CN106582892B - Nano-TiO2Coating structure and its preparation method and application - Google Patents

Nano-TiO2Coating structure and its preparation method and application Download PDF

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CN106582892B
CN106582892B CN201610273985.4A CN201610273985A CN106582892B CN 106582892 B CN106582892 B CN 106582892B CN 201610273985 A CN201610273985 A CN 201610273985A CN 106582892 B CN106582892 B CN 106582892B
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coating
tio
nano
matrix
glass
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CN106582892A (en
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李宇展
白安洋
王�华
范江峰
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Beijing Titanium Hi Tech Co Ltd
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Beijing Titanium Hi Tech Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0215Coating
    • B01J37/0219Coating the coating containing organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • B01J35/004Photocatalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • B01J35/0046Physical properties of the active metal ingredient
    • B01J35/006Physical properties of the active metal ingredient metal crystallite size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0215Coating
    • B01J37/0228Coating in several steps
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23Oxides
    • C03C17/27Oxides by oxidation of a coating previously applied
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/212TiO2

Abstract

The present invention provides a kind of nano-TiO2Coating structure comprising matrix and the nano-TiO for being carried on matrix surface2Coating.Additionally provide nano-TiO2The preparation method of coating structure, wherein coating basis material using linear titanyl polymer solution, dry, sintering obtains loading nano-TiO on basis material2Coating structure.The nano-TiO prepared by the linear titanyl polymer2Coating structure has excellent photocatalytic effect and super hydrophilic effect, is thus had broad application prospects in the fields such as air purification, water process, deodorization, antibacterial, antifouling, automatically cleaning.

Description

Nano-TiO2Coating structure and its preparation method and application
Technical field
The present invention relates to TiO2Photochemical catalyst field, more particularly to nano-TiO2Coating structure and preparation method thereof and use On the way.
Background technology
In recent years, with the acceleration of global industry process, problem of environmental pollution getting worse, environmental improvement is by generation The extensive attention of national governments of boundary and ordinary populace, wherein government put into terms of environmental improvement huge human and material resources and Financial resources provide support, wherein catalysis material and photocatalysis to the research and industrialization of surrounding purifying material and depollution of environment technology Technology is particularly important.The photochemical catalyst that scholars have researched and developed so far has TiO2、ZnO、WO3、CdS、ZnS、SnO2、Fe3O4 Deng wherein TiO2It is active it is high, stability is good, do not generate secondary pollution, it is harmless, cheap many advantages, such as, As most being paid attention to and the photochemical catalyst with broad prospect of application.
Due to nano-TiO2Surface has oxygenolysis effect and super hydrophilic effect, thus has and decomposes the harmful gas of environment The functions such as body, automatically cleaning, antifog, antibacterial, so nano-TiO2Photochemical catalyst can be used for the depollution of environment, automatically cleaning, efficiently resist Multiple Disciplinary Frontiers such as bacterium.
Nano-TiO in photocatalysis technology2There are mainly two types of forms for the use of photochemical catalyst, i.e., directly use nano-TiO2Powder The suspension system of body, and by nano-TiO2It loads on matrix.Directly use nano-TiO2The suspension system of powder exists saturating Photosensitiveness is poor, light efficiency is low, is needed to nano-TiO after water process2The shortcomings of particle recycled, complex process;By nano-TiO2It is negative Be downloaded on matrix is uniformly to adhere to nano-TiO in matrix surface by certain method2Coating.Nano-TiO2It can be by it after load As stationary phase, pending waste water or gas are generally not present post-processing problem, it can be achieved that continuous operation as mobile phase. In addition, the nano-TiO after load2Than the nano-TiO of suspension2Catalysis Rate is fast, high catalytic efficiency, because of powder in suspension system Easily reunite, keeps the reduction of light-catalyzed reaction contact surface, effective active center few, therefore loaded nano TiO2The development of photochemical catalyst With very important realistic meaning.
Existing load nano-TiO2There are mainly three types of the methods of photochemical catalyst:First method is to utilize sol-gal process Directly nano-TiO is prepared in matrix surface2Film is simultaneously heat-treated;Second method is by nano-TiO2Powder directly disperses At suspension, and matrix surface is loaded to, is then heat-treated;The third method is received using inorganic and organic binder handle Rice TiO2Photocatalyst is heat-treated to matrix surface.
Nano-TiO prepared by above-mentioned second method2Photochemical catalyst is due to TiO2Very loose, photochemical catalyst is combined with carrier It is easy to fall off, practical application is more difficult.Nano-TiO prepared by the third above-mentioned method2Photochemical catalyst, due to inorganic and have Machine binder is to nano-TiO2The coating function of photochemical catalyst, photocatalysis efficiency are low.Therefore using it is more be it is above-mentioned the first Method prepares nano-TiO using sol-gal process on matrix2Film.
CN102888598A discloses a kind of TiO2The preparation method of absorbing membrane is selected, preparing main points includes:By titanium Sour four butyl esters are stirred with complexant acetylacetone,2,4-pentanedione or dimethylformamide, obtained solution A;By catalyst, water and carbon source Additive is added in alcohol solvent, is stirred obtained solution B, and wherein catalyst is acetic acid, salicylic acid or ammonium hydroxide, carbon source addition Object is the polyethylene glycol of molecular weight 2000 or the polyvinyl pyrrolidone of K30 standards;Solution B is added in solution A, is stirred Uniformly, colloidal sol is obtained;Colloidal sol is aged at room temperature, then gel is spin-coated on substrate using spin coating instrument, drying simultaneously obtains Dry film;Finally obtained dry film is heat-treated, obtains a kind of TiO2Select absorbing membrane.
CN102983005A discloses a kind of with TiO2The preparation method of the light anode of compacted zone, is directed to TiO2 The preparation method of colloidal sol, this method include:Butyl titanate, acetylacetone,2,4-pentanedione and ethyl alcohol are uniformly mixed, A liquid is obtained;By lauryl amine, HCl, the mixing of second alcohol and water, obtain B liquid;A liquid is mixed with B liquid, and is stirred, dark place ageing is positioned over, obtains TiO2Clear gel, By TiO2Clear gel is coated on electro-conductive glass, is then placed in calcining at constant temperature in Muffle furnace, is obtained equal on electro-conductive glass Even smooth TiO2Compacted zone.
