CN102219395A - Method for preparing ultra-hydrophilic zinc oxide/titanium oxide film by using layer-by-layer self-assembling method - Google Patents
Method for preparing ultra-hydrophilic zinc oxide/titanium oxide film by using layer-by-layer self-assembling method Download PDFInfo
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Abstract
The invention relates to a method for preparing an ultra-hydrophilic zinc oxide/titanium oxide film by using a layer-by-layer self-assembling method. The method comprises the following steps that: (1) a substrate is immersed in zinc oxide colloid for 3 to 20 minutes, then is washed or rinsed by deionized water, and is dried, such that a substrate with positive electricity on the surface is obtained; (2) the substrate with positive electricity on the surface is immersed in titanium dioxide colloid for 3 to 20 minutes, then is washed or rinsed by deionized water, and is dried, such that a substrate with negative electricity on the surface is obtained; (3) the step (1) and the step (2) are repeated, and finally the substrate is sintered for 0.5 to 4 hours at a temperature of 400 to 500 DEG C, such that an ultra-hydrophilic zinc oxide/titanium oxide film is obtained. The method has advantages of simple equipment and low cost. The obtained film has good hydrophilic performance, and can be used for the determination of chemical oxygen demand in water quality analysis.
Description
Technical field
The invention belongs to the preparation field of super-hydrophilic film, particularly relate to a kind of usefulness layer by layer self-assembly method prepare the method for super hydrophilic zinc oxide/thin film of titanium oxide.
Background technology
In high temperature, the high humidity weather, behind the open cold air-conditioning, windshield glass is easy to form the water smoke of obstructing the view in the automobile.Open warm air conditioner in the northern area car in winter and can cause windshield glass knot mist even frosting equally, when fog condenses in transparent body surface, can cause very big influence, influence officer's the visual field seeing through of light.Surface wettability is the important physico-chemical property of solid surface, and static state by liquid or dynamic contact angle are weighed.When the contact angle on solid surface during less than 5 °, people are referred to as super water wetted material.Film with super hydrophilicity can be applied to aspects such as the window glass of automobile, camera gun, bathroom mirror, this is an anti-fog performance of having used the film of Superhydrophilic, rainy water droplet can have been opened at film surface in very fast tiling, and do not form drop, dielectric surface is very fast wetting by water layer, thereby prevent that water droplet from forming scattering of light on the surface, so just embody the anti-mist characteristic of super-hydrophilic film.
Now had much and can retrieve relevant for patent at formation super-hydrophilic film on glass.Majority is to adopt methods such as spraying, evaporation, electrochemistry, sputter.Chinese patent CN101665328A is disclosed to deposit thin film of titanium oxide with magnetron sputtering method on glass substrate, it has Superhydrophilic.The electrochemical method of the disclosed employing of Chinese patent CN10173637A obtains super-hydrophilic diamond-like carbon composite film with the methanol solution of the titanium dioxide effect deposition by high voltage electric.But these two kinds of methods are owing to its complicated process of preparation, and influence factor is many, and control is difficulty.
Layer-by-Layer (LbL) self-assembly (translations self-assembly layer by layer usually) is a kind of accurately method of controlled function film of thickness for preparing.The substrate of washes clean alternately is immersed in the ionogen or colloid of band xenogenesis electric charge; pass through electrostatic interaction; micelle in ionogen or the colloid can attract each other, and alternating deposit is at substrate surface, and assembling so in layer can obtain the function film of different thickness.
