CN108529892A - A kind of glass with clean and preparation method with efficient visible light catalysis and Superhydrophilic function - Google Patents
A kind of glass with clean and preparation method with efficient visible light catalysis and Superhydrophilic function Download PDFInfo
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- CN108529892A CN108529892A CN201810307577.5A CN201810307577A CN108529892A CN 108529892 A CN108529892 A CN 108529892A CN 201810307577 A CN201810307577 A CN 201810307577A CN 108529892 A CN108529892 A CN 108529892A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/256—Coating containing TiO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2042—Barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2045—Calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
Abstract
A kind of preparation method of the glass with clean with efficient visible light catalysis and Superhydrophilic function, it is characterized in that using sol-gal process, using sol-gal process, including：The proportioning between orthotitanate film forming matter, alcohol aqueous solvent, rare earth element and sulfur doping element, hydrolysis rate conditioning agent i.e. acid is first established, colloidal sol is prepared by this preparation；Then clean glass substrate is impregnated in sol solutions, process lifts upwards for several times forms compound titanium-based gel wet film on substrate；Finally that wet film is dry, heating firing processing；After measured, film thickness is 0.25~0.3 μm, average grain diameter is 10~20nm, absorption region to light is more than 500nm, sideband expands to 620nm, and to visible light transmittance 70%, which has Superhydrophilic, film is firmly combined with glass matrix, has good function to degradable organic pollutant and sterilizing etc..
Description
Technical field
The present invention relates to self-cleaning glass and preparations with efficient visible light catalysis and Superhydrophilic function, belong to inorganic non-gold
Belong to material manufacture technical field.
Technical background
Glass with clean is also known as easy clean glass, from clear glass etc..It is to refer to one layer of special painting of smearing on the glass surface
After material so that dust either dirty liquid (including aqueous or even oil-containing liquid) be all difficult to be attached to the surface of glass or
It is relatively easily rinsed out by water (or rainwater), such glass surface is very easy to keep cleaning, reduces cleaning glass table
The trouble in face can also reduce water resource waste.
It researches and develops at most at present, has been used with TiO2And TiO2With other metals or the table of other element dopings
Face functional material.This glass with clean has the function of two kinds of photocatalytic and Superhydrophilic etc.：Photo-catalysis function can decompose collection
Gather the volatile organic pollution in glass surface, kills various bacteriums and virus；Photic Superhydrophilic can then make glass sharp
It is washed away with natural rain and reaches removal glass surface dust, glass is made to keep cleaning.Related report is also more, as paper is inscribed
For：《TiO2Glass with clean prepares and its application》,《The discussion of Several Problems in Research for Self-Cleaning Glass》,《Influence glass with clean
The heat treatment process research of photocatalysis performance》,《Influence of the zinc acetate to bacteriostasis rate is adulterated in glass with clean skin covering of the surface》,《It is novel
Ecological Building Materials-glass with clean》,《Fe3+Adulterate TiO2The development of catalytic self-cleaning glass》,《Use ZnFe2O4-TiO2Film improves certainly
Catalytic efficiency under clean glass daylight》,《The development and application of glass with clean and market prospects》Etc..In the market in relation to glass with clean
Commodity are also more.
CN101117273 discloses a kind of glass with clean and its manufacturing method, and glass with clean includes two layers, and first layer is glass
Glass plate, the second layer are self-cleaning coat,.Self-cleaning composition used in the self-cleaning coat is consisting of (weight percent) nanometer two
Titanium oxide 9~23, nano silicon dioxide 0.3~0.75, nanometer metal additive 0.4~2.4, surfactant 0.1~1.0,
Deionized water 75~90.Its manufacturing method is that self-cleaning composition is transported to spray gun, using the compressed air of dry decontamination as
Self-cleaning composition is sprayed to the glass pane surface of the movement of heat, automatically cleaning combination by carrier gas under carrier gas drive
Object is 550~620 DEG C in the solidification temperature of glass surface, and after plated film, hot glass sheet is made by annealing, cutting, bottom sheet
Self-cleaning glass finished product.The product has the function of hydrophilic, degradable organic pollutant and pernicious gas etc..
