CN106582892A - Nanometer TiO2 coating structure, preparation method and uses thereof - Google Patents
Nanometer TiO2 coating structure, preparation method and uses thereof Download PDFInfo
- Publication number
- CN106582892A CN106582892A CN201610273985.4A CN201610273985A CN106582892A CN 106582892 A CN106582892 A CN 106582892A CN 201610273985 A CN201610273985 A CN 201610273985A CN 106582892 A CN106582892 A CN 106582892A
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- tio
- nano
- coating structure
- coating
- matrix
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Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 248
- 238000000576 coating method Methods 0.000 title claims abstract description 248
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 148
- 229920000642 polymer Polymers 0.000 claims abstract description 72
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- 239000010936 titanium Substances 0.000 claims description 33
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
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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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/27—Oxides by oxidation of a coating previously applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- C03C2217/21—Oxides
- C03C2217/212—TiO2
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The present invention provides a nanometer TiO2 coating structure, which comprises a substrate and a nanometer TiO2 coating supported on the substrate surface. The invention further provides a preparation method of the nanometer TiO2 coating structure, wherein the substrate material is coated with a linear titanium oxygen polymer solution, and drying and sintering are performed to obtain the coating structure with the nanometer TiO2 loaded on the substrate material. According to the present invention, the nanometer TiO2 coating structure prepared from the linear titanium oxygen polymer has advantages of excellent photocatalytic effect and super-hydrophilic effect, such that the nanometer TiO2 coating structure has wide application prospects in the fields of air purification, water treatment, deodorization, antibacterial treatment, antifouling treatment, self-cleaning, and the like.
Description
Technical field
The present invention relates to TiO2Photocatalyst field, more particularly to nano-TiO2Coating structure and its production and use.
Background technology
In recent years, with the acceleration of global industry process, problem of environmental pollution is increasingly serious, environmental improvement has been subject to the extensive attention of countries in the world government and ordinary populace, wherein government has put into research and industrialization of the huge human and material resources and financial resources to surrounding purifying material and depollution of environment technology in terms of environmental improvement and provides support, and wherein catalysis material and photocatalysis technology is particularly important.The photocatalyst that so far scholars have researched and developed has TiO2、ZnO、WO3、CdS、ZnS、SnO2、Fe3O4Deng wherein TiO2Active high, good stability, many advantages, such as do not produce secondary pollution, harmless, low price, becomes the photocatalyst most paid attention to and with broad prospect of application.
Due to nano-TiO2Surface has oxidation Decomposition effect and super hydrophilic effect, thus with the functions such as environment harmful gas, automatically cleaning, antifog, antibacterial are decomposed, so nano-TiO2Photocatalyst can be used for multiple Disciplinary Frontiers such as the depollution of environment, automatically cleaning, high-efficiency antimicrobial.
Nano-TiO in photocatalysis technology2The use of photocatalyst mainly has two kinds of forms, i.e., directly use nano-TiO2The suspension system of powder body, and by nano-TiO2Load on matrix.Directly use nano-TiO2The suspension system of powder body has that light transmission is poor, light efficiency is low, need to nano-TiO after water process2Particle is reclaimed, complex process the shortcomings of；By nano-TiO2Load on matrix is uniformly to adhere to nano-TiO in matrix surface by certain method2Coating.Nano-TiO2Can be as fixing phase after load, pending waste water or gas are generally not present post processing problem as mobile phase, are capable of achieving continuous operation.In addition, the nano-TiO after load2Than the nano-TiO for suspending2Catalysis Rate is fast, high catalytic efficiency, because powder is easily reunited in suspension system, makes the reduction of light-catalyzed reaction contact surface, effective active center few, therefore loaded nano TiO2The development of photocatalyst has very important realistic meaning.
Existing load nano-TiO2The method of photocatalyst mainly has three kinds：First method is directly to prepare nano-TiO in matrix surface using sol-gal process2Thin film simultaneously carries out heat treatment；Second method is by nano-TiO2Powder body is directly dispersed into suspension, and loads to matrix surface, then carries out heat treatment；The third method is nano-TiO using inorganic and organic binder bond2Photocatalyst carries out heat treatment to matrix surface.
Nano-TiO prepared by above-mentioned second method2Photocatalyst is due to TiO2Combined with carrier very loosely, photocatalyst is easy to come off, and practical application is more difficult.Nano-TiO prepared by above-mentioned the third method2Photocatalyst, because inorganic and organic binder bond is to nano-TiO2The coating function of photocatalyst, photocatalysis efficiency is low.Therefore using it is more be above-mentioned first method, i.e., nano-TiO is prepared on matrix using sol-gal process2Thin film.
CN102888598A discloses a kind of TiO2The preparation method of absorbing membrane is selected, it prepares main points includes：Butyl titanate is mixed with complexant acetylacetone,2,4-pentanedione or dimethylformamide stirring, obtained solution A；Catalyst, water and carbon source additive are added in alcohol solvent, stirring is mixed to prepare solution B, and wherein catalyst is acetic acid, salicylic acid or ammonia, and carbon source additive is the Polyethylene Glycol of molecular weight 2000 or the polyvidon of K30 standards；Solution B is added in solution A, is uniformly mixed, obtain colloidal sol；Colloidal sol is aged at room temperature, then gel is spin-coated on substrate using spin coating instrument, be dried and obtain dry film；Finally the dry film to obtaining carries out heat treatment, 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 TiO2The preparation method of colloidal sol, the method includes：By butyl titanate, acetylacetone,2,4-pentanedione and ethanol mix homogeneously, A liquid is obtained；By lauryl amine, HCl, the mixing of second alcohol and water, B liquid is obtained；A liquid is mixed with B liquid, and is stirred, be positioned over dark place ageing, obtain TiO2Clear gel, by TiO2Clear gel is coated on electro-conductive glass, is then placed in calcining at constant temperature in Muffle furnace, obtains the TiO of the uniform ground on electro-conductive glass2Compacted zone.
CN101890358A discloses a kind of float type N-TiO2The preparation method and application of floating bead photocatalyst, is directed to TiO2The preparation method of colloidal sol：By the mixing of butyl titanate, dehydrated alcohol, acetylacetone,2,4-pentanedione, carbamide and water, with concentrated nitric acid its pH to 3.5～5.5 is adjusted, stirring makes it fully react, and is subsequently adding Polyethylene Glycol, heat and stir and be allowed to fully dissolving, obtain the TiO that yellow transparent mixes N2Colloidal sol；To the TiO for mixing N2Floating bead is added in colloidal sol, after dipping floating bead is taken out and is dried, then be placed in calcining in Muffle furnace.