CN101890358A discloses a kind of float type N-TiO2The preparation method and application of floating bead photochemical catalyst, wherein relating to And arrive TiO2The preparation method of colloidal sol:Butyl titanate, absolute ethyl alcohol, acetylacetone,2,4-pentanedione, urea and water are mixed, with concentrated nitric acid tune Save its pH to 3.5~5.5, stirring makes it fully react, and polyethylene glycol is then added, and heats and stirs and is allowed to fully dissolve, and obtains The TiO of N is mixed to yellow transparent2Colloidal sol;To the TiO for mixing N2Floating bead is added in colloidal sol, floating bead is taken out and dried after dipping, then is set It is calcined in Muffle furnace.
One common feature of above three patent application is exactly to be with butyl titanate, acetylacetone,2,4-pentanedione, absolute ethyl alcohol, water Raw material adjusts pH with acid or alkali, obtains TiO2Colloidal sol, ageing obtain gel, be then thermally treated resulting in TiO again2
Nano-TiO prepared by above-mentioned sol-gel method2Photochemical catalyst has grain size is small, reaction is easy to control, side reaction is few etc. Advantage, but a disadvantage is that being formed by TiO2Coating is that non-porous structure, specific surface area are small;In addition, TiO prepared by sol-gal process2 Coating is easy dry and cracked in the drying process, objectively limits the thickness of manufactured coating, load capacity is limited, leads to its quantum efficiency Low, poor catalytic activity etc. is slow to the purification speed of air and sewage, cannot meet the needs of practical application;Meanwhile gel TiO prepared by sol method2The binding force of coating and matrix is also weaker, is easy to fall off, influences practical effect.Therefore, it carries High TiO2Photocatalysis performance improves load capacity, ensures TiO2It is not easy to split away off from carrier in use, is urgently to solve Certainly the problem of.
Invention content
For current TiO2Technical limitation present in photocatalytic coating, the present invention provides nano-TiOs2 Coating structure, and its preparation method and application.In the nano-TiO of the present invention2In coating structure, nano-TiO2Coating has porous Structure, large specific surface area, coating are firmly combined with matrix, have good photocatalytic effect and super hydrophilic effect.Based on nanometer TiO2The photocatalytic effect of coating has oxygenolysis organic matter, and the functions such as sterilization, antibacterial, mould proof;Meanwhile based on receiving Rice TiO2The super hydrophilic effect of coating, has the function of automatically cleaning, antifog, antifouling etc..
In one aspect of the invention, a kind of nano-TiO is provided2Coating structure, including matrix and it is carried on matrix surface Nano-TiO2Coating, the nano-TiO2Coating includes the nano-TiO of the average grain diameter with 10~50nm2Particle, it is described to receive Rice TiO2The load capacity of coating is per cm2Matrix on 1.0~100 μ g TiO2
In another aspect of the present invention, provides and prepare nano-TiO2The method of coating structure, this method include following step Suddenly:
1) in a solvent by the dissolving of linear titanyl polymer, be configured to solution, wherein in terms of titanium, the solution it is a concentration of 0.3~2 weight %;
2) optionally the surface of coated matrix is pre-processed;
3) prepared linear titanyl polymer solution is uniformly applied on matrix, dry, sintering obtains nano-TiO2 Coating structure,
Wherein, the linear titanyl polymer described in step 1) is the Ti-O keys to repeat to be connected in main chain, side group The linear titanyl polymer of machine group, it includes structural units below:
Wherein R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11;R2Represent OR1Or it represents and is selected from CH3COCHCOCH3And CH3COCHCOOC2H5Complexing group;Condition is to be based on R2The total amount of group, at least 50% R2Base Group represents the complexing group;The number-average molecular weight Mn that the linear titanyl polymer is measured with vapor-pressure osmometry is 2000~ 3000;Not solvent-laden pure titanyl polymer has softening point, and the softening point range that ring and ball method measures is 90~127 DEG C.
It is still another aspect of the present invention to provide nano-TiOs2Coating structure is as photochemical catalyst and/or Superhydrophilic material Expect the purposes in air purification, water process purification, deodorization, antibacterial, fungi-proofing, mould proof, automatically cleaning, antifog and antifouling field.
Description of the drawings
Fig. 1-1 is the infrared spectrum of the linear titanyl polymer in an embodiment of the invention;
Fig. 1-2 is the nuclear magnetic resonance spectroscopy of the linear titanyl polymer in an embodiment of the invention;
Fig. 2-1 is the infrared spectrum of the linear titanyl polymer in another embodiment of the invention;
Fig. 2-2 is the nuclear magnetic resonance spectroscopy of the linear titanyl polymer in another embodiment of the invention;
Fig. 3-1 is the stereoscan photograph of an angle of the coating structure in an embodiment of the invention;
Fig. 3-2 is the stereoscan photograph of another angle of the coating structure in an embodiment of the invention;
Fig. 4 is the stereoscan photograph of the coating structure in another embodiment of the invention;
Fig. 5 is the stereoscan photograph of the coating structure in the another embodiment of the present invention;
Fig. 6 is the stereoscan photograph of the coating structure in yet further embodiment of the invention.
Specific implementation mode
Unless otherwise defined, all technical and scientific terms used herein have fields ordinary skill of the present invention The identical meanings that personnel are generally understood.In the case of inconsistent, the definition in this specification shall prevail.
The present invention provides a kind of nano-TiO2Coating structure, including matrix and the nano-TiO for being carried on matrix surface2Coating, The nano-TiO2Coating includes the nano-TiO of the average grain diameter with 10~50nm2Particle, the nano-TiO2Coating is born Carrying capacity is per cm2Matrix on 1.0~100 μ g TiO2
In the nano-TiO of the present invention2In coating structure, the preferably described nano-TiO2Each nano-TiO in coating2Particle It is made of the fundamental particle or crystallite cluster of a diameter of 2~5nm.
Herein, the grain size of particle or particle is by scanning electron microscopy measurement.
In the nano-TiO of the present invention2In coating structure, the nano-TiO2The thickness of coating is preferably 10nm~500nm, More preferably 50nm~200nm, particularly preferably 80nm~150nm.
In the nano-TiO of the present invention2In coating structure, the nano-TiO2The thickness of coating is equivalent to TiO2Load capacity For every cm2Matrix on 1.0~100 μ g TiO2, preferably per cm2Matrix on about 1.0~3 μ g TiO2, more preferably Per cm2Matrix on about 1.0~1.5 μ g TiO2
In the nano-TiO of the present invention2In coating structure, nano-TiO2TiO in coating2For Anatase, in ultraviolet light It can cause light-catalyzed reaction under excitation.The TiO of Anatase2Its catalytic activity is high, and as the TiO of Rutile Type2When appearance, Its catalytic activity reduces.In addition, under ultraviolet excitation, nano-TiO can be also induced2The Superhydrophilic of coating reacts.