CN2015100640394 discloses a kind of preparation method of novel nano self-cleaning glass, including glass substrate
And the titanium dioxide layer of setting on the glass substrate, titanium dioxide layer is by the titania nanotube group perpendicular to glass substrate
At the pipe range of titania nanotube is 500~3500nm, and thickness of pipe wall is 10~35nm, and aperture is 10~80nm, two neighboring
The distance of two aperture centers is 60~130nm between titania nanotube, and the crystal structure of titania nanotube is rutile titania
Mine structure.The invention self-cleaning glass has very excellent light transmittance and photocatalytic and self-cleaning performance, can use extensively
In in the industry for having light transmission requirement, playing light transmission, dust-proof, antifog purpose, there is good application prospect.
CN2014102843187 discloses a kind of preparation method of novel self-cleaning glass, which is related to novel self-cleaning glass
The preparation of glass, including pre-process, prepare TiO2Complex sol, spraying, drying and heat treatment, make it have it is super hydrophilic,
The functions such as decomposing organic matter and releasing negative oxygen ion have self-cleaning function.The light transmission rate of the glass with clean up to 90% with
On, wherein the TiO prepared in the preparation method2Complex sol has many advantages, such as nontoxic, tasteless, energy conservation and environmental protection.In addition, should be certainly
The preparation method of clean glass is simple for process, at low cost, easy to operate, self-cleaning effect is good, easy to spread and use.
CN2012103392369 discloses a kind of preparation method of the TiO 2 sol for self-cleaning glass, step
It is as follows：The alcohol that titanium source is titrated to the titanium ion that a concentration of 0.1~4mol/L is obtained in anhydrous alcohols solvent in ice-water bath is molten
Hydrogen peroxide is slowly dropped into alcoholic solution by liquid, the ratio for being 2~10: 1 according to volume ratio, is by mass percentage 1%~5%
Doped source is added, 2~6h of reaction aging obtains sol precursor at room temperature after stirring evenly；PH adjusting agent is added in again will
PH value is adjusted to 6~8 and obtains precursors, is obtained suitable for film forming from clearly after 1~48h of hydro-thermal process at 60~150 DEG C
Clean colloidal sol.The preparation method of the invention can obtain be suitable for film and with visible light-responded ability, be used for self-cleaning glass
The nitrogen-doped titanium dioxide colloidal sol of preparation, self-cleaning glass improves self-cleaning performance to the utilization rate of light after effectively improving film forming.
It is mainly the shortcomings that glass with clean at present：First, photochemical catalyst is low to the utilization rate of visible light, to photocatalysis Decomposition
Organic matter is inefficient with killing bacterium；Second is that the binding strength of photocatalzed film and glass matrix is inadequate, it is still necessary to go deep into
Research is solved.
Invention content
The purpose of the present invention is：It is low to the utilization rate of visible light for current glass with clean photochemical catalyst, to photocatalysis point
The defects of binding strength of the inefficient and photocatalzed film and glass matrix that solve organic matter and killing bacterium is inadequate, this
Invention uses sol-gel method by improving the composition of photocatalysis membrana, it is intended to which being made a kind of having efficient visible light response light
The glass with clean of catalysis and Superhydrophilic function.
The technical scheme is that：A kind of system of the glass with clean with efficient visible light catalysis and Superhydrophilic function
Preparation Method first establishes film forming matter (orthotitanate), solvent (alcohol, water), doped chemical (rare earth member using sol-gel method
Element, sulphur), the optimum proportioning between hydrolysis rate conditioning agent (acid), prepare colloidal sol by this preparation；Then by clean glass substrate
It is impregnated in sol solutions, process lifts upwards for several times forms compound titanium-based gel wet film on substrate；Finally that wet film is dry,
Heat firing processing；
The film forming matter is compound for titanium-based colloidal sol：Orthotitanate is slowly added dropwise and is mixed into the pH alcohol for being 1~3 and acid
In solution, 0.5~2h of high degree of agitation obtains A liquid at room temperature；The rare earth of doping and element sulphur are dissolved in the mixed of alcohol and deionized water
It closes in liquid, mixing obtains B liquid；A liquid is slowly added dropwise into B liquid again, 3~6h of high degree of agitation, is answered at 50~80 DEG C
The titanium-based colloidal sol of conjunction；
The volume ratio of A liquid and B liquid is 3~7: 0.5~3.