One common feature of above three patent application is exactly, with butyl titanate, acetylacetone,2,4-pentanedione, dehydrated alcohol, water as raw material, with acid or alkali pH to be adjusted, and obtains TiO2Colloidal sol, ageing obtain gel, TiO is then thermally treated resulting in again2。
Nano-TiO prepared by above-mentioned sol-gel process2Photocatalyst has the advantages that little particle diameter, easy control of reaction system, side reaction are few, but a disadvantage is that the TiO for being formed2Coating is that non-porous structure, specific surface area are little；In addition, TiO prepared by sol-gal process2Coating is easily dry and cracked in dry run, objectively limits the thickness of manufactured coating, and load capacity is limited, causes its quantum efficiency low, and poor catalytic activity etc. is slow to the purification speed of air and sewage, it is impossible to meet the needs of practical application；Meanwhile, TiO prepared by sol-gel process2Coating is also weaker with the adhesion of matrix, easily comes off, and affects practical effect.Therefore, TiO is improved2Photocatalysis performance, raising load capacity, guarantee TiO2It is difficult in use to be split away off from carrier, is problem demanding prompt solution.
The content of the invention
For current TiO2Technical limitation existing for photocatalytic coating, the invention provides nano-TiO2Coating structure, and its production and use.In the nano-TiO of the present invention2In coating structure, nano-TiO2Coating has loose structure, and specific surface area is big, and coating is firmly combined with matrix, with good photocatalytic effect and super hydrophilic effect.Based on nano-TiO2The photocatalytic effect of coating, with oxidation Decomposition Organic substance, and the function such as sterilization, antibacterial, mould proof；Meanwhile, based on nano-TiO2The super hydrophilic effect of coating, with the function such as automatically cleaning, antifog, antifouling.
In one aspect of the invention, there is provided 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 mean diameter with 10～50nm2Granule, the nano-TiO2The load capacity of coating is every cm2Matrix on 1.0～100 μ g TiO2
In another aspect of the present invention, there is provided prepare nano-TiO2The method of coating structure, the method is comprised the following steps：
1) linear titanyl polymer is dissolved in a solvent, is configured to solution, wherein in terms of titanium, the concentration of the solution is 0.3～2 weight %；
2) surface of the matrix optionally to being applied carries out pretreatment；
3) the linear titanyl polymer solution for preparing is uniformly applied on matrix, is dried, sinters, obtain nano-TiO2Coating structure,
Wherein, step 1) described in linear titanyl polymer, be linear titanyl polymer that the Ti-O keys to repeat connect organic group as main chain, in side base, it includes following construction unit：
Wherein R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11；R2Represent OR1Or represent selected from CH3COCHCOCH3And CH3COCHCOOC2H5Complexation group；Condition is based on R2The total amount of group, at least 50% R2Group represents described complexation group；Number-average molecular weight Mn that the linear titanyl polymer is determined with vapor-pressure osmometry is as 2000～3000；Not solvent-laden pure titanyl polymer possesses softening point, and the softening point range that ring and ball method is determined is 90～127 DEG C.
It is still another aspect of the present invention to provide nano-TiO2Purposes of the coating structure as photocatalyst and/or Superhydrophilic material in purification of air, water process purification, deodorize, 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 proton nmr spectra 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 proton nmr spectra 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 further embodiment of the present invention；
Fig. 6 is the stereoscan photograph of the coating structure in yet further embodiment of the invention.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have the identical meanings that one skilled in the art of the present invention are generally understood.In the case of inconsistent, the definition in this specification is defined.
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 mean diameter with 10～50nm2Granule, the nano-TiO2The load capacity of coating is every cm2Matrix on 1.0～100 μ g TiO2。
In the nano-TiO of the present invention2In coating structure, the preferred nano-TiO2Each nano-TiO in coating2Granule is made up of the fundamental particle or crystallite cluster of a diameter of 2～5nm.
Herein, the particle diameter of granule or microgranule 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, particularly preferably more preferably 50nm～200nm, 80nm～150nm.
In the nano-TiO of the present invention2In coating structure, the nano-TiO2The thickness of coating is equivalent to TiO2Load capacity be 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, light-catalyzed reaction can be caused under the exciting of ultraviolet light.The TiO of Anatase2Its catalysis activity is high, and works as the TiO of Rutile Type2During appearance, its catalysis activity is reduced.In addition, under ultraviolet excitation, can also induce nano-TiO2The Superhydrophilic reaction of coating.
In the nano-TiO of the present invention2In coating structure, described nano-TiO2Coating is colourless and/or transparent.Colourless and/or transparent coating has high light transmittance, can effectively by ultraviolet light and visible ray.
It is preferred that the nano-TiO of the present invention2The visible light transmittance rate of coating structure is more than 80%, more preferably more than 90%.
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, described nano-TiO2The shape of coating can change with the change of base shape, e.g. plane or curved surface, spherical or hollow Arbitrary 3 D shape, with very big adaptability and compatibility.
In the nano-TiO of the present invention2In coating structure, described matrix can be arbitrary shape, e.g. tabular, cellular, fibrous, spherical or hollow ball-shape.
Described matrix includes but is not limited to silicon substrate class, metal class, category of glass, ceramic-like, adsorbing material class or their combination in any.In certain embodiments of the present invention, the example of metal class matrix includes：Steel plate, aluminium sheet, titanium plate, copper coin, zine plate, nickel foam, foamed aluminium, aluminum honeycomb etc.；The example of category of glass matrix includes：Sheet glass, glass fabric, hollow glass micro-ball, bead, glass spring etc.；The example of ceramic-like matrix includes：Hollow ceramic microspheres, ceramic tile, ceramic wafer, ceramic honey comb etc.；The example of adsorbing material class matrix includes：Silicon oxide, silica gel, activated carbon, zeolite, molecular sieve etc..The matrix of the present invention is also selected from other materials, such as cement, quartz sand, expanded perlite, firebrick particle, wood flour, organic polymer, fabric etc., and is not limited to matrix exemplified as above.
In the nano-TiO of the present invention2In coating structure, the top layer of preferred described matrix is coarse, the outer surface of the projection with nano-grade size and/or hollow.The outer surface of Nanometer Roughness can strengthen nano-TiO2The adhesion of coating and matrix.
Also offer of the invention prepares nano-TiO2The method of coating structure, the method is comprised the following steps：
1) linear titanyl polymer is dissolved in a solvent, is configured to solution, wherein in terms of titanium, the concentration of the solution is 0.3～2 weight %；
2) surface of the matrix optionally to being applied carries out pretreatment；
3) the linear titanyl polymer solution for preparing uniformly is coated on matrix, is dried, sinters, obtain nano-TiO2Coating structure.