In the nano-TiO of the present invention2In coating structure, the nano-TiO2Coating is colourless and/or transparent.Nothing Color and/or transparent coating have high light transmittance, can effectively pass through ultraviolet light and visible light.
It is preferred that the nano-TiO of the present invention2The visible light transmittance rate of coating structure is 80% or more, more preferable 90% or more.
It is preferred that the nano-TiO of the present invention2The water contact angle of coating structure is less than 10o, more preferably less than 5o.
In the nano-TiO of the present invention2In coating structure, the nano-TiO2The shape of coating can be with base shape Change and change, e.g. plane or curved surface, spherical or hollow Arbitrary 3 D shape, there is prodigious adaptability and compatibility Property.
In the nano-TiO of the present invention2In coating structure, described matrix can be arbitrary shape, e.g. plate, honeycomb Shape, threadiness, spherical or hollow ball-shape.
Described matrix include but not limited to silicon substrate class, metal class, category of glass, ceramic-like, sorbing material class or they Arbitrary combination.In certain embodiments of the present invention, the example of metal class matrix includes:Steel plate, aluminium sheet, titanium plate, copper coin, zinc Plate, nickel foam, foamed aluminium, aluminum honeycomb etc.;The example of category of glass matrix includes:Sheet glass, glass fabric, hollow glass are micro- Ball, bead, glass spring etc.;The example of ceramic-like matrix includes:Hollow ceramic microspheres, ceramic tile, ceramic wafer, ceramic honey comb Deng;The example of sorbing material class matrix includes:Silica, silica gel, activated carbon, zeolite, molecular sieve etc..The matrix of the present invention may be used also To be selected from other materials, such as cement, quartz sand, expanded perlite, firebrick particle, sawdust, organic polymer, fabric etc., And it is not limited to matrix exemplified as above.
In the nano-TiO of the present invention2In coating structure, the surface layer of preferably described matrix is coarse, carries nanoscale ruler The outer surface of very little protrusion and/or hollow.The outer surface of Nanometer Roughness can enhance nano-TiO2The combination of coating and matrix Power.
The present invention also provides prepare nano-TiO2The method of coating structure, this approach includes the following steps:
1) in a solvent by the dissolving of linear titanyl polymer, be configured to solution, wherein in terms of titanium, the solution it is a concentration of 0.3~2 weight %;
2) optionally the surface of coated matrix is pre-processed;
3) prepared linear titanyl polymer solution is uniformly coated on matrix, dry, sintering obtains nano-TiO2 Coating structure.
Nano-TiO is prepared in the present invention2In the method for coating structure, the linear titanyl polymer described in step 1), It is linear titanyl polymer of the Ti-O keys to repeat to connect organic group in main chain, side group, it includes structure lists below Member:
Wherein R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11;R2Represent OR1Or it represents and is selected from CH3COCHCOCH3And CH3COCHCOOC2H5Complexing group;Condition is to be based on R2The total amount of group, at least 50% R2Base Group represents the complexing group;The number-average molecular weight Mn that the titanyl polymer is measured with vapor-pressure osmometry is 2000~ 3000;Not solvent-laden pure titanyl polymer has softening point, and the softening point range that ring and ball method measures is 90~127 DEG C.
It is preferred that the linear titanyl polymer dissolves in monohydric alcohol with 2~5 carbon atoms or dihydric alcohol, with 3 It is one or more in the ethylene glycol mono-ethers of~8 carbon atoms, toluene or dimethylbenzene.
It is preferred that linear titanium oxide used in the present invention is prepared via a method which:
1) titanate esters are added into reaction vessel, at 50~90 DEG C, chelating agent are added, heating stirring 0.5~5.0 is small When;
2) at 50~90 DEG C, the mixed solution of water and alcohol is added dropwise, stirring 1.5~6 is small at 80~110 DEG C after dripping off When, solvent is removed under reduced pressure after cooling and obtains linear titanyl polymer.
In the method for preparing linear titanium oxide of the present invention, the structure of the preferably described titanate esters is Ti (OR1)4, Middle R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11.It is preferred that butyl titanate.
In the method for preparing linear titanium oxide of the present invention, preferably the chelating agent is acetylacetone,2,4-pentanedione, acetyl second One or both of acetoacetic ester.
The present invention the method for preparing linear titanium oxide in, preferably described in titanate esters, chelating agent and water mole Than being 1:(0.5~1.4):(0.8~1.3).
In the method for preparing linear titanium oxide of the present invention, preferably in the mixed solution of the water and alcohol, alcohol is Water and alcohol rubs in the mixed solution of one or more of monohydric alcohol with 2~5 carbon atoms, the preferably described water and alcohol You are than being 1:(3~20).
Linear titanyl polymer prepared by the present invention can be as nano-TiO2Source, can also as surface modifier, It can disperse in organic solvent to molecule rank, and good film-forming property can improve adhesive force of the coating in different matrix.Such as background Described in technology segment, TiO in the prior art2Photochemical catalyst is prepared by sol-gal process, and there is powders easily to reunite, load capacity It is less, the problems such as insecure is bonded, these problems seriously limit TiO2The application of photochemical catalyst in practice.Using the present invention The linear titanyl polymer-coated basis material prepared, nano-TiO has been obtained after pyrolysis2Coating structure, coating uniform, TiO2It is negative Carrying capacity increases, and is improved with the adhesion strength of matrix, the shortcomings that overcoming the prior art.
Nano-TiO is prepared in the present invention2In the method for coating structure, preferred steps 1) described in solvent include having The monohydric alcohol or dihydric alcohol of 2~5 carbon atoms, the low-boiling methyl ether with 3~8 carbon atoms, toluene or dimethylbenzene It is one or more of.In the solution of linear titanyl polymer, in terms of titanium, preferably solution concentration is 0.1~3 weight %, more preferably For 0.3~2 weight %.
Nano-TiO is prepared in the present invention2In the method for coating structure, the coated matrix in step 2) can be appointed The shape of meaning, e.g. plate, cellular, fibrous, spherical or hollow ball-shape.