When preparing composite titanium colloidal sol, the orthotitanate in A liquid: alcohol: sour mass ratio is 14.2~26.1: 53.9~67.2
: 0.7~5.1；The element sulphur compound adulterated in B liquid: rare earth element be hydrated salt made from earth containing a comparatively high percentage of sodium chloride: alcohol: the mass ratio of deionized water be 0.3~
1.8: 0.2~1.1: 15.8~28.1: 0.6~2.1.
Be metatitanic acid n-propyl or tetrabutyl titanate to prepare the orthotitanate described in colloidal sol, acid be glacial acetic acid, n Propanoic acid or
Hydrochloric acid, the alcohol are ethyl alcohol, normal propyl alcohol or isopropanol, and the rare earth element is lanthanum La, cerium Ce, holmium Ho, erbium Er or thulium Tm
In one kind, the sulphur be thiocarbamide (NH2)2CS, calcium sulfate CaSO4Or barium sulfate BaSO4In one kind.
Glass matrix need to be cleaned up, there must not be trace after drying.
Clean glass substrate is impregnated in 3~10min in sol solution, it is then slow with the linear velocity of 1~5cm/min
Lifting upwards, makes the titanium-based gel wet film for forming doping on substrate, dries.Repeatable " dipping-is lifted-dried " operation, with
Increase the thickness of film.
After the wet film of glass substrate load dries, temperature, which is risen to 460~520 DEG C, with programmed temperature method makes film layer cure,
Obtain sample after cooling.
Beneficial effects of the present invention：1. efficient visible light responsible photocatalytic glass with clean sample obtained, it can respond 400~
The visible light of 760nm carries out photocatalysis, and the hydroxyl radical free radical isoreactivity state oxygen of generation can make the volatility in water and air organic
Pollutant is decomposed into nontoxic water, carbon dioxide and simple inorganic matter, can also kill bacterium；2. sample uses sol-gel
Prepared by method, so as to get the grain size of catalyst is nanoscale in film, and film thickness is less than 0.3 μm and uniform, it is to visible light
Light transmittance is up to 70%, but ultraviolet light and infrared light not easily pass through；3. since the thin-film material of load is hydrophily TiO2, doping
Rare earth and the elements such as sulphur can increase TiO again2Hydrophily, therefore water mist is difficult in upper aggregation；4. the product can be used as roof glass
Glass, door glass, glass curtain wall, a variety of places such as automobile and yacht glass.
Specific implementation mode
Preparation method is sol-gel method.First establish film forming matter (orthotitanate), solvent (alcohol, water), doped chemical
Optimum proportioning between (rare earth element, sulphur), hydrolysis rate conditioning agent (acid) can form height by the composite titan-based colloidal sol of this preparation
Quality thin film layer；Then clean glass substrate is impregnated in sol solutions, process lifts upwards for several times to be formed again on substrate
The titanium-based gel wet film of conjunction；It is finally that wet film is dry, fire processing to get to efficient visible light responsible photocatalytic glass with clean sample
Product.Include the following steps：
1, the preparation of composite titan-based colloidal sol
Film forming matter (orthotitanate), solvent (alcohol, water), doped chemical (rare earth element, sulphur), hydrolysis rate is established to adjust
Optimum proportioning between agent (acid).Orthotitanate is slowly added dropwise in the alcohol and sour mixed solution that pH is 1~3, is swashed at room temperature
0.5~2h of strong stirring obtains A liquid, wherein orthotitanate: alcohol: sour mass ratio be 14.2~26.1: 53.9~67.2: 0.7~
5.1；The rare earth of doping and element sulphur are dissolved in alcohol and the mixed liquor of deionized water, mixing obtains B liquid, wherein element sulphur
Compound: rare earth element is hydrated salt made from earth containing a comparatively high percentage of sodium chloride: alcohol: the mass ratio of deionized water is 0.3~1.8: 0.2~1.1: 15.8~28.1: 0.6
~2.1；A liquid is slowly added dropwise into B liquid again, the volume ratio of wherein A liquid and B liquid is 3~7: 0.5~3；It is fierce at 50~80 DEG C
3~6h is stirred, compound titanium-based colloidal sol is obtained.
