO that PVP modifies
2microballoon; By the solid-liquid ratio of (0.1 ~ 0.25) g:10mL, by the SiO that PVP modifies
2microballoon adds ultrasonic combination treatment in dehydrated alcohol, obtains containing SiO
2the emulsion of microballoon;
2) by 1:(1 ~ 3) mass ratio get lithium hydroxide and zinc acetate, lithium hydroxide and zinc acetate are used anhydrous alcohol solution respectively, are uniformly mixed, obtain lithium hydroxide-alcohol mixeding liquid and zinc acetate-alcohol mixeding liquid respectively; Zinc acetate-alcohol mixeding liquid is processed under 50 ~ 70 DEG C of waters bath with thermostatic control after stablizing to system temperature, by the volume ratio of 1:1, lithium hydroxide-alcohol mixeding liquid is added drop-wise in zinc acetate-alcohol mixeding liquid, stirs, obtained mixed solution;
3) by 1:(10 ~ 14) volume ratio, by step 1) in obtained containing SiO
2the emulsion of microballoon is added drop-wise to step 2) in obtained mixed solution, filter after abundant stirring reaction, to precipitate after washing, centrifugal, drying treatment, at 300 ~ 500 DEG C of thermal treatment 2 ~ 6h, obtain the SiO2@ZnO nucleocapsid structure microballoon with photo-catalysis function;
4) SiO2@ZnO core-shell particles is added dehydrated alcohol, be made into the mixed solution that mass percent is 0.25 ~ 0.45%, by mixed solution ultrasonic disperse, the obtained emulsion containing SiO2@ZnO nucleocapsid structure microballoon;
5) glass substrate of cleaning is vertically put into the emulsion containing SiO2@ZnO nucleocapsid structure microballoon, in 40 ~ 60 DEG C of vacuum-dryings to ethanol after volatilization completely, generate the red photon crystalline structure look film with photocatalytic effect at glass substrate surface.
2. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, is characterized in that, step 1) described in abundant stirring reaction be adopt magnetic agitation reaction 2 ~ 4h.
3. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, is characterized in that, step 1) be according to every 1.5 ~ 2.0g SiO
2microballoon powder adds the consumption proportion of 100mL water to SiO
2deionized water is added in microballoon powder and the mixed system of polyvinylpyrrolidone.
4. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, is characterized in that, step 3) described in stir be adopt magnetic agitation reaction 2 ~ 6h.
5. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, is characterized in that, step 1) described in the ultrasonic combination treatment time be 10 ~ 20min.
6. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, it is characterized in that, step 2) described in aluminium hydroxide-alcohol mixeding liquid be the lithium hydroxide of 0.08 ~ 0.12g to be dissolved in 100mL dehydrated alcohol obtained; Described zinc acetate-alcohol mixeding liquid is dissolved in by the zinc acetate of 0.08 ~ 0.36g in 100mL dehydrated alcohol obtaining.
7. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, is characterized in that, step 1) and 3) described in centrifugal be under 4000 ~ 8000r/min process 10 ~ 20min.
8. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, it is characterized in that, step 1) and 3) described in washing be by precipitation first through deionization washing 2 ~ 4 times, then through washes of absolute alcohol 2 ~ 4 times; Described drying carries out at 60 ~ 80 DEG C.
9. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, is characterized in that, step 4) described in the ultrasonic disperse time be 10 ~ 30min.
10. a kind of preparation method with the red photon crystalline structure look film of photocatalytic effect according to claim 1, it is characterized in that, step 5) described in the glass substrate of cleaning be first soak 10h in the hydrogen peroxide solution of 30% in mass concentration by glass substrate, then to obtain after deionized water and washes of absolute alcohol 2 ~ 3 times.
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Cited By (6)
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| CN105113006A (en) * | 2015-09-21 | 2015-12-02 | 陕西科技大学 | Mono-dispersed spherical zinc sulfide photonic crystal with rough surface and preparation method thereof |
| CN110003882A (en) * | 2019-04-04 | 2019-07-12 | 东华大学 | A kind of structure of controlling temperature color dyestuff and its preparation and application |
| CN114122415A (en) * | 2021-11-24 | 2022-03-01 | 西安交通大学 | Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof |
| CN114392771A (en) * | 2022-02-08 | 2022-04-26 | 西北大学 | Composite nano photocatalytic material and preparation method and application thereof |
| CN114392771B (en) * | 2022-02-08 | 2022-09-30 | 西北大学 | Composite nano photocatalytic material and preparation method and application thereof |
| CN114799162A (en) * | 2022-04-18 | 2022-07-29 | 陕西科技大学 | Mo @ Ag @ Ni core-shell structure powder prepared by chemical plating and preparation method thereof |
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