Nano-TiO is prepared in the present invention2In the method for coating structure, step 1) described in linear titanyl polymer, be linear titanyl polymer that the Ti-O keys to repeat connect organic group as main chain, in side base, it includes following construction unit：
Wherein R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11；R2Represent OR1Or represent selected from CH3COCHCOCH3And CH3COCHCOOC2H5Complexation group；Condition is based on R2The total amount of group, at least 50% R2Group represents described complexation group；Number-average molecular weight Mn that the titanyl polymer is determined with vapor-pressure osmometry is as 2000～3000；Not solvent-laden pure titanyl polymer possesses softening point, and the softening point range that ring and ball method is determined is 90～127 DEG C.
It is preferred that described linear titanyl polymer dissolves in one or more in the monohydric alcohol with 2～5 carbon atoms or dihydroxylic alcohols, the ethylene glycol mono-ether with 3～8 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, adds chelating agen, heated and stirred 0.5～5.0 hour；
2) at 50～90 DEG C, the mixed solution of water and alcohol is added dropwise over, is stirred 1.5～6 hours at 80～110 DEG C after dripping off, removal of solvent under reduced pressure obtains linear titanyl polymer after cooling.
In the method for preparing linear titanium oxide of the present invention, preferably the structure of the titanate esters is Ti (OR1)4, wherein 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 described chelating agen is one or two in acetylacetone,2,4-pentanedione, ethyl acetoacetate.
In the method for preparing linear titanium oxide of the present invention, the mol ratio of preferably described titanate esters, chelating agen and water is 1:(0.5～1.4):(0.8～1.3).
In the method for preparing linear titanium oxide of the present invention, in preferably described water and the mixed solution of alcohol, alcohol is one or more in the monohydric alcohol with 2～5 carbon atoms, and water and the mol ratio of alcohol are 1 in the mixed solution of preferred described water and alcohol:(3～20).
Linear titanyl polymer prepared by the present invention can be as nano-TiO2Source, it is also possible to 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.As described in the background section, TiO in prior art2Photocatalyst by sol-gal process prepare, there is powder body and easily reunite, load capacity is less, bond it is insecure the problems such as, these problems seriously limit TiO2Photocatalyst application in practice.The linear titanyl polymer-coated matrix material prepared using the present invention, has obtained nano-TiO after pyrolysis2Coating structure, coating uniform, TiO2Load capacity increases, and improves with the adhesion of matrix, overcomes the shortcoming of prior art.
Nano-TiO is prepared in the present invention2In the method for coating structure, preferred steps 1) described in solvent include the monohydric alcohol with 2～5 carbon atoms or dihydroxylic alcohols, lower boiling methyl ether, toluene or dimethylbenzene with 3～8 carbon atoms one or more.In the solution of linear titanyl polymer, in terms of titanium, preferred solution concentration be 0.1～3 weight %, more preferably 0.3～2 weight %.
Nano-TiO is prepared in the present invention2In the method for coating structure, step 2) in coated matrix can be arbitrary shape, e.g. tabular, cellular, fibrous, spherical or hollow ball-shape.
Described matrix includes but is not limited to silicon substrate class, metal class, category of glass, ceramic-like, adsorbing material class or their combination in any.In certain embodiments of the present invention, the example of metal class matrix includes：Steel plate, aluminium sheet, titanium plate, copper coin, zine plate, nickel foam, foamed aluminium, aluminum honeycomb etc.；The example of category of glass matrix includes：Sheet glass, glass fabric, hollow glass micro-ball, bead, glass spring etc.；The example of ceramic-like matrix includes：Hollow ceramic microspheres, ceramic tile, ceramic wafer, ceramic honey comb etc.；The example of the matrix of adsorbing material class includes：Silicon oxide, silica gel, activated carbon, zeolite, molecular sieve etc..The matrix of the present invention is also selected from other materials, such as cement, quartz sand, expanded perlite, firebrick particle, wood flour, organic polymer, fabric etc., and is not limited to matrix exemplified as above.
Nano-TiO is prepared in the present invention2In the method for photocatalytic coating structure, step 2) described in the matrix to being applied pretreatment preferably include to carry out matrix oil removing, derust, thermal activation, polishing, one or more in pickling and anodic oxidation.For example metal class matrix is cleaned and polished, surface cleaning and thermal activation etc. are carried out to category of glass and ceramic-like matrix.Matrix surface is cleaned by pretreatment, or causes the top layer of matrix material roughening or projection and/or hollow with nano-grade size.The outer surface of Nanometer Roughness can strengthen nano-TiO2The adhesion of coating and matrix.
Nano-TiO is prepared in the present invention2In the method for coating structure, preferred steps 3) described in one or more methods in spin coating, spraying, layer painting, roller coat, flow coat and dipping of coating.
Nano-TiO is prepared in the present invention2In the method for coating structure, preferred steps 3) described in nano-TiO2Coating is, at 400～550 DEG C, preferably 450～520 DEG C, for example in atmosphere, to be sintered what is obtained.The step carries out heat treatment to the titanium oxide coating for being coated in matrix surface, and titanyl polymer is resolved into into nano-TiO2, accelerate nano-TiO2Granule is acted in the scattering and permeating of matrix surface, is increased it and is firmly combined with degree with matrix.Wherein selected matrix should be able to tolerate the heat treatment temperature of 450～550 DEG C of certain hour.For the category of glass matrix that softening occurs at 400～550 DEG C, general heat treatment time is 0.5～2 hour.
The nano-TiO prepared by the inventive method2In coating structure, TiO2The thickness of coating is preferably 10nm～500nm, more preferably 50nm～200nm, and particularly preferably 80nm～150nm.
The nano-TiO prepared by the inventive method2In coating structure, preferred TiO2The amount of coating is equivalent to every cm2Matrix on 1.0～3 μ g TiO2, more preferably per cm2Matrix on about 1.0～1.5 μ g TiO2。
The nano-TiO prepared by the inventive method2In photocatalytic coating structure, the TiO for being formed2Granule preferably has the mean diameter of 20～50nm, particularly 20～30nm.The TiO2Granule is preferably made up of the fundamental particle or crystallite cluster of a diameter of 2～3nm.SEM scanning figures on the Si pieces of an embodiment of the invention can be seen that：TiO2The size of granule is in 20nm or so.