COD is a kind of composite target of evaluation water pollution degree commonly used.It is the abbreviation of English chemical oxygen demand, and Chinese is " chemical oxygen demand (COD) " or " chemical oxygen demand ", is meant to utilize chemical oxidizing agent with the reducing substances in the water (as organism) the oxygen amount that oxygenolysis consumed.It has reflected that water body is subjected to the degree that reducing substances pollutes.Because modal reducing substances is generally organism in water body, therefore, COD has reflected that to a certain extent water body is subjected to the degree of Organic pollutants.COD is high more, pollutes serious more.At present, the measuring method of COD mainly contains potassium dichromate process, acid potassium permanganate oxidation style, clears up spectrophotometry etc. fast.But these above-mentioned methods often all exist water wasting, time-consuming, expense electricity in the process of measuring, energy consumption is high, cost is high, and cause heavy metal contamination.In order to address the above problem, in recent years, many new COD measuring methods are based on reactions such as electrocatalysis, photochemical catalysis or photoelectrocatalysiss, for on-line monitoring COD provides possibility.What research was more at present is the method that the plumbous oxide catalytic oxidation is measured COD, people such as Ai utilize lead dioxide electrode to measure COD[S.Y.Ai, M.G.Gao, Y.Yang, et al. Eletrocatalytic sensor for the determination of chemical oxygen demand using a lead Dioxide modified
Summary of the invention
Technical problem to be solved by this invention provide a kind of usefulness layer by layer self-assembly method prepare the method for super hydrophilic zinc oxide/thin film of titanium oxide, the equipment of this method is simple, and cost is low, the film of acquisition, hydrophilicity is good, also can be used for the mensuration of chemical oxygen demand (COD) in the water quality analysis.
A kind of usefulness of the present invention self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, comprising:
(1) substrates such as glass, quartz or conductive glass are immersed in the zinc oxide colloid 3-20 minute, then with deionized water rinsing or rinsing, remove the unnecessary nano particle that accumulates in the surface, drying obtains the substrate that the surface has positive electricity;
(2) substrate that above-mentioned surface is had positive electricity is immersed in the colloidal tio 2 3-20 minute, then with deionized water rinsing or rinsing, removes the unnecessary nano particle that accumulates in the surface, and drying obtains the substrate that the surface has negative electricity;
(3) repeat above-mentioned step (1) and (2) n-1 time, 1≤n≤12 promptly got super hydrophilic zinc oxide/thin film of titanium oxide at last in 400-500 ℃ of sintering 0.5-4 hour.
Glass described in the above-mentioned steps (1), quartz substrate before use will be through overpicklings, alkali cleaning, drying; Wherein the process of pickling is: it is 7: 3 98wt%H that glass or quartz substrate are immersed in 70-100 ℃ volume ratio
2SO
4With 30wt%H
2O
2In the mixed aqueous solution, soak time is 15-25 minute, soaks the back and cleans up with deionized water; The process of alkali cleaning is: adopting volume ratio is the mixing solutions of 1: 4: 20 25-28wt% strong aqua, 30wt% hydrogen peroxide and deionized water, under room temperature glass or quartz substrate is soaked 15-25 minute, soaks the back and cleans up with deionized water.
Conductive glass substrate described in the above-mentioned steps (1) will clean with acetone and ethanol before use; Wherein to clean be conductive glass to be immersed in the acetone soln 15-30 minute under room temperature to acetone, soaks the back and cleans up with deionized water; It is conductive glass to be immersed in the ethanolic soln 15-30 minute under room temperature that ethanol cleans, and soaks the back and cleans up with deionized water.
Zinc oxide colloidal liquid medium described in the above-mentioned steps (1) is a deionized water, and the mass percent that contains zinc oxide is: 0.01-1wt%, pH value scope is 7-10.
Drying described in above-mentioned steps (1) or (2), its condition is: at nitrogen or air drying.
The liquid medium of the colloidal tio 2 described in the above-mentioned steps (2) is a deionized water, and the massfraction that contains titanium dioxide is: 0.01-1wt%, and the pH scope is 7-10; The anatase phase titanium dioxide colloid is negative in neutrality to the alkaline condition lower surface.
The super hydrophilic zinc oxide/thin film of titanium oxide of gained is (Zinc oxide/titanium dioxide) n in the above-mentioned steps (3), 1≤n≤12, and thickness is 10～500nm, can change thickness by regulating n easily.
Zinc oxide colloid described in the present invention, its preparation process is: two hydration zinc acetates are dissolved in the dehydrated alcohol, stir and backflow 20-120 minute under 80 ℃ condition, form solution A, simultaneously, highly basic is dissolved in the dehydrated alcohol, under the room temperature, magnetic agitation 20-120 minute, form solution B; Wherein, highly basic is lithium hydroxide, sodium hydroxide or potassium hydroxide; Slowly be titrated to solution B in the solution A, and controlled temperature is at 40-80 ℃, after after titration is finished solution being carried out supersound process 40-80 minute in ultrasonic wave, obtain nano zine oxide colloidal sol, wherein two hydration zinc acetates, highly basic and alcoholic acid mol ratio are 1: 1-2: 150-250, and mass percent is two hydration zinc acetate 0.8%-1.2%, highly basic 0.1%-0.5%, dehydrated alcohol 95.3%-99.2%; Because zinc oxide micelle surface in the scope of pH＜9 all has stronger positive electricity (electrokinetic potential), the Coulomb repulsion effect is strong, and colloid has stability preferably.