Described matrix include but not limited to silicon substrate class, metal class, category of glass, ceramic-like, sorbing material class or they Arbitrary combination.In certain embodiments of the present invention, the example of metal class matrix includes:Steel plate, aluminium sheet, titanium plate, copper coin, zinc Plate, nickel foam, foamed aluminium, aluminum honeycomb etc.;The example of category of glass matrix includes:Sheet glass, glass fabric, hollow glass are micro- Ball, bead, glass spring etc.;The example of ceramic-like matrix includes:Hollow ceramic microspheres, ceramic tile, ceramic wafer, ceramic honey comb Deng;The example of the matrix of sorbing material class includes:Silica, silica gel, activated carbon, zeolite, molecular sieve etc..The matrix of the present invention is also Other materials, such as cement, quartz sand, expanded perlite, firebrick particle, sawdust, organic polymer, fabric can be selected from Deng, and it is not limited to matrix exemplified as above.
Nano-TiO is prepared in the present invention2In the method for photocatalytic coating structure, described in step 2) to be coated Matrix pretreatment preferably include to matrix carry out oil removing, derust, one kind in thermal activation, polishing, pickling and anodic oxidation Or it is several.Such as metal class matrix is cleaned and polished, surface cleaning is carried out to category of glass and ceramic-like matrix and heat is lived Change etc..Matrix surface is cleaned by pretreatment, or makes the surface layer of basis material roughening or dashing forward with nano-grade size Rise and/or hollow.The outer surface of Nanometer Roughness can enhance nano-TiO2The binding force of coating and matrix.
Nano-TiO is prepared in the present invention2In the method for coating structure, preferred steps 3) described in coating be selected from rotation One or more of painting, spraying, layer painting, roller coating, flow coat and dipping method.
Nano-TiO is prepared in the present invention2In the method for coating structure, preferred steps 3) described in nano-TiO2Coating It is such as in air, to be sintered at 400~550 DEG C, preferably 450~520 DEG C.The step is to being coated in matrix The titanium oxide coating on surface is heat-treated, and titanyl polymer is resolved into nano-TiO2, accelerate nano-TiO2Particle is in matrix The scattering and permeating on surface acts on, and increases it and is firmly combined with degree with matrix.Wherein selected matrix should be able to be resistant to centainly 450~550 DEG C of the heat treatment temperature of time.For will appear the category of glass matrix of softening, general heat at 400~550 DEG C Processing time is 0.5~2 hour.
The nano-TiO prepared by the method for the present invention2In coating structure, TiO2The thickness of coating is preferably 10nm~500nm, More preferable 50nm~200nm, and particularly preferably 80nm~150nm.
The nano-TiO prepared by the method for the present invention2In coating structure, preferably TiO2The amount of coating is equivalent to every cm2Matrix The TiO of upper 1.0~3 μ g2, more preferably per cm2Matrix on about 1.0~1.5 μ g TiO2
The nano-TiO prepared by the method for the present invention2In photocatalytic coating structure, it is formed by TiO2Particle preferably has The average grain diameter of 20~50nm, particularly 20~30nm.The TiO2Particle is preferably the fundamental particle by a diameter of 2~3nm Or crystallite cluster composition.It can be seen that in the SEM scanning figures of the Si on pieces of an embodiment of the invention:TiO2The size of particle In 20nm or so.
The nano-TiO prepared by the method for the present invention2In photocatalytic coating structure, it is formed by TiO2For Anatase, Photocatalysis hair can be caused under the excitation of ultraviolet light to answer.The TiO of Anatase2Its catalytic activity is high, and as the TiO of Rutile Type2 When appearance, catalytic activity reduces.In addition, under ultraviolet excitation, Superhydrophilic reaction can be also induced.
The nano-TiO prepared by the method for the present invention2In photocatalytic coating structure, preferably TiO2Coating be it is colourless and/or Transparent.Colourless and/or transparent coating has high light transmittance, can effectively pass through ultraviolet light and visible light.
The nano-TiO prepared by the method for the present invention2In photocatalytic coating structure, TiO2The shape of coating is with matrix shape The change of shape and change, e.g. plane or curved surface, spherical shape or hollow Arbitrary 3 D shape, there is prodigious adaptability and simultaneous Capacitive.
The nano-TiO of the present invention2Coating structure can effectively utilize ultraviolet degradation organic pollution, inorganic matter, resist Bacterium, sterilization, mould proof, automatically cleaning, antifog, antifouling etc..
The nano-TiO of the present invention2Coating structure can solve the problems in practical application.As background technology part carries It arrives, the TiO obtained by sol-gal process2Coating is non-porous structure and TiO2Particle is easily reunited, so TiO2Ratio table Face is small, and the photocatalytic activity center of generation is few;Simultaneously because coating is easy cracking, load capacity usually will not be very big.The prior art Another method be use TiO2Organic or inorganic binder is added, since binder is to nano-TiO in suspension wherein2Light The coating function of catalyst, photocatalysis efficiency are low.Linear titanyl polymer in the present invention serves not only as TiO2Source, and It can play the role of surface modifier, be soluble in usual vehicle, solution film forming is good, can improve coating in matrix On binding force, solve TiO2The reunion of particle and the adhesion problem on matrix, while in linear titanyl polymer solution The content of Ti can be adjusted in terms of Ti between 0.1~3 weight %, and load capacity is controllable and can be bigger, such as in glass Load capacity can reach 30 weight % or more on glass fibrofelt.
The nano-TiO of the present invention2Different matrixes may be used in coating structure, using various matrixes, develops nano-TiO2It applies Application and large-scale production of the layer structure in different field.Nano-TiO is formed in matrix surface2Coating can effectively utilize Ultraviolet degradation organic matter, inorganic matter have antibacterial, sterilization, automatically cleaning, antifog, anti-pollution function etc..In air purification, sewage The fields such as processing, self-cleaning glass are with a wide range of applications.
The nano-TiO of the present invention2Coating is combined with metal, glass, ceramics, sorbing material and other types of matrix, meeting Generate different applications.When the nano-TiO of the present invention2Coating is formed on glass, the shape especially on the glass of substantially transparent At coating, self-cleaning glass can be manufactured, it can simultaneously antipollution, water vapor and anti-coagulation, can be applied to double glazing The glass of glass of building, windshield, rear window, roof glass, side glass, the rearview mirror of type etc.;Also it can be used In train, the glass of aircraft, the glass of steamer and public utility, such as aquarium glass, glass of cupboard, garden glass, with And for the glass in interior decoration, urban facilities;It can be also used for the displays such as video screen, computer screen, call screen In screen;This kind of coating structure can also be applied to electric control glass, such as liquid crystal electrochomeric glass, electroluminescent glass and light It sends a telegraph in pressure glass.