The nano-TiO prepared by the inventive method2In photocatalytic coating structure, the TiO for being formed2For Anatase, photocatalysis can be caused to send out under the exciting of ultraviolet light should.The TiO of Anatase2Its catalysis activity is high, and works as the TiO of Rutile Type2During appearance, its catalysis activity is reduced.In addition, under ultraviolet excitation, can also induce Superhydrophilic reaction.
The nano-TiO prepared by the inventive method2In photocatalytic coating structure, preferred TiO2Coating is colourless and/or transparent.Colourless and/or transparent coating has high light transmittance, can effectively by ultraviolet light and visible ray.
The nano-TiO prepared by the inventive method2In photocatalytic coating structure, TiO2The shape of coating changes with the change of base shape, e.g. plane or curved surface, spherical or hollow Arbitrary 3 D shape, with very big adaptability and compatibility.
The nano-TiO of the present invention2Coating structure can effectively utilize ultraviolet degradation organic pollution, inorganic matters, antibacterial, sterilization, mould proof, automatically cleaning, antifog, antifouling etc..
The nano-TiO of the present invention2Coating structure can solve the problem that the problems in practical application.As background section is mentioned, the TiO obtained by sol-gal process2Coating is non-porous structure and TiO2Granule is easily reunited, so TiO2Specific surface it is little, the photocatalytic activity center of generation is few；Simultaneously because coating easily ftractures, load capacity generally will not be very big.Another kind of method of prior art is to use TiO2Suspension, adds wherein organic or inorganic binding agent, because binding agent is to nano-TiO2The coating function of photocatalyst, photocatalysis efficiency is low.Linear titanyl polymer in the present invention serves not only as TiO2Source, and surface modifier can be played a part of, it is soluble in usual vehicle, and solution film forming is good, can improve adhesion of the coating on matrix, solves TiO2The reunion of granule and the adhesion problem on matrix, while the content of Ti is in terms of Ti in linear titanyl polymer solution, can adjust between 0.1～3 weight %, load capacity is controllable and can be than larger, such as load capacity can reach more than 30 weight % on glass mat.
The nano-TiO of the present invention2Coating structure can adopt different matrixes, using various matrixes, develop nano-TiO2Application and large-scale production of the coating structure in different field.Nano-TiO is formed in matrix surface2Coating, can effectively utilize ultraviolet degradation Organic substance, inorganic matters, with antibacterial, sterilization, automatically cleaning, antifog, anti-pollution function etc..It is with a wide range of applications in fields such as purification of air, sewage disposal, self-cleaning glass.
The nano-TiO of the present invention2Coating is combined with metal, glass, ceramics, adsorbing material and other types of matrix, can produce different applications.When the nano-TiO of the present invention2Coating is formed on glass, particularly form coating on the glass of substantially transparent, self-cleaning glass can be manufactured, it can be while antipollution, water vapor and anti-coagulation, can apply to the glass of glass of building, windshield, rear window, roof glass, side glass, the rearview mirror of double glazing type etc.；The glass of train, aircraft, steamer, and the glass of public utility, such as aquarium glass, glass of cupboard, garden glass are can be additionally used in, and for the glass in interior decoration, urban facilities；In can be also used for the display screens such as telescreen, computer screen, call screen；This kind of coating structure can also be applied to electric control glass, such as in liquid crystal electrochomeric glass, electroluminescent glass and photovoltaic glass.
When using glass fabric as matrix material, the glass fabric-nano-TiO for being obtained2Coating structure can serve as filtering material, including purify air, purification sewage, removing stink, it is also possible to for manufacturing furred ceiling for not allowing easy cleaning etc..TiO2Coating can be with degradation of organic substances and inorganic beyond the region of objective existence, while can be with antibacterial, sterilization etc. except in filter process.
When using Hollow Glass Sphere as matrix material, the Hollow Glass Sphere-nano-TiO for being obtained2Coating structure can be used for filter water, the Organic substance and inorganic matters in degradation water, while the function with sterilization.
When using porous ceramicss as matrix material, the porous ceramicss-nano-TiO for being obtained2Coating structure can be used for the filtration of water, sterilization, and for adding the trace element beneficial to health, while can be used for the filtration and sterilization of air.
When using ceramic wafer as matrix material, the ceramic wafer-nano-TiO for being obtained2Coating structure can realize the photocatalytic degradation of Organic substance, have broad application prospects in terms of pollution control, indoor air purification, automatic cleaning coating.TiO2The light-catalyzed reaction for itself exciting makes ceramics with more antibacterial effect.This ceramic tile is applied to into hospital can kill the antibacterial that is attached to metope；The sticky mass that the soap due to gathering on ground and metope causes because of bacterial action can be reduced for bathroom, anti-skidding, antifouling effect is played；Ammonia concentration therein is can obviously reduce for toilet, the sensation for not having discomfort is made one；For keeping a public place clean ceramics as antibacterial in room, noxious bacteria can be not only killed, harmful gass are also removed to a certain extent, be purified the air of a room；City Building exterior wall be can be also used for as photocatalysis ceramics exterior wall tile, be possible to mitigate the atmospheric pollution in city to a certain extent.
The present invention is linear titanyl polymer to be added into certain solvent to obtain homogeneous scattered solution, is then coated on different matrix surface, and 400～550 DEG C of Jing is thermally treated resulting in the nano-TiO being supported on matrix under air conditionses2Coating.The method is raw material using titanyl polymer, does not use any surfactant, and Jing after 400～550 DEG C of heat treatments uniform coating is formed, coating is firmly combined with matrix, and light degradation organic pollution effect is good, and antibiotic and sterilizing ability is strong, good hydrophilic property, automatical cleaning ability is strong, long service life.
The method of the present invention is simple and convenient, the nano-TiO prepared2Coating is firm, stable, can be mass-produced.Using ultraviolet photo-induced light-catalyzed reaction, with higher catalysis activity, the TiO2Coating has broad application prospects in photocatalysis fields such as water process, purification of air, sterilization antibacterial, automatically cleanings.
Embodiment
Technical scheme is addressed further under with reference to specific embodiment, but the present invention is not limited to the embodiment or implementation result given by embodiment.
Embodiment 1:The preparation of linear titanyl polymer
1) 1mol tetrabutyl titanates are added into reaction vessel, adjusts the temperature to 50 DEG C, add 0.8mol acetylacetone,2,4-pentanediones, reacted 1 hour in 50 DEG C of heated and stirred；
2) adjust the temperature to 80 DEG C, instill the mixed solution of 0.8mol water and 2.5mol isobutanol, drip off continuation in 80 DEG C of heated and stirred 2 hours, removal of solvent under reduced pressure obtains the titanyl polymer of yellow after cooling.