The negative electricity layer is selected colloidal tio 2 for use among the present invention, described colloidal tio 2, its preparation process is: adopt the presoma of water miscible titanium to come hydrolysis, used presoma is the dihydroxyl lactic acid titanium ammonium of 50wt% or is stable butyl (tetra) titanate or the isopropyl titanate of methyl ethyl diketone.After with deionized water above-mentioned substance being mixed with the aqueous solution that titaniferous concentration is 0.1M-1.0M, add urea as precipitation agent, the mol ratio of urea and titanium is 2: 1-20: 1, urea can not be urged the hydrolysis of materials such as dihydroxyl lactic acid titanium ammonium under the normal temperature, by mixing solutions is heated to 90 degrees centigrade or more than, and refluxed 2 hours or more than, obtain the colloidal sol or the precipitation of anatase phase titanium dioxide.Colloidal sol still precipitates by reflux temperature, reactant concn and return time and decides.If what obtain is precipitation, with the careful washed twice of deionized water, add again in the deionized water through ultra-sonic dispersion and can obtain transparent anatase titanic oxide sol, be weakly alkaline colloidal sol, add a spot of acid or alkali and further regulate its potential of hydrogen.If what obtain is colloid, then remove excessive foreign ion with the method for dialysis.In the dialysis process with colloid to going in the dialysis bag that permeable membrane makes to be immersed in the deionized water, the volume ratio of colloid and deionized water is 1: 5.Soak the deionized water that renews aquatic foods after 24 hours again, three times repeatedly, the colloid of titanium dioxide is able to purifying.
Unless stated otherwise, substrate two sides used among the present invention all deposits multilayer, heterogeneous membrane equally, specially one side is not sealed or handle especially to prepare the single face film.
Prepare multilayer film on the conductive glass of the present invention, the mensuration that can be used for chemical oxygen demand (COD) in the water quality analysis, its concrete grammar of the mensuration of chemical oxygen demand (COD) is in the described water quality analysis: with conductive glass/(Zinc oxide/titanium dioxide) n as anode, with Ag-AgCl is reference electrode, and Pt is a counter electrode, and ultraviolet lighting is incident upon on this transmitter, apply bias voltage simultaneously, measure its photoelectric current curve,, determine the chemical oxygen demand value by the variation of electrochemical properties in the organism photoelectrocatalysioxidization oxidization process.
Common white glass generally is respectively 89% and 11% at transmitance and the reflectivity of wavelength 550nm, and by preparation double-sided multi-layer film, its transmitance and reflectivity at 550nm is respectively greater than 92% with less than 8%.
Water is about 37 ° at the contact angle without the blank glass surface of any processing, by the preparation multilayer film, says that the contact angle at the multilayer film table is almost 0 °.
By on conductive glass, preparing multilayer film, can be used for the mensuration of chemical oxygen demand (COD) in the water quality analysis, have characteristics quick, accurate, non-secondary pollution.
Glass or quartzy iso-electric point are about pH=2.0, and in pH＞2.0 o'clock, glass or quartz surfaces are electronegative; The conductive glass iso-electric point is about pH=4.0, and in pH＞4.0 o'clock, conductive glass surface is electronegative, attracts the Zinc oxide nanoparticle of positively charged by electrostatic interaction.
The present invention utilizes in the scope of pH＜9; it is positive electricity layer that the micelle surface is positively charged zinc oxide; is negative electricity layer to the electronegative silica particle of alkaline range internal surface or in neutrality to the electronegative anatase phase titanium dioxide micelle of weakly alkaline scope internal surface with slightly acidic, has prepared the super hydrophilic multilayer film of (Zinc oxide/titanium dioxide) n by the LbL self-assembly method.Make film pass through LbL self-assembly several times and just can obtain super hydrophilic effect, and, need not to use electrolyte molecule or ion in the preparation process.