When using glass fabric as basis material, glass fabric-nano-TiO for being obtained2Coating structure can For use as filtering material, including purification air, purification sewage, removing stink, the furred ceiling that easy cleaning is not allowed in manufacture can also be used to Deng.TiO2Coating, while can be with antibacterial, sterilization etc. other than can be with degradation of organic substances and inorganic matter in filter process.
When using Hollow Glass Sphere as basis material, Hollow Glass Sphere-nano-TiO for being obtained2Coating structure can For crossing drainage, organic matter and inorganic matter in degradation water, while having the function of sterilization.
When using porous ceramics as basis material, porous ceramics-nano-TiO for being obtained2Coating structure can be used for Filtering, the sterilization of water, and for adding the trace element beneficial to health, while can be used for the filtering of air and killing Bacterium.
When using ceramic wafer as basis material, ceramic wafer-nano-TiO for being obtained2Coating structure may be implemented The photocatalytic degradation of machine object has broad application prospects in terms of pollution control, indoor air purification, automatic cleaning coating. TiO2The light-catalyzed reaction of excitation itself makes ceramics have more antibacterial effect.This ceramic tile can be killed applied to hospital and be attached to The bacterium of metope;The thick object because of caused by bacterial action can be reduced due to the soap that is gathered on ground and metope for bathroom Matter plays anti-skidding, antifouling effect;Ammonia concentration therein is can obviously reduce for toilet, makes one not have uncomfortable sense Feel;For keeping a public place clean ceramics as antibacterial in room, harmful bacteria can be not only killed, also removes to a certain extent and is harmful to gas Body purifies the air of a room;City Building exterior wall be can be also used for as photocatalysis ceramics exterior wall tile, having to a certain extent can The atmosphere pollution in city can be mitigated.
The present invention is that linear titanyl polymer is added into certain solvent to obtain the solution of uniform dispersion, is then coated on Different matrix surface is thermally treated resulting in the nano-TiO being supported on matrix under air conditions through 400~550 DEG C2Coating.It should Method is raw material using titanyl polymer, does not use any surfactant, is formed after 400~550 DEG C of heat treatment uniform Coating, coating are firmly combined with matrix, and light degradation organic pollution effect is good, and antibiotic and sterilizing ability is strong, good hydrophilic property, automatically cleaning Ability is strong, and service life is long.
The method of the present invention is simple and convenient, the nano-TiO prepared2Coating is secured, stablizes, and can be mass-produced.It utilizes Ultraviolet photo-induced light-catalyzed reaction has higher catalytic activity, the TiO2Coating water process, air purification, sterilization antibacterial, The photocatalysis fields such as automatically cleaning have broad application prospects.
Embodiment
Technical scheme of the present invention is addressed further under with reference to specific embodiment, but the present invention is not limited to embodiment Given embodiment or implementation result.
Embodiment 1:The preparation of linear titanyl polymer
1) 1mol tetrabutyl titanates are added into reaction vessel, adjust the temperature to 50 DEG C, 0.8mol levulinics are added Ketone reacts 1 hour in 50 DEG C of heating stirrings;
2) 80 DEG C are adjusted the temperature to, the mixed solution of 0.8mol water and 2.5mol isobutanols is instilled, drips off continuation at 80 DEG C Heating stirring 2 hours is removed under reduced pressure solvent and obtains the titanyl polymer of yellow after cooling.
It is 92 DEG C that ring and ball method, which measures softening point, and vapour pressure osmometry measures number-average molecular weight Mn=2750.
Yellow 1~2mg of titanyl polymer of gained and the pure KBr of 200mg is finely ground uniformly, it is placed in mold, in tablet press machine On be pressed into transparent sheet, be used for IR spectral characterizations, see Fig. 1-1;In Fig. 1-1,2959cm-1、2922cm-1、2872cm-1Place Peak is the stretching vibration peak of C-H, 1592cm-1、 1531cm-1The peak at place belongs to the C=O (keto in acetyl acetone ligands Form), C=C (enol form), 425cm-1And 543cm-1Absorption peak demonstrate in polymer architecture that there are Ti-O keys.
The yellow titanyl polymer of gained is dissolved in deuterochloroform, is characterized for NMR, the result is shown in Figure 1-2.
Embodiment 2:The preparation of linear titanyl polymer
1) 1mol butyl titanates are added into reaction vessel, 0.5mol acetylacetone,2,4-pentanediones are added, in 90 DEG C of heating stirrings 1.5h;
2) 70 DEG C are adjusted the temperature to, the mixed liquor of 1.2mol water and 6mol n-butanols is instilled, is stirred at 100 DEG C after dripping off 2.5h is depressurized after cooling except solvent obtains the titanyl polymer.
It is 98 DEG C that ring and ball method, which measures softening point, and vapour pressure osmometry measures number-average molecular weight Mn=2930.
1~2mg of titanyl polymer of gained and the pure KBr of 200mg is finely ground uniformly, it is placed in mold, is pressed on tablet press machine At transparent sheet, IR spectral characterizations are used for, see Fig. 2-1;
The titanyl polymer of gained is dissolved in deuterochloroform, is characterized for NMR, as a result sees Fig. 2-2.
Embodiment 3:Nano-TiO is loaded on silicon chip2Coating structure preparation
1) the linear titanyl polymer dissolving prepared embodiment 1 in ethanol, prepares a concentration of 0.4 weight %'s of Ti Solution;
2) silicon chip is dried in the air respectively in acetone, absolute ethyl alcohol and deionized water with the ultrasonic cleaning of 20-40Hz 15 minutes It is dry;
3) titanyl polymer solution is coated on the silicon chip of 2cm × 2cm by the way of spin coating, it is dry, in 500 DEG C of air Lower heat treatment 30 minutes, obtains the uniform load nano-TiO on silicon chip2Coating structure.
To the TiO in the coating structure of gained2Carry out XRD analysis, it was demonstrated that the linear titanyl polymer is after heat treatment Obtained TiO2For Detitanium-ore-type.
Clap from different perspectives the coating structure electromicroscopic photograph as shown in Fig. 3-1 and Fig. 3-2.Found out by figure, gained applies Layer surface is smooth, and thickness is uniform, has porous structure, TiO2The average grain diameter of particle about 20nm.The experimental results showed that:The titanyl Polymer has good film forming, TiO after heat treatment2Coating is carried on Si on pieces well.