Ring and ball method measures softening point for 92 DEG C, and vapour pressure osmometry measures number-average molecular weight Mn=2750.
Yellow 1～the 2mg of titanyl polymer of gained and the pure KBr of 200mg is finely ground uniform, in being placed in mould, transparent sheet is pressed on tablet machine, for IR spectral characterizations, see Fig. 1-1；In Fig. 1-1,2959cm-1、2922cm-1、2872cm-1The peak at place for C-H stretching vibration peak, 1592cm-1、1531cm-1The peak at place belongs to C=O (keto form), C=C (enol form) in acetyl acetone ligands, 425cm-1And 543cm-1Absworption peak demonstrate and exist in polymer architecture Ti-O keys.
The yellow titanyl polymer of gained is dissolved in deuterochloroform, for NMR signs, Fig. 1-2 is as a result seen.
Embodiment 2：The preparation of linear titanyl polymer
1) 1mol butyl titanates are added into reaction vessel, 0.5mol acetylacetone,2,4-pentanediones is added, in 90 DEG C of heated and stirred 1.5h；
2) 70 DEG C are adjusted the temperature to, the mixed liquor of 1.2mol water and 6mol n-butyl alcohol is instilled, 2.5h is stirred at 100 DEG C after dripping off, reduced pressure after cooling except solvent obtains described titanyl polymer.
Ring and ball method measures softening point for 98 DEG C, and vapour pressure osmometry measures number-average molecular weight Mn=2930.
1～the 2mg of titanyl polymer of gained and the pure KBr of 200mg is finely ground uniform, in being placed in mould, transparent sheet is pressed on tablet machine, for IR spectral characterizations, see Fig. 2-1；
The titanyl polymer of gained is dissolved in deuterochloroform, for NMR signs, Fig. 2-2 is as a result seen.
Embodiment 3：Nano-TiO is loaded on silicon chip2Coating structure preparation
1) the linear titanyl polymer for preparing embodiment 1 dissolves in ethanol, prepares the solution that Ti concentration is 0.4 weight %；
2) silicon chip is dried respectively in acetone, dehydrated alcohol and deionized water with the ultrasonic cleaning 15 minutes of 20-40Hz；
3) titanyl polymer solution is coated with the silicon chip of 2cm × 2cm by the way of spin coating, is dried, heat treatment 30 minutes under 500 DEG C of air obtain 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 TiO that the linear titanyl polymer is obtained after heat treatment2For Detitanium-ore-type.
The electromicroscopic photograph for obtaining the coating structure is clapped from different perspectives as shown in Fig. 3-1 and Fig. 3-2.Found out by figure, gained coating surface is smooth, thickness is uniform, with loose structure, TiO2The mean diameter of granule about 20nm.Test result indicate that：The titanyl polymer has good film property, TiO after heat treatment2Coating is carried on well on Si pieces.
Embodiment 4：Nano-TiO is loaded on silicon chip2Coating structure preparation
It is identical with the step of embodiment 2, the concentration counted with Ti except the solution of linear titanyl polymer prepared as 0.8 weight %, using identical condition on silicon chip spin coating, drying, heat treatment, obtain the uniform load nano-TiO on silicon chip2Coating structure.
The electromicroscopic photograph of the coating structure is shown in Fig. 4, and gained coating layer thickness is 50nm.
Embodiment 5：Nano-TiO is loaded on quartz glass2Coating structure preparation
1) the titanyl polymer for preparing embodiment 1 dissolves in ethanol, prepares the solution that Ti concentration is 0.4 weight %；
2) quartz glass plate is dried respectively in acetone, dehydrated alcohol and deionized water with the ultrasonic cleaning 15 minutes of 20-40Hz；
3) titanyl polymer solution is coated with 2cm × 2cm quartz glasss by the way of spin coating, is dried, the thickness for measuring wet film in step instrument is 80nm；Then the quartz glass plate of wet film heat treatment 30 minutes under 500 DEG C of air are coated with, the uniform load nano-TiO on quartz glass is obtained2Coating structure, coating layer thickness 30nm.
By nano-TiO obtained as above2- non catalytic crystal coating structure carries out the transmission test under visible ray, and absorbance is 89.2%.
Under room temperature environment, before coating titanyl polymer solution, the contact angle of 5 diverse locations of quartz glass is measured with contact angle measurement, be 72o；Loading TiO2After coating, the contact angle of 5 diverse locations in coating structure surface is measured, contact angle is 5o, illustrate the TiO that the method is prepared2Coating has Superhydrophilic, and this characteristic causes TiO2Coating structure has automatically cleaning decontamination, is readily cleaned and the performance such as water-mist-proof.
Embodiment 6：Nano-TiO is loaded on quartz glass2Coating structure preparation
1) the titanyl polymer for preparing embodiment 1 dissolves in ethanol, prepares the solution that Ti concentration is 0.8 weight %；
2) quartz glass plate is dried respectively in acetone, dehydrated alcohol and deionized water with the ultrasonic cleaning 15 minutes of 20-40Hz；
3) titanyl polymer solution is coated with 2cm × 4cm quartz glasss by the way of dipping, is dried；Then the quartz glass plate of wet film heat treatment 60 minutes under 500 DEG C of air are coated with, the uniform load nano-TiO on quartz glass is obtained2Coating structure.
Take 5 nano-TiOs for being obtained2- non catalytic crystal coating structure, grid is drawn using grid method is drawn on the surface of the coating structure, is then pasted repeatedly, is torn with transparent adhesive tape, observes TiO2The integrated degree of coating, to paste number of times coating structure surface TiO is evaluated2The adhesive force of coating.Afterwards, observe water droplet to insert in water in the contact angle on coating structure surface or by coating structure, after lifting out, observe the integrity of coating surface moisture film.
Quartz glass-nano-TiO that the present embodiment is obtained2Coating structure carries out contrast test with uncoated quartz glass：In quartz glass-nano-TiO that the present embodiment is obtained2The surface sprinkling tap water of coating structure, after having sprayed, in coating surface continuous moisture film is formed, and moisture film is all flowed down along matrix, and coating surface is without washmarking；And uncoated quartz glass is after spray water, its surface forms globule, and matrix surface leaves washmarking after water flows away.This explanation coating of the present invention has good hydrophilic.
Using the quartz glass-nano-TiO of the present embodiment2The Superhydrophilic of coating structure, can serve as automobile rearview mirror, anti-steam and antifouling glass without wiping etc., be particularly suitable for outdoor building glass.In addition, can also apply the performance of its photocatalyst to be used to develop a variety of 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 art of photovoltaic.