Beneficial effect
(1) making equipment of the present invention is simple, cost is low, good practical values is arranged, and zinc oxide, titanium dioxide are inorganic materials, and stable in properties, good heat resistance are suitable for long-acting anti-reflection film, the controllable thickness of film;
(2) the present invention does not use polymer dielectric in the process of preparation film, by having the mineral ion self-assembly of xenogenesis electric charge, even without calcining, does not have possibility to influence the ionogen of performance in the film yet;
(3) the present invention utilizes the LBL method, just can obtain thicker film by simple repetition, obtains the good super-hydrophilic film of hydrophilicity;
(4) the present invention can be used for the mensuration of chemical oxygen demand (COD) in the water quality analysis by prepare multilayer film on conductive glass, has characteristics quick, accurate, non-secondary pollution.
Description of drawings
Fig. 1: a is glass/(Zinc oxide/titanium dioxide) n (n=8) transmittance curve; B is the transmittance curve of blank glass.
Fig. 2: the atomic force microscope photo of glass/(Zinc oxide/titanium dioxide) n (n=12).
Fig. 3: a is the contact angle photo of glass/(Zinc oxide/titanium dioxide) n (n=12), and water tiled fully at the film surface of full nano particle within 5 seconds, and contact angle is almost 0 °; B is the contact angle photo of water at the blank glass substrate surface, and water is about about 37 ° at the contact angle of the glass surface that does not pass through any processing.
Fig. 4: the conductive glass/photocurrent response curve of (Zinc oxide/titanium dioxide) n (n=12) in the electrolytic solution of different concns; Wherein, 4a is the glucose potassium nitrate solution, and the concentration of saltpetre is 1.1mol, and glucose is 0.95mmol; 4b is pure potassium nitrate solution, and its concentration is 1.1mol.
Fig. 5: the absorption spectrum of quartz plate/(Zinc oxide/titanium dioxide) n, (a) n=12 wherein, (b) n=8, (c) n=4, (d) quartz plate/(zinc oxide)
4, (e) blank quartz substrate.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
After glass substrate carried out pickling, alkali cleaning, drying, the white glass substrate on average was about 89% in the transmitance of visible region, as Fig. 1 b.With the dilution of homemade zinc oxide, the mass percent of zinc oxide: 0.01wt% wherein, the pH value is 7.5.Colloidal tio 2 is self-control, and titanium dioxide wherein is the anatase octahedrite phase, and grain-size is about 7nm, and wherein the mass percent of titanium dioxide is 0.01wt%, and the pH value is 7.9.Under the room temperature normal pressure, at first will long 76.2mm, the white glass sheet of wide 25.4mm, thick 1mm is immersed in the colloid that contains zinc oxide 10 minutes, use rinsed with deionized water after 5 minutes then, be immersed in the colloidal tio 2 15 minutes again, this is one deck, successively repeatedly 7 times again, make it reach 8 layers, thickness is 160nm.Its transmitance is measured in dry back.Rete becomes water white transparency, and its transmitance can reach more than 92%, and transmitance can reach 92.7% at wavelength 550nm place, shown in its transmitance Fig. 1 a.
Fig. 1 a can reach 92.7% in wavelength 500nm place transmitance, and the transmitance of the blank glass substrate of Fig. 1 b is 91.5% at the 500nm place; As can be seen, the film of the full nano particle of sedimentary on glass substrate (Zinc oxide/titanium dioxide) n (n=8) can be not influential to the transparency of glass itself, and after plating film, glass still keeps the transparency, can not cause negative impact to its normal use.
Embodiment 2
Under the room temperature normal pressure, at first will long 76.2mm, the sheet glass of wide 25.4mm, thick 1mm is immersed in the colloid that contains zinc oxide 20 minutes, use deionized water rinsing after 5 minutes then, drying is immersed in the colloid of titanium dioxide 10 minutes again, uses deionized water rinsing then 5 minutes, this is one deck for a drying, successively repeatedly 11 times again, make it reach 12 layers, thickness is 260nm.Colloidal tio 2 is self-control, and titanium dioxide wherein is the anatase octahedrite phase, and grain-size is about 7nm, and wherein the mass percent of titanium dioxide is 0.952wt%, and the pH value is 9.1.With homemade zinc oxide colloid with the preparation of distilled water water ultra-sonic dispersion, the mass percent 0.948wt% of zinc oxide wherein, the pH value is 8.9.Its contact angle is measured in film oven dry back.Water tiles fully on zinc oxide/thin film of titanium oxide surface within 5 seconds, and contact angle is almost 0 °, and shown in Fig. 3 (a), in general, water is about 37 ° at the contact angle that does not pass through the glass surface of any processing, shown in Fig. 3 (b).