Embodiment 4:Nano-TiO is loaded on silicon chip2Coating structure preparation
The step of with embodiment 2, is identical, in addition to prepared linear titanyl polymer solution in terms of Ti a concentration of 0.8 Weight %, using identical condition, spin coating, drying, heat treatment on silicon chip, obtain the uniform load nano-TiO on silicon chip2's Coating structure.
The electromicroscopic photograph of the coating structure is shown in that Fig. 4, gained coating layer thickness are 50nm.
Embodiment 5:Nano-TiO is loaded on quartz glass2Coating structure preparation
1) the titanyl polymer dissolving prepared embodiment 1 in ethanol, prepares the solution of a concentration of 0.4 weight % of Ti;
2) quartz glass plate is divided in acetone, absolute ethyl alcohol and deionized water with the ultrasonic cleaning of 20-40Hz 15 respectively Clock dries;
3) titanyl polymer solution is coated on 2cm × 2cm quartz glass by the way of spin coating, it is dry, in step instrument The thickness for measuring wet film is 80nm;Then the quartz glass plate for being coated with wet film is heat-treated 30 minutes under 500 DEG C of air, Obtain the uniform load nano-TiO on quartz glass2Coating structure, coating layer thickness 30nm.
By nano-TiO obtained as above2Non catalytic crystal coating structure carries out the transmission test under visible light, and transmissivity is 89.2%.
Under room temperature environment, before being coated with titanyl polymer solution, quartz glass 5 is measured with contact angle measurement The contact angle of different location is 72o;Loading TiO2After coating, 5, coating structure surface different location is measured Contact angle, contact angle 5o, illustrate the TiO that this method is prepared2There is coating Superhydrophilic, this characteristic to make TiO2It applies Layer structure has automatically cleaning decontamination, is readily cleaned and the performances such as water-mist-proof.
Embodiment 6:Nano-TiO is loaded on quartz glass2Coating structure preparation
1) the titanyl polymer dissolving prepared embodiment 1 in ethanol, prepares the solution of a concentration of 0.8 weight % of Ti;
2) quartz glass plate is divided in acetone, absolute ethyl alcohol and deionized water with the ultrasonic cleaning of 20-40Hz 15 respectively Clock dries;
3) titanyl polymer solution is coated on 2cm × 4cm quartz glass by the way of dipping, it is dry;Then it will apply The quartz glass plate for being furnished with wet film is heat-treated 60 minutes under 500 DEG C of air, obtains the uniform load nanometer on quartz glass TiO2Coating structure.
Take 5 nano-TiOs obtained2Non catalytic crystal coating structure, using stroke grid method on the surface of the coating structure Grid is drawn, then pasted, torn repeatedly with transparent adhesive tape, observes TiO2The integrated degree of coating evaluates coating knot to paste number Structure surface TiO2The adhesive force of coating.Later, observation water droplet is inserted into water in the contact angle on coating structure surface or by coating structure In, after lifting out, observe the integrality of coating surface moisture film.
Quartz glass-nano-TiO that the present embodiment is obtained2Coating structure is compared with uncoated quartz glass Experiment:In quartz glass-nano-TiO that the present embodiment is obtained2Tap water is sprayed on the surface of coating structure, after having sprayed, Coating surface forms continuous moisture film, and moisture film is all flowed down along matrix, and coating surface is without washmarking;And uncoated quartz glass After spray water, surface forms droplet, and there are washmarkings for matrix surface after water flows away.It is good that this illustrates that coating of the present invention has Hydrophily.
Utilize the quartz glass-nano-TiO of the present embodiment2The Superhydrophilic of coating structure may be used as without wiping Automobile rearview mirror, anti-steam and antifouling glass etc., particularly suitable for outdoor building glass.In addition, can also be urged using its light The performance of agent is for developing various products such as antifouling liquid crystal display.
Current self-cleaning glass is to be applied to building trade, actually can be applied in the super glass neck of photovoltaic Domain.
Take above-described quartz glass-nano-TiO2Coating structure 2cm × 4cm is added in 50ml methyl orange solutions (concentration 15mg/L), the degradation rate with test methyl orange solution after 500W mercury lamps illumination 5 hours are 50%;After 8 hours, methyl orange The degradation rate of solution reaches 80%.
It can be seen that by above experiment:The self-cleaning function of Superhydrophilic self-cleaning glass is shown as:By its coating table In face of the compatibility of water, the contact angle of the drop of water on the coating surface is made to go to zero.When water touches coating, rapidly at it Surface spreading forms uniform moisture film, shows super hydrophilic property, and spot is taken away by the gravity fall of uniform water film, leads to Most of organic or inorganic spot can be removed by crossing which.
It is big that the present invention uses the attainable advantageous effect of above-mentioned technical solution institute mainly to solve self-cleaning glass Crawling caused by when large-scale production, the problems such as appearance of coat is of poor quality, while coating being enabled to more firmly to be incorporated in Glass matrix surface ensure that the service life of coating structure.Self-cleaning glass appearance of coat prepared by the present invention is bright, has Antireflective effect.
Embodiment 7:Nano-TiO is loaded on aluminium flake2Coating structure preparation
1) the linear titanyl polymer dissolving prepared embodiment 2 in ethanol, prepares a concentration of 0.4 weight %'s of Ti Solution;
2) by long 9cm, width 2cm, thickness 0.1cm aluminium flake respectively in acetone, absolute ethyl alcohol with the ultrasonic cleaning of 20-40Hz 15 minutes, the oil stain on its surface is removed, is then aoxidized in phosphoric acid, surface is washed with deionized water after oxidation Residual, dries;
3) titanyl polymer solution is coated on aluminium flake using impregnation method, it is dry, it is small that 2 are heat-treated under 500 DEG C of air When, obtain the uniform load nano-TiO on aluminium flake2Coating structure.
For the SEM photograph of the coating structure as shown in figure 5, it can be seen from Fig. 5 that gained coating surface is smooth, thickness is uniform, transparent Good, the TiO of property2Particle size is 20nm, coating layer thickness 30nm.
Take above-described aluminium flake-nano-TiO2It is molten to be added to 50 ml methyl oranges by coating structure, quality 1.4407g In liquid (concentration 15mg/L), with the absorption spectrum for testing methyl orange solution after 500W mercury lamps illumination 5 hours, degradation rate is 67.5%, after degradation 8 hours, degradation rate 79.3%.