It is metatitanic acid n-propyl or tetrabutyl titanate to prepare the orthotitanate described in colloidal sol, and acid is glacial acetic acid, n Propanoic acid or salt
Acid, the alcohol are ethyl alcohol, normal propyl alcohol or isopropanol, and the rare earth element is in lanthanum La, cerium Ce, holmium Ho, erbium Er or thulium Tm
One kind, the sulphur be thiocarbamide (NH2)2CS, calcium sulfate CaSO4Or barium sulfate BaSO4In one kind.
2, on glass matrix prepared by composite titan-based wet film
Glass matrix is cleaned up, is dried, 3~10min in sol solution is impregnated in, then with the line of 1~5cm/min
Speed slowly lifts upwards, makes the titanium-based gel wet film for forming doping on substrate, dries.Repeatable " dipping-is lifted-is dried "
Operation, to increase the thickness of film.
3, the heating cure of titanium-based wet film
Glass substrate after drying loads wet film, and temperature, which is risen to 460~520 DEG C, with programmed temperature method makes film layer cure,
It is cooling to get to the glass with clean sample with efficient visible light catalysis and Superhydrophilic function.
4, composite Nano TiO2It is prepared by powder
Composite Nano TiO2Powder, be by compound titanium-based colloidal sol obtained by temperature programming to 460~520 DEG C, grind
200 mesh are milled to, sample is for used in XRD, UV-vis DRS spectrum, sterile test and the measurement of organic matter degradation experiment.
5, sample object phase and catalytic performance characterization
(1) by composite Nano TiO obtained2Powder XRD determining, analyze sample it is qualitative and quantitative composition, crystallization
Form simultaneously calculates granularity using Scherrer formula.
(2) by composite Nano TiO obtained2Powder UV-vis DRS spectrometer, absorption of the determination sample to light
Range and light transmittance.
(3) by composite Nano TiO obtained2Film scanning electron microscope method (SEM), measurement TiO2The configuration of surface and thickness of film
Degree.
(4) weighing method is used, composite Nano TiO is measured2The weight that film loads on glass.
(5) it uses ultrasonic oscillation washing method to shake 1h, measures load composite Nano TiO on glass2The expulsion rate of film.
(6) ocular estimate is used, composite Nano TiO on glass is observed2The Superhydrophilic of film, and with unsupported glass ratio
Compared with.
(7) use 300W fluorescent lamps (wavelength 400-800nm) for light source, composite Nano TiO is added in irradiation2The methyl of powder
Orange aqueous solution measures the variation (Detection wavelength 466nm) of methyl orange absorbance with spectrophotometry, acquires percent of decolourization.
(8) by composite Nano TiO2Powder is added in sewage containing bacterium, and sterilization rate is measured with " infusion method ".It is thin in sample solution
Bacterium measures the flat band method according to national standards in GB5750-85 and carries out, and coil determination is according to national standards in sample solution
MTF method in GB5750-85 carries out.
Embodiment 1：It is doped with the TiO of La, S2It is prepared by fixed film and powder
1, the preparation of composite titan-based colloidal sol
Tetrabutyl titanate is slowly added dropwise in the ethyl alcohol and glacial acetic acid mixed solution that pH is 3, at room temperature high degree of agitation 1h
Obtain A liquid, wherein orthotitanate: ethyl alcohol: the mass ratio of glacial acetic acid is 22.3: 65.2: 3.0；By the La (NO of doping3)3·6H2O
(NH2)2CS is dissolved in ethyl alcohol and deionized water mixed liquor, and mixing obtains B liquid, wherein (NH2)2CS∶La(NO3)3·
6H2O: ethyl alcohol: the mass ratio of deionized water is 0.3~1.8: 0.2~1.1: 15.8~28.1: 0.6~2.1；It is again that A liquid is slow
It is added dropwise in B liquid, the volume ratio of wherein A liquid and B liquid is 5: 2；High degree of agitation 4h at 50~80 DEG C, it is molten to obtain compound titanium-based
Glue.
2, on glass matrix composite titan-based wet film preparation
The float glass piece of 200mm × 200mm × 4mm is cleaned up, dries, is impregnated in 6min in above-mentioned colloidal sol, so
It is slowly lifted upwards with the linear velocity of 3cm/min afterwards, makes the titanium-based gel wet film for forming doping on substrate, dry.Repeat " leaching
Stain-is lifted-is dried " it operates 1 time.