Cut a fritter sample and carry out the surface topography analysis with atomic force microscope, film is a vesicular structure, as shown in Figure 2; Can observe from Fig. 2, film forming particle is more even, and is not the fine and close vesicular structure that belongs to, and does not produce a large amount of reunions.
Embodiment 3
Under the normal temperature, preparation contains the colloid of zinc oxide, and will make the zinc oxide colloid by oneself and be diluted to mass percent: 0.037wt%, the pH value is 9.2.Preparation contains colloidal tio 2, and homemade TiO 2 sol is obtained with the deionized water dilution, and wherein the mass percent of titanium dioxide is: 0.072wt%, the pH value is 8.5.After conductive substrate FTO carried out acetone, alcoholic acid ultrasonic clean, be dried, under the room temperature normal pressure, at first will long 76.2mm, the white glass sheet of wide 25.4mm, thick 1mm is immersed in the colloid that contains zinc oxide 15 minutes, uses rinsed with deionized water after 3 minutes then, is immersed in the colloidal tio 23 minutes again, this is one deck, successively repeatedly 11 times again, make it reach 12 layers, count FTO/ (Zinc oxide/titanium dioxide)
12, thickness is 260nm.
In the preparation of the colloidal tio 2 of herein using, adopting the dihydroxyl lactic acid titanium ammonium of water miscible 50wt% is precursor.After with deionized water above-mentioned substance being mixed with the aqueous solution that titaniferous concentration is 0.5M, add urea as precipitation agent.The mol ratio of urea and titanium is 5: 1, and mixing solutions is heated to 90 degrees centigrade, and refluxes 5 hours, obtains the precipitation of anatase phase titanium dioxide.Remove unnecessary ion with the method for dialysis, pass through ultrasonicly again, obtain the colloidal sol of titanium dioxide, wherein titanium dioxide is the anatase octahedrite phase, and grain-size is about 5nm.
Adopt this transmitter as anode, putting into starting point concentration is the pure sodium nitrate solution of 1.1mol, is reference electrode with Ag-AgCl, and Pt is a counter electrode, and ultraviolet lighting is incident upon on this transmitter, applies bias voltage simultaneously, measures its photoelectric current curve, as Fig. 4 b.Put into the 0.95mmol glucose potassium nitrate solution that is disposed again after this transmitter cleaned, organism in same reactor in the photoelectrocatalysioxidization oxidization electrolytic solution to be measured, by the variation of electrochemical properties in the organic photoelectric catalytic process, determine the COD value, as Fig. 4 a.
Embodiment 4
After glass substrate carried out pickling, alkali cleaning, drying, the white glass substrate on average was about 89% in the transmitance of visible region, as Fig. 1 b.Preparation contains the colloid of zinc oxide, and colloid is obtained by the dilution of self-control oxide powder and zinc colloid, the mass percent of zinc oxide: 0.082wt% wherein, and the pH value is 8.0.Preparation contains colloidal tio 2, and homemade TiO 2 sol is obtained with the deionized water dilution, and wherein the mass percent of titanium dioxide is: 0.028wt%, the pH value is 8.2.Under the room temperature normal pressure, at first will long 76.2mm, the white glass sheet of wide 25.4mm, thick 1mm is immersed in the colloid that contains zinc oxide 3 minutes, use rinsed with deionized water after 5 minutes then, be immersed in the colloidal tio 2 20 minutes again, this is one deck, successively repeatedly 11 times again, make it reach 12 layers, count glass/(Zinc oxide/titanium dioxide)
12, thickness is 260nm.To resulting glass/(Zinc oxide/titanium dioxide)
12Carry out the mensuration of absorption spectrum, as shown in Figure 5, wherein can find out that from Fig. 5 e blank quartz substrate does not absorb basically to light, Fig. 5 d is the absorption spectrum of pure zinc oxide, its λ
OnsetFor about 368nm, along with adding titanium oxide layer in the film, ABSORPTION EDGE generation blue shift, as Fig. 5 a-5c, this illustrates in the film of full nano particle and exists zinc oxide and two kinds of materials of titanium oxide simultaneously, simultaneously, along with the increase of thicknesses of layers, absorbs and strengthens.