The TiO of 0.0019g is coated on above-described aluminium flake2, the roughness on surface is not considered, it is average in every cm2Coating The TiO of 5.8 μ g2
Take 5 aluminium flake-nano-TiOs obtained2Coating structure draws lattice using grid method is drawn on the surface of the coating structure Then son is pasted with transparent adhesive tape, is torn repeatedly, observe TiO2The integrated degree of coating evaluates coating structure table to paste number Face TiO2The adhesive force of coating.Later, observation water droplet is inserted into the contact angle on coating structure surface or by coating structure in water, is carried After pulling out, the integrality of coating surface moisture film is observed.
To the TiO on aluminium flake2Coating carries out hydrophilicity experiment, can form continuous moisture film in coating surface, moisture film along Coating surface all flows down, and coating surface is without washmarking, without being loaded with TiO2For the aluminium flake of coating after spray water, surface forms water Pearl, there are washmarkings for matrix surface after water flows away.This illustrates that the coating of the present invention has good hydrophily.
According to the above experiment as can be seen that the nano-TiO of the present invention2Coating structure, not only can be with degradation of organic substances, but also had Hydrophily has certain self-cleaning function, can apply on household electrical appliance indoors, have purification air, deodorization, sterilization and Self-cleaning function.
Embodiment 8:Nano-TiO is loaded in titanium sheet2Coating structure preparation
1) linear titanyl polymer dissolving prepared by embodiment 2 is obtained into the molten of a concentration of 0.4 weight % of Ti in ethanol Liquid;
2) by long 9cm, width 2cm, thickness 0.1cm titanium sheet respectively in acetone, absolute ethyl alcohol, pure water with 20-40Hz's It is cleaned by ultrasonic 15 minutes, drying;
3) titanyl polymer solution is coated in titanium sheet using impregnation method, it is dry, 30 points are heat-treated under 500 DEG C of air Clock obtains the uniform load nano-TiO in titanium sheet2Coating structure.
It takes above-described coating structure 1.3459g to be added in 50ml methyl orange solutions (15 mg/L of concentration), uses 500W The degradation rate of mercury lamp illumination 5 hours, methyl orange solution is 82%;After illumination 8 hours, methyl orange is degradable.
The TiO of 0.0020g is coated in above-described titanium sheet2, the roughness on surface is not considered, it is average in every cm2Coating The TiO of 6.2 μ g2
Take 5 titanium sheet-nano-TiOs obtained2Coating structure draws lattice using grid method is drawn on the surface of the coating structure Then son is pasted with transparent adhesive tape, is torn repeatedly, observe TiO2The integrated degree of coating evaluates coating structure table to paste number Face TiO2The adhesive force of coating.Later, observation water droplet is inserted into the contact angle on coating structure surface or by coating structure in water, is carried After pulling out, the integrality of coating surface moisture film is observed.
To the TiO in titanium sheet2Coating carries out hydrophilicity experiment, can form continuous moisture film in coating surface, moisture film along Coating surface all flows down, and coating surface is without washmarking, and without carrying cated titanium sheet after spray water, surface forms droplet, There are washmarkings for matrix surface after water flows away.This illustrates that the coating of the present invention has good hydrophily.
According to the above experiment as can be seen that loading nano-TiO in titanium sheet2Coating structure both can with degradation of organic substances, There is hydrophily again, there is certain self-cleaning function, therefore can apply on household electrical appliance indoors, have purification air, Deodorization, sterilization and self-cleaning function.
Embodiment 9:Nano-TiO is loaded in nickel foam2Coating structure preparation
1) linear titanyl polymer dissolving prepared by embodiment 1 is obtained into the molten of a concentration of 0.4 weight % of Ti in ethanol Liquid;
2) by long 9cm, width 2cm nickel foam respectively in acetone, absolute ethyl alcohol and pure water with the ultrasound of 20-40Hz Cleaning 15 minutes, drying;
3) linear titanyl polymer solution is coated in nickel foam using impregnation method, it is dry, under 500 DEG C of air at heat Reason 30 minutes, obtains the uniform load nano-TiO in nickel foam2Coating structure.
Above-described coating structure 0.5525g is taken to be added in 50ml methyl orange solutions (15 mg/L of concentration), 500W mercury After light shines 8 hours, the degradation rate of methyl orange solution is 57.2%.
On the ultrasonic instrument of working frequency 20Hz, above-described coating structure be ultrasonically treated 2 hours, it is several It falls off without powder.
It is manufactured in the present embodiment that nano-TiO is loaded in nickel foam2Coating structure it is with good stability, through excessive After secondary use, recovery photocatalytic activity can be regenerated completely by the straightforward procedures such as heating and washing, and continue to keep good Stability.
The coating structure utilizes TiO2Photocatalysis coating can be applied to organic matter degradation, the indoor formaldehyde that can degrade, It can sterilize, deodorization etc., can be used for filtering.
Embodiment 10:Nano-TiO is loaded on glass fabric2Coating structure preparation
1) linear titanyl polymer dissolving prepared by embodiment 2 is obtained into the molten of a concentration of 0.4 weight % of Ti in ethanol Liquid;
2) glass fabric is cut into the square that the length of side is 2cm, activated in the hot water;
3) titanyl polymer solution is coated on glass fabric using impregnation method, it is dry, under 480 DEG C of air at heat Reason 30 minutes, obtains the uniform load nano-TiO on glass fabric2Coating structure.
For the electromicroscopic photograph of the coating structure as shown in fig. 6, it can be seen from Fig. 6 that gained coating surface is smooth, thickness is uniform.
It takes above-described coating structure 0.2859g to be added in 50ml methyl orange solutions (15 mg/L of concentration), uses 500W The degradation rate of methyl orange solution is 88.8% after mercury lamp illumination 8 hours.
On the ultrasonic instrument of working frequency 20Hz, TiO is coated with to this2The glass fabric of coating is ultrasonically treated 2 hours, 0.1 weight % of powder expulsion rate.
It is manufactured in the present embodiment that TiO is loaded on glass fabric2Coating structure, may be used as filtering material degradation water In pollutant;It can also be sterilized using glass fabric, deodorization etc..
Embodiment 11:Nano-TiO is loaded on porous ceramics2Coating structure preparation
1) linear titanyl polymer dissolving prepared by embodiment 1 is obtained into the molten of a concentration of 0.9 weight % of Ti in ethanol Liquid;
2) porous ceramics is cleaned;
3) linear titanyl polymer solution is coated on porous ceramics using impregnation method, it is dry, under 520 DEG C of air Heat treatment 1.5 hours, obtains loading nano-TiO on porous ceramics2Coating structure.