Take above-described quartz glass-nano-TiO2Coating structure 2cm × 4cm is added to (concentration 15mg/L) in 50ml methyl orange solutions, is 50% with the degradation rate that methyl orange solution is tested after 500W mercury lamps illumination 5 hours；After 8 hours, the degradation rate of methyl orange solution reaches 80%.
Test by more than can be seen that：The self-cleaning function of Superhydrophilic self-cleaning glass shows as：By affinity of its coating surface to water, the drop of water contact angle on the coating surface is set to go to zero.When water touches coating, rapidly in its surface spreading, uniform moisture film is formed, show super hydrophilic property, spot is taken away by the gravity fall of uniform water film, most of organic or inorganic spot can be removed by this way.
The present invention using the above-mentioned technical solution beneficial effect to be reached be mainly solve cause during self-cleaning glass large-scale production crawling, appearance of coat is of poor quality the problems such as, enable to coating simultaneously more firmly to combine on glass basis surface, it is ensured that the service life of coating structure.Self-cleaning glass appearance of coat prepared by the present invention is bright, with anti-reflection effect.
Embodiment 7：Nano-TiO is loaded on aluminium flake2Coating structure preparation
1) the linear titanyl polymer for preparing embodiment 2 dissolves in ethanol, prepares the solution that Ti concentration is 0.4 weight %；
2) by long 9cm, wide 2cm, thickness 0.1cm aluminium flake respectively in acetone, dehydrated alcohol with the ultrasonic cleaning 15 minutes of 20-40Hz, remove the oil stain on its surface, then aoxidized in phosphoric acid, oxidation terminates the residual that rear deionized water washes surface, dries；
3) titanyl polymer solution is coated with aluminium flake using impregnation method, is dried, heat treatment 2 hours under 500 DEG C of air obtain the uniform load nano-TiO on aluminium flake2Coating structure.
The SEM photograph of the coating structure by Fig. 5 as shown in figure 5, found out, gained coating surface is smooth, thickness is uniform, good, the TiO of the transparency2Particle size is 20nm, and coating layer thickness is 30nm.
Take above-described aluminium flake-nano-TiO2Coating structure, its quality is 1.4407g, is added to (concentration 15mg/L) in 50ml methyl orange solutions, with the absorption spectrum that methyl orange solution is tested after 500W mercury lamps illumination 5 hours, its degradation rate is 67.5%, and after degraded 8 hours, its degradation rate is 79.3%.
The TiO of 0.0019g is coated with above-described aluminium flake2, the roughness on surface is not considered, averagely in every cm2It is coated with the TiO of 5.8 μ g2。
Take 5 aluminium flake-nano-TiOs for being obtained2Coating structure, grid is drawn using grid method is drawn on the surface of the coating structure, is then pasted repeatedly, is torn with transparent adhesive tape, observes TiO2The integrated degree of coating, to paste number of times coating structure surface TiO is evaluated2The adhesive force of coating.Afterwards, observe water droplet to insert in water in the contact angle on coating structure surface or by coating structure, after lifting out, observe the integrity of coating surface moisture film.
To the TiO on aluminium flake2Coating carries out hydrophilicity experiment, can form continuous moisture film in coating surface, and moisture film is all flowed down along coating surface, and coating surface is not loaded with TiO without washmarking2After spray water, its surface forms the globule to the aluminium flake of coating, and matrix surface leaves washmarking after water flows away.The coating of this explanation present invention has good hydrophilic.
The test according to more than is as can be seen that the nano-TiO of the present invention2Coating structure, both with degradation of organic substances, and with hydrophilic, can there is certain self-cleaning function, can apply on household electrical appliance indoors, with purify air, deodorization, sterilization and self-cleaning function.
Embodiment 8：Nano-TiO is loaded in titanium sheet2Coating structure preparation
1) the linear titanyl polymer dissolving for preparing embodiment 2 obtains in ethanol the solution that Ti concentration is 0.4 weight %；
2) by long 9cm, wide 2cm, thickness 0.1cm titanium sheet respectively in acetone, dehydrated alcohol, pure water with the ultrasonic cleaning 15 minutes of 20-40Hz, dry up；
3) titanyl polymer solution is coated with titanium sheet using impregnation method, is dried, heat treatment 30 minutes under 500 DEG C of air obtain the uniform load nano-TiO in titanium sheet2Coating structure.
Take above-described coating structure 1.3459g and be added to (concentration 15mg/L) in 50ml methyl orange solutions, with 500W mercury lamps illumination 5 hours, the degradation rate of methyl orange solution was 82%；After illumination 8 hours, methyl orange is degradable.
The TiO of 0.0020g is coated with above-described titanium sheet2, the roughness on surface is not considered, averagely in every cm2It is coated with the TiO of 6.2 μ g2。
Take 5 titanium sheet-nano-TiOs for being obtained2Coating structure, grid is drawn using grid method is drawn on the surface of the coating structure, is then pasted repeatedly, is torn with transparent adhesive tape, observes TiO2The integrated degree of coating, to paste number of times coating structure surface TiO is evaluated2The adhesive force of coating.Afterwards, observe water droplet to insert in water in the contact angle on coating structure surface or by coating structure, after lifting out, observe the integrity of coating surface moisture film.
To the TiO in titanium sheet2Coating carries out hydrophilicity experiment, can form continuous moisture film in coating surface, and moisture film is all flowed down along coating surface, and coating surface does not carry cated titanium sheet after spray water without washmarking, and its surface forms the globule, and matrix surface leaves washmarking after water flows away.The coating of this explanation present invention has good hydrophilic.
Test in titanium sheet as can be seen that load nano-TiO according to more than2Coating structure both can have certain self-cleaning function with degradation of organic substances, and with hydrophilic, therefore can apply on household electrical appliance indoors, with purify air, deodorization, sterilization and self-cleaning function.
Embodiment 9：Nano-TiO is loaded in nickel foam2Coating structure preparation
1) the linear titanyl polymer dissolving for preparing embodiment 1 obtains in ethanol the solution that Ti concentration is 0.4 weight %；
2) by long 9cm, wide 2cm nickel foam respectively in acetone, dehydrated alcohol and pure water with the ultrasonic cleaning 15 minutes of 20-40Hz, dry up；
3) linear titanyl polymer solution is coated with nickel foam using impregnation method, is dried, heat treatment 30 minutes under 500 DEG C of air obtain the uniform load nano-TiO in nickel foam2Coating structure.