3, the heating cure of titanium-based wet film
Film layer is set to cure the sheet glass programmed temperature method for having loaded wet film, step is：With the speed of 5 DEG C/min from room
Temperature heating, 100 DEG C, 200 DEG C, 300 DEG C, 400 DEG C it is each keep 30min, final temperature to rise to 500 DEG C, keep after 60min with stove
It is cooled to room temperature to get to finished product.
4, composite Nano TiO2It is prepared by powder
By the compound titanium-based colloidal sol obtained above for being doped with La and S, with the speed of 5 DEG C/min from room temperature,
100 DEG C, 200 DEG C, 300 DEG C, 400 DEG C of each holding 30min, final temperature rise to 500 DEG C, room are cooled to the furnace after keeping 60min
Temperature, grinding obtain finished product.
5, properties of sample testing result
According to the method described in " object phase and catalytic performance characterization " in " specific implementation mode ", to preparing sample tests
It is as follows：
(1) XRD determining shows that the anatase crystal face characteristic peak of sample is clear, is shown to be Detitanium-ore-type, crystalline size is
10nm。
(2) test of ultraviolet-visible diffuse reflectance spectrum instrument shows that sample is more than 500nm to the strong absorption region of light, and sideband expands
610nm is opened up, the light transmittance of sample reaches 70%.
(3) scanning electron microscope method measurement shows TiO2Film surface is smooth, and the thickness of film is about 300nm, and thickness is uniform；TiO2Grain
Diameter is about 10nm, identical as XRD determining result.
(4) TiO is measured using weighing method2Load capacity of the film on glass is 0.13mg/cm2。
(5) ultrasonic oscillation washing method is used to shake 1h, it is 8% to measure expulsion rate, shows that solidification of the film on glass is secured.
(6) hydrophily of visual observations sample and simple glass, water droplet easily disperses after surface sample gets wet.
(7) photodissociation of methyl orange shows that percent of decolourization for 24 hours is 95%.
(8) it is respectively 98.5% and 99% that " infusion method ", which measures bacterium for 24 hours and the sterilization rate of Escherichia coli,.
Embodiment 2：It is doped with the TiO of La2It is prepared by fixed film and powder
Sample preparation is same as Example 1, and (NH is not added with when only preparing composite titan-based colloidal sol2)2The performance of CS, sample are surveyed
Examination is also the same as embodiment 1.The physical property of measurement is as follows：
XRD determining result, ultraviolet-visible diffuse reflectance spectrum instrument test result, scanning electron microscope result, load capacity and expulsion rate
As a result identical or close as 1 corresponding result of embodiment.But sample falls to 85% to the percent of decolourization of methyl orange for 24 hours, for 24 hours carefully
The sterilization rate of bacterium and Escherichia coli falls to 88.5% and 89% respectively, and the hydrophily of sample also has decline.
Embodiment 3：It is doped with the TiO of S2It is prepared by fixed film and powder
Sample preparation and embodiment 1 are identical, and La (NO are not added with when only preparing composite titan-based colloidal sol3)3·6H2O, sample
Performance test is also same
Embodiment 1.The physical property of measurement is as follows：
XRD determining result, ultraviolet-visible diffuse reflectance spectrum instrument test result, scanning electron microscope result, load capacity and expulsion rate
As a result identical or close as 1 corresponding result of embodiment.But sample falls to 81% to the percent of decolourization of methyl orange for 24 hours, for 24 hours carefully
The sterilization rate of bacterium and Escherichia coli falls to 84.2% and 85.1% respectively, and the hydrophily of sample also has decline.
Embodiment 4：Pure TiO2It is prepared by fixed film and powder
Sample preparation and embodiment 1 are identical, and La (NO are not added with when only preparing composite titan-based colloidal sol3)3·6H2O and (NH2)2CS, the performance test of sample is also the same as embodiment 1.The physical property of measurement is as follows：
XRD determining result, ultraviolet-visible diffuse reflectance spectrum instrument test result, scanning electron microscope result, load capacity and expulsion rate
As a result identical or close as 1 corresponding result of embodiment.But sample falls to 35% to the percent of decolourization of methyl orange for 24 hours, for 24 hours carefully
The sterilization rate of bacterium and Escherichia coli falls to 32.8% and 33.1% respectively, and the hydrophily of sample also has decline.