Above-described coating structure 6.1924g is taken, is added in 50ml methyl orange solutions (15 mg/L of concentration), is used After 500W mercury lamps illumination 5 hours, the degradation rate of methyl orange solution is 58.0%;After illumination 8 hours, degradation rate 78.0%.
On the ultrasonic instrument of working frequency 20Hz, TiO is coated with to this2The porous ceramics of coating is ultrasonically treated 120 minutes, powder was almost without falling off.
It is manufactured in the present embodiment that nano-TiO is loaded on porous ceramics2Coating structure utilize TiO2Photocatalysis coating, can With indoor formaldehyde of degrading, can sterilize, deodorization etc..
Embodiment 12:Nano-TiO is loaded over a molecular sieve2Coating structure preparation
1) linear titanyl polymer dissolving prepared by embodiment 1 is obtained into the molten of a concentration of 0.2 weight % of Ti in ethanol Liquid;
2) molecular sieve is cleaned;
3) linear titanyl polymer solution is coated using impregnation method over a molecular sieve, it is dry, under 500 DEG C of air at heat Reason 1.0 hours, obtains uniform load nano-TiO over a molecular sieve2Coating structure.
Above-described coating structure 0.2500g is taken, is added in 50ml methyl orange solutions (15 mg/L of concentration), is used After 500W mercury lamps illumination 4 hours, the degradation rate of methyl orange solution is 76.2%.
It is manufactured in the present embodiment to load nano-TiO over a molecular sieve2Coating structure utilize TiO2Photocatalysis coating, can be with For indoor organic matter in degradation water, inorganic matter, can also sterilize, deodorization etc..
The basic principles and main features and advantages of the present invention of the present invention are described above by embodiment.This field For technical staff it should be appreciated that the present invention is not limited to the above embodiments, what is described in the above embodiment and the description is only say Bright the principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention.

Claims (11)

1. preparing nano-TiO2The method of coating structure, this approach includes the following steps:
1) it in a solvent by the dissolving of linear titanyl polymer, is configured to solution, wherein the solvent, which is selected from, has 2~5 carbon originals The monohydric alcohol of son is one or more in dihydric alcohol, the ethylene glycol mono-ether with 3~8 carbon atoms, toluene and dimethylbenzene, and And in terms of titanium, a concentration of 0.3~2 weight % of the solution;
2) optionally the surface of coated matrix is pre-processed, wherein described matrix is arbitrary shape, the nanometer TiO2The shape of coating changes with the change of base shape;
3) prepared linear titanyl polymer solution is uniformly applied on matrix, dry, sintering obtains loading on matrix Nano-TiO2Coating structure;
Wherein, the linear titanyl polymer described in step 1) is the Ti-O keys to repeat to connect organic group in main chain, side group The linear titanyl polymer of group, it includes structural units below:
Wherein R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11;R2Represent OR1Or it represents and is selected from CH3COCHCOCH3 And CH3COCHCOOC2H5Complexing group;Condition is to be based on R2The total amount of group, at least 50% R2Group represents described Group is complexed;The number-average molecular weight Mn that the linear titanyl polymer is measured with vapor-pressure osmometry is 2000~3000;Without molten The purely linear titanyl polymer of agent has softening point, and the softening point range that ring and ball method measures is 90~127 DEG C.
2. preparing nano-TiO as described in claim 12The method of coating structure, wherein the linear titanyl polymer passes through It is prepared by following method:
A) titanate esters are added in reaction vessel, at 50~90 DEG C, addition chelating agent, heating stirring 0.5~5.0 hour, Described in chelating agent be acetylacetone,2,4-pentanedione, one or both of ethyl acetoacetate;
B) at 50~90 DEG C, the mixed solution of water and alcohol is added dropwise, is stirred 1.5~6 hours at 80~110 DEG C after dripping off, Solvent is removed under reduced pressure after cooling and obtains linear titanyl polymer;
Wherein the molar ratio of titanate esters, chelating agent and water is 1:(0.5~1.4):(0.8~1.3).
3. preparing nano-TiO as claimed in claim 22The method of coating structure, wherein it is poly- to be used to prepare the linear titanyl The structure for closing the titanate esters of object is Ti (OR1)4, wherein R1It is independently from each other-C2H5,-C3H7,-C4H9, and-C5H11
4. preparing nano-TiO as claimed in claim 22The method of coating structure, wherein preparing the linear titanyl polymerization During object, in the mixed solution of the water and alcohol, alcohol is one kind or several in the monohydric alcohol with 2~5 carbon atoms Kind, and the molar ratio of water and alcohol is 1 in the mixed solution of water and alcohol:(3~20).
5. according to any one of claims 1-4 prepare nano-TiO2The method of coating structure, wherein described matrix be plate, Cellular, fibrous, spherical or hollow ball-shape.
6. according to any one of claims 1-4 prepare nano-TiO2The method of coating structure, wherein described matrix include silicon substrate Class, metal class, category of glass, ceramic-like and sorbing material class or their arbitrary combination.
7. preparing nano-TiO as claimed in claim 62The method of coating structure, wherein the metal class matrix include steel plate, Aluminium sheet, titanium plate, copper coin, zine plate, nickel foam, foamed aluminium and aluminum honeycomb;The category of glass matrix includes sheet glass, glass fibre Cloth, hollow glass micro-ball, bead and glass spring;The ceramic-like matrix include hollow ceramic microspheres, ceramic tile, ceramic wafer and Ceramic honey comb;The sorbing material class matrix includes silica, silica gel, activated carbon, zeolite and molecular sieve.
8. according to any one of claims 1-4 prepare nano-TiO2The surface layer of the method for coating structure, wherein described matrix is Coarse, the outer surface of protrusion and/or hollow with nano-grade size.
9. according to any one of claims 1-4 prepare nano-TiO2The method of coating structure, to being coated wherein in step 2) The pretreatment of matrix include that oil removing is carried out to matrix, is derusted, one kind in thermal activation, polishing, pickling and anodic oxidation or several Kind.
10. according to any one of claims 1-4 prepare nano-TiO2The method of coating structure, wherein described in step 3) Apply selected from one or more of spin coating, spraying, layer painting, roller coating, flow coat and dipping mode.
11. according to any one of claims 1-4 prepare nano-TiO2The method of coating structure, wherein described in step 3) Nano-TiO2Coating is sintered to obtain in air, in 450~550 DEG C.
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