Claims (10)
1. one kind prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide with self-assembly method layer by layer, comprising:
(1) glass, quartz or conductive glass substrate are immersed in the zinc oxide colloid 3-20 minute, then with deionized water rinsing or rinsing, drying obtains the substrate that the surface has positive electricity;
(2) substrate that above-mentioned surface is had positive electricity is immersed in the colloidal tio 2 3-20 minute, and then with deionized water rinsing or rinsing, drying obtains the substrate that the surface has negative electricity;
(3) repeat above-mentioned step (1) and (2) n-1 time, 1≤n≤12 promptly got super hydrophilic zinc oxide/thin film of titanium oxide at last in 400-500 ℃ of sintering 0.5-4 hour.
2. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, and it is characterized in that: the glass described in the step (1), quartz substrate before use will be through overpicklings, alkali cleaning, drying.
3. a kind of usefulness according to claim 2 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, and it is characterized in that: the process of described pickling is: it is 7: 3 98wt%H that glass or quartz substrate are immersed in 70-100 ℃ volume ratio
2SO
4With 30wt%H
2O
2In the mixed aqueous solution, soak time is 15-25 minute, soaks the back and cleans up with deionized water.
4. a kind of usefulness according to claim 2 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, it is characterized in that: the process of described alkali cleaning is: adopting volume ratio is the mixing solutions of 1: 4: 20 25-28wt% strong aqua, 30wt% hydrogen peroxide and deionized water, under room temperature, glass or quartz substrate were soaked 15-25 minute, soak the back and clean up with deionized water.
5. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, it is characterized in that: the conductive glass substrate described in the step (1) will clean with acetone and ethanol before use.
6. a kind of usefulness according to claim 5 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, it is characterized in that: it is conductive glass to be immersed in the acetone soln 15-30 minute under room temperature that described acetone cleans, and soaks the back and cleans up with deionized water; It is conductive glass to be immersed in the ethanolic soln 15-30 minute under room temperature that ethanol cleans, and soaks the back and cleans up with deionized water.
7. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, it is characterized in that: the zinc oxide colloidal liquid medium described in the step (1) is a deionized water, the mass percent that contains zinc oxide is: 0.01-1wt%, pH value scope is 7-10.
8. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, and it is characterized in that: the drying described in step (1) or (2), its condition is: at nitrogen or air drying.
9. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, it is characterized in that: the liquid medium of the colloidal tio 2 described in the step (2) is a deionized water, the massfraction that contains titanium dioxide is: 0.01-1wt%, the pH scope is 7-10.
10. a kind of usefulness according to claim 1 self-assembly method layer by layer prepares the method for super hydrophilic zinc oxide/thin film of titanium oxide, it is characterized in that: the super hydrophilic zinc oxide/thin film of titanium oxide of gained is (Zinc oxide/titanium dioxide) n in the step (3), 1≤n≤12, thickness are 10～500nm.
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| CN105669187A (en) * | 2016-01-14 | 2016-06-15 | 上海大学 | Method for preparing nanometer titanium dioxide film by layer by layer self-assembly method |
| CN113295670A (en) * | 2021-05-21 | 2021-08-24 | 合肥工业大学 | Preparation method of micro-fluidic chip detection device based on SERS substrate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701599A (en) * | 2012-06-08 | 2012-10-03 | 洛阳理工学院 | Method for manufacturing surface bright film of glass handicraft |
| CN102701599B (en) * | 2012-06-08 | 2014-08-13 | 洛阳理工学院 | Method for manufacturing surface bright film of glass handicraft |
| CN103466960A (en) * | 2013-08-27 | 2013-12-25 | 天津儒创新材料科技有限公司 | Preparation method of photoinduction self-cleaning glass |
| CN105669187A (en) * | 2016-01-14 | 2016-06-15 | 上海大学 | Method for preparing nanometer titanium dioxide film by layer by layer self-assembly method |
| CN113295670A (en) * | 2021-05-21 | 2021-08-24 | 合肥工业大学 | Preparation method of micro-fluidic chip detection device based on SERS substrate |
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