Above-described embodiment shows pure TiO2Ultraviolet light of the photochemical catalyst only to wavelength less than 380nm has response, in visible light
It is poor to the degradation capability and sterilization effect of organic matter down；Doping La and S can expand TiO2The photoresponse range of photochemical catalyst,
The purifying rate of the Escherichia coli to sub- methylene blue, bacterium can be improved again, and the hydrophilicity of sample is also improved.
Claims (7)
1. a kind of preparation method of the glass with clean with efficient visible light catalysis and Superhydrophilic function, it is characterized in that using molten
Glue-gel method, including：First establish orthotitanate film forming matter, alcohol aqueous solvent, rare earth element and sulfur doping element, hydrolysis rate
Conditioning agent is the proportioning between acid, and colloidal sol is prepared by this preparation；Then clean glass substrate is impregnated in sol solutions, is passed through
Lifting forms compound titanium-based gel wet film on substrate upwards for several times；Finally that wet film is dry, heating firing processing；
The film forming matter is compound for titanium-based colloidal sol：Orthotitanate is slowly added dropwise into the pH alcohol for being 1~3 and sour mixed solution
In, 0.5~2h of high degree of agitation obtains A liquid at room temperature；The rare earth of doping and element sulphur are dissolved in alcohol and the mixed liquor of deionized water
In, mixing obtains B liquid；A liquid is slowly added dropwise into B liquid again, 3~6h of high degree of agitation at 50~80 DEG C is obtained compound
Titanium-based colloidal sol；
The volume ratio of A liquid and B liquid is 3~7: 0.5~3.
2. a kind of glass with clean preparation side with efficient visible light catalysis and Superhydrophilic function according to claim 1
Method, it is characterized in that when preparing composite titanium colloidal sol, the orthotitanate in A liquid: alcohol: sour mass ratio is 14.2~26.1: 53.9~
67.2: 0.7~5.1；The element sulphur compound adulterated in B liquid: rare earth element is hydrated salt made from earth containing a comparatively high percentage of sodium chloride: alcohol: the mass ratio of deionized water is
0.3~1.8: 0.2~1.1: 15.8~28.1: 0.6~2.1.
3. prepared by a kind of glass with clean with efficient visible light catalysis and Superhydrophilic function according to claim 1 or claim 2
Method, it is characterized in that it is metatitanic acid n-propyl or tetrabutyl titanate to prepare the orthotitanate described in colloidal sol, acid is glacial acetic acid, n Propanoic acid
Or hydrochloric acid, the alcohol are ethyl alcohol, normal propyl alcohol or isopropanol, the rare earth element is lanthanum La, cerium Ce, holmium Ho, erbium Er or thulium
One kind in Tm, the sulphur are thiocarbamide (NH2)2CS, calcium sulfate CaSO4Or barium sulfate BaSO4In one kind.
4. the glass with clean preparation method according to claim 1 with efficient visible light catalysis and Superhydrophilic function,
Characterized by need to be cleaned up to glass matrix, there must not be trace after drying.
5. according to the system of the glass with clean with efficient visible light catalysis and Superhydrophilic function described in one of Claims 1-4
Preparation Method, it is characterized in that clean glass substrate is impregnated in 3~10min in sol solution, then with the line of 1~5cm/min
Speed slowly lifts upwards, makes the titanium-based gel wet film for forming doping on substrate, dries；Repeat " dipping-is lifted-dried " behaviour
Make, to increase the thickness of film.
6. a kind of glass with clean and preparation with efficient visible light catalysis and Superhydrophilic function according to claim 1,
It is characterized in that after the wet film of glass substrate load dries, temperature, which is risen to 460~520 DEG C, with programmed temperature method makes film layer cure,
Obtain sample after cooling.
7. having the function of efficient visible light catalysis and Superhydrophilic according to what one of claim 1~6 preparation method obtained
Glass with clean.
Priority Applications (1)
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| CN110004705A (en) * | 2019-03-07 | 2019-07-12 | 江苏康润净化科技有限公司 | A kind of fabric preparation method with high efficiency photocatalysis function and service graphene |
| CN113385192A (en) * | 2021-05-31 | 2021-09-14 | 中国十七冶集团有限公司 | Sulfur-doped TiO for water purification system of construction site2Method for producing thin film |
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Application publication date: 20180914 |