Take above-described coating structure 0.5525g and be added to (concentration 15mg/L) in 50ml methyl orange solutions, after 500W mercury lamps illumination 8 hours, the degradation rate of methyl orange solution is 57.2%.
On the ultrasonic instrument of operating frequency 20Hz, supersound process is carried out 2 hours to above-described coating structure, come off almost without powder body.
It is manufactured in the present embodiment that nano-TiO is loaded in nickel foam2Coating structure there is good stability, after being used for multiple times, by the straightforward procedure such as heating and washing recovery photocatalytic activity can be completely regenerated, and continue to keep good stability.
The coating structure utilizes TiO2Photocatalysis coating, can apply to organic matter degradation, the formaldehyde of the interior that can degrade, can sterilize, deodorization etc., it is also possible to for filtering.
Embodiment 10：Nano-TiO is loaded on glass fabric2Coating structure preparation
1) the linear titanyl polymer dissolving for preparing embodiment 2 obtains in ethanol the solution that Ti concentration is 0.4 weight %；
2) glass fabric is cut into into the square that the length of side is 2cm, is activated in the hot water；
3) titanyl polymer solution is coated with glass fabric using impregnation method, is dried, heat treatment 30 minutes under 480 DEG C of air obtain the uniform load nano-TiO on glass fabric2Coating structure.
The electromicroscopic photograph of the coating structure by Fig. 6 as shown in fig. 6, found out, gained coating surface is smooth, and thickness is uniform.
Take above-described coating structure 0.2859g and be added to (concentration 15mg/L) in 50ml methyl orange solutions, be 88.8% with the degradation rate of methyl orange solution after 500W mercury lamps illumination 8 hours.
On the ultrasonic instrument of operating frequency 20Hz, TiO is coated with to this2The glass fabric of coating carries out supersound process 2 hours, weight % of powder body expulsion rate 0.1.
It is manufactured in the present embodiment that TiO is loaded on glass fabric2Coating structure, can serve as the pollutant in filtering material degradation water；Can also be sterilized using glass fabric, deodorization etc..
Embodiment 11：Nano-TiO is loaded on porous ceramicss2Coating structure preparation
1) the linear titanyl polymer dissolving for preparing embodiment 1 obtains in ethanol the solution that Ti concentration is 0.9 weight %；
2) porous ceramicss are cleaned；
3) linear titanyl polymer solution is coated on porous ceramicss using impregnation method, is dried, heat treatment 1.5 hours under 520 DEG C of air obtain loading nano-TiO on porous ceramicss2Coating structure.
Above-described coating structure 6.1924g is taken, is added to (concentration 15mg/L) in 50ml methyl orange solutions, after 500W mercury lamps illumination 5 hours, the degradation rate of methyl orange solution is 58.0%；After illumination 8 hours, its degradation rate is 78.0%.
On the ultrasonic instrument of operating frequency 20Hz, TiO is coated with to this2The porous ceramicss of coating carry out supersound process 120 minutes, and powder body does not almost come off.
It is manufactured in the present embodiment that nano-TiO is loaded on porous ceramicss2Coating structure utilize TiO2Photocatalysis coating, the formaldehyde of the interior that can degrade, can sterilize, deodorization etc..
Embodiment 12：Nano-TiO is loaded over a molecular sieve2Coating structure preparation
1) the linear titanyl polymer dissolving for preparing embodiment 1 obtains in ethanol the solution that Ti concentration is 0.2 weight %；
2) molecular sieve is cleaned；
3) linear titanyl polymer solution is coated over a molecular sieve using impregnation method, is dried, heat treatment 1.0 hours under 500 DEG C of air obtain uniform load nano-TiO over a molecular sieve2Coating structure.
Above-described coating structure 0.2500g is taken, is added to (concentration 15mg/L) in 50ml methyl orange solutions, 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 used in degradation water indoor Organic substance, inorganic matters, can also sterilize, deodorization etc..
Ultimate principle, principal character and the advantages of the present invention of the present invention are described above by embodiment.Those skilled in the art it should be appreciated that the present invention is not restricted to the described embodiments, merely illustrating the principles of the invention described in above-described embodiment and description, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications.
Claims (27)
1. nano-TiO2Coating structure, including matrix and the nano-TiO for being carried on matrix surface2Coating, institute
State nano-TiO2Coating includes the nano-TiO that mean diameter is 10～50nm2Granule, the nano-TiO2
The load capacity of coating is every cm2Matrix on 1.0～100 μ g TiO2。
2. nano-TiO as claimed in claim 12Coating structure, wherein the nano-TiO2Coating it is negative
Carrying capacity is every cm2Matrix on 1.0～3 μ g TiO2。
3. nano-TiO as claimed in claim 12Coating structure, wherein the nano-TiO2In coating
TiO2For Anatase.
4. nano-TiO as claimed in claim 12Coating structure, wherein the nano-TiO2Coating be by
Linear titanyl polymer solution is sintered and formed.
5. nano-TiO as claimed in claim 42Coating structure, wherein for forming the nano-TiO2
The linear titanyl polymer of coating is that the Ti-O keys to repeat connect organic group as main chain, in side base
Linear titanyl polymer, it includes following construction unit：
Wherein R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11；R2Represent OR1Or
Represent and be selected from CH3COCHCOCH3And CH3COCHCOOC2H5Complexation group；Condition is base
In R2The total amount of group, at least 50% R2Group represents described complexation group；The linear titanium
Number-average molecular weight Mn that oxygen polymer is determined with vapor-pressure osmometry is as 2000～3000；Without solvent
Pure titanyl polymer possess softening point, the softening point range that ring and ball method is determined is 90～127 DEG C.
6. the nano-TiO as any one of claim 1-52Coating structure, wherein the nanometer
TiO2Coating is colourless and/or transparent, and its visible light transmittance rate is more than 80%.
7. the nano-TiO as any one of claim 1-52Coating structure, wherein the nanometer
TiO2The water contact angle of coating structure is less than 10 °.
8. the nano-TiO as any one of claim 1-52Coating structure, wherein described matrix are
Arbitrary shape, the nano-TiO2The shape of coating changes with the change of base shape.
9. nano-TiO as claimed in claim 82Coating structure, wherein described matrix are tabular, honeybee
Nest shape, threadiness, spherical or hollow ball-shape.
10. the nano-TiO as any one of claim 1-52Coating structure, wherein described matrix
Including silicon substrate class, metal class, category of glass, ceramic-like and adsorbing material class or theirs is any
Combination.
11. nano-TiOs as claimed in claim 102Coating structure, wherein the metal class matrix bag
Include steel plate, aluminium sheet, titanium plate, copper coin, zine plate, nickel foam, foamed aluminium and aluminum honeycomb；The glass
Class matrix includes sheet glass, glass fabric, hollow glass micro-ball, bead and glass spring；Institute
Ceramic-like matrix is stated including hollow ceramic microspheres, ceramic tile, ceramic wafer and ceramic honey comb；The adsorption material
Material class matrix includes silicon oxide, silica gel, activated carbon, zeolite and molecular sieve.
12. nano-TiOs as claimed in claim 112The top layer of coating structure, wherein described matrix is
Coarse, the outer surface of the projection with nano-grade size and/or hollow.
13. prepare the nano-TiO as described in any one of claim 1-122The method of coating structure, should
Method is comprised the following steps：
1) linear titanyl polymer is dissolved in a solvent, is configured to solution, wherein in terms of titanium, it is described
The concentration of solution is 0.3～2 weight %；
2) surface of the matrix optionally to being applied carries out pretreatment；
3) the linear titanyl polymer solution for preparing is uniformly applied on matrix, is dried, sinters,
Obtain loading nano-TiO on matrix2Coating structure,
Wherein, step 1) described in linear titanyl polymer, be the Ti-O keys to repeat as main chain,
Connect the linear titanyl polymer of organic group in side base, it includes following construction unit：
Wherein R1It is independently from each other-C2H5,-C3H7,-C4H9,-C5H11；R2Represent OR1Or
Represent and be selected from CH3COCHCOCH3And CH3COCHCOOC2H5Complexation group；Condition is base
In R2The total amount of group, at least 50% R2Group represents described complexation group；The linear titanium
Number-average molecular weight Mn that oxygen polymer is determined with vapor-pressure osmometry is as 2000～3000；Without solvent
Purely linear titanyl polymer possess softening point, the softening point range that ring and ball method is determined is 90～127 DEG C.
14. prepare as claimed in claim 13 nano-TiO2The method of coating structure, wherein described
Linear titanyl polymer dissolves in the monohydric alcohol with 2～5 carbon atoms or dihydroxylic alcohols, with 3～8
One or more in the ethylene glycol mono-ether of individual carbon atom, toluene or dimethylbenzene.
15. prepare as claimed in claim 13 nano-TiO2The method of coating structure, wherein described
Linear titanium oxide is prepared via a method which：
A) titanate esters are added in reaction vessel, at 50～90 DEG C, adds chelating agen, heated and stirred
0.5～5.0 hour；
B) at 50～90 DEG C, the mixed solution of water and alcohol is added dropwise over, at 80～110 DEG C after dripping off
Stirring 1.5～6 hours, removal of solvent under reduced pressure obtains linear titanyl polymer after cooling.
16. prepare as claimed in claim 15 nano-TiO2The method of coating structure, wherein for making
The structure of the titanate esters of standby described linear titanium oxide is Ti (OR1)4, wherein R1Independently of one another
Selected from-C2H5,-C3H7,-C4H9, and-C5H11。
17. prepare as claimed in claim 15 nano-TiO2The method of coating structure, wherein for making
The chelating agen of standby described linear titanium oxide is the one kind or two in acetylacetone,2,4-pentanedione, ethyl acetoacetate
Kind.
18. prepare as claimed in claim 15 nano-TiO2The method of coating structure, wherein preparing
During described linear titanium oxide, the mol ratio of titanate esters, chelating agen and water is 1:(0.5～1.4):
(0.8～1.3).
19. prepare as claimed in claim 15 nano-TiO2The method of coating structure, wherein preparing
During described linear titanium oxide, in described water and the mixed solution of alcohol, alcohol is with 2～5
Water and alcohol rubs in one or more in the monohydric alcohol of individual carbon atom, and the mixed solution of water and alcohol
You are than being 1:(3～20).
20. prepare nano-TiO as described in any one of claim 13-192The method of coating structure,
Wherein step 1) described in solvent include the monohydric alcohol or dihydroxylic alcohols, tool with 2～5 carbon atoms
Have the methyl ether, toluene or dimethylbenzene of 3～8 carbon atoms one or more.
21. prepare nano-TiO as described in any one of claim 13-192The method of coating structure, its
Described in matrix include silicon substrate class, metal class, category of glass, ceramic-like and adsorbing material class or
Their combination in any.
22. prepare as claimed in claim 21 nano-TiO2The method of coating structure, wherein the gold
Category class matrix includes 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 fabric, hollow glass micro-ball, bead and glass
Spring；The ceramic-like matrix includes hollow ceramic microspheres, ceramic tile, ceramic wafer and ceramic honey comb；Institute
Adsorbing material class matrix is stated including silicon oxide, silica gel, activated carbon, zeolite and molecular sieve.
23. prepare nano-TiO as described in any one of claim 13-192The method of coating structure,
Wherein step 2) in matrix to being applied pretreatment include carrying out matrix oil removing, derust, heat it is living
One or more in change, polishing, pickling and anodic oxidation.
24. prepare nano-TiO as described in any one of claim 13-192The method of coating structure,
Wherein step 3) described in coating in spin coating, spraying, layer painting, roller coat, flow coat and dipping
One or more sides.
25. prepare nano-TiO as described in any one of claim 13-192The method of coating structure,
Wherein step 3) described in nano-TiO2Coating is to be sintered in atmosphere, in 450～550 DEG C
Obtain.
26. nano-TiOs as described in any one of claim 1-122Coating structure or such as claim
Nano-TiO prepared by the method described in any one of 13-252Coating structure is used as photocatalyst and/or super close
Water-based material purification of air, water process purification, deodorize, antibacterial, fungi-proofing, mould proof, automatically cleaning,
Purposes in antifog and antifouling field.
27. purposes as claimed in claim 26, wherein described nano-TiO2Coating structure is used as certainly
Cleaning glass, purification filtering material and antibiotic ceramic tile.
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| PCT/CN2017/077068 WO2017157328A1 (en) | 2016-03-18 | 2017-03-17 | Linear titanium-oxide polymer, titanium dioxide coating, photocatalyst coating and preparation method therefor |
| US16/086,004 US20200282387A1 (en) | 2016-03-18 | 2017-03-17 | Linear titanium-oxide polymer, titanium dioxide coating, photocatalytic coating and preparation method therefor |
| US17/218,240 US20210213437A1 (en) | 2016-03-18 | 2021-03-31 | Linear titanium-oxide polymer, titanium dioxide coating, photocatalytic coating and preparation method therefor |
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