CN1522954A - Tourmaline/titanium dioxide composite collosol and preparing method and use thereof - Google Patents
Tourmaline/titanium dioxide composite collosol and preparing method and use thereof Download PDFInfo
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- CN1522954A CN1522954A CNA031442587A CN03144258A CN1522954A CN 1522954 A CN1522954 A CN 1522954A CN A031442587 A CNA031442587 A CN A031442587A CN 03144258 A CN03144258 A CN 03144258A CN 1522954 A CN1522954 A CN 1522954A
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Abstract
The present invention relates to a tourmaline/titanium dioxide compound sol. Its raw material compositions include (by mass percent) 5-15% of titanium salt, 60-88% of absolute ethyl alcohol, 3-13% of organic acid, 2-15% of inorganic acid, 0.5-1.5% of deionized water and 0.001-3% of tourmaline, in which the titanium salt is any one of butyl titanate, methyl titanate, titanium tetrachloride and titanyl sulfate, the organic acid is any one of acetic acid, oxalic acid, formic acid and benzensulfonic acid, the inorganic acid is any one of concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloride acid, and the tourmaline is one or several kinds of ferrotourmaline, elbaite and dravite. Said invention also provides its preparation method.
Description
Technical field
The present invention relates to sol-gel technique, be specially a kind of tourmalinite/titanium dioxide complex sol and preparation method thereof and purposes technology.International monopoly Main classification number plan is Int.Cl
7C01B 015/00, C01G023/047.
Background technology
Japanese rattan island titanium dioxide such as clear (Fujishima) report (TiO in 1972
2) since the electrode glazing brine electrolysis phenomenon, at Nano semiconductor TiO
2The preparation of material, structure, performance, and aspect such as photochemical catalysis theory carried out deep research both at home and abroad, finds TiO
2And matrix material has very wide application prospect in the environmental protection field, will become 21 century to utilize a new technology revolution of solar energy purification environment.
But because semi-conductor TiO
2Can band gap Eg=3.2eV, only can absorb the ultraviolet part of wavelength less than 387.5nm, light induced electron and hole recombination rate again are higher, cause solar energy utilization ratio and quantum yield low, industrial application is subjected to very big restriction.For this reason, both at home and abroad scientist around how realizing that the high efficiency photocatalysis technical theme under the visible light condition carried out a large amount of exploration work.As: (1) adopts ion implantation at TiO
2In mix rare earth or transition metals such as Ce, Pr, Fe so that in being with, increase new surface level, enlarge the wavelength absorption scope of light-catalyzed reaction, realize visible light photocatalysis; (2) at TiO
2Metallic elements such as area load Cu, Ag, Pt, Au to reduce the compound of electronics and hole, improve the photochemical catalysis quantum yield; (3) utilize different valence state element doping production rutile TiO such as Na, Mg, Al
2, be implemented in the photocatalytic effect under the 550nm light wave.For example, the TiO of central authorities of Japanese Toyota Research Institute
2-XN
XFilm just can absorb the light of 520nm wavelength.In the above method, the complex process of (1), (3) method; The material anti-photooxidation ability of method (2) preparation.
In addition, microwave-assisted photochemical catalysis, electric field are assisted technology such as photochemical catalysis, also can increase substantially photocatalysis efficiency.Especially the light-catalyzed reaction that has electric field to participate in can improve photocatalysis efficiency more than 3 times.Electric field assists photocatalysis technology usually TiO
2Make membrane electrode, and this membrane electrode is applied tens of anodic bias that arrive hundreds of millivolts, cause the easier catalyst surface that leaves of light induced electron, thereby improve photocatalysis efficiency.
Boot Field people such as (Butterfield) is TiO
2Make membrane electrode, find that photocatalysis efficiency is improved significantly.But because this system is the membrane electrode system of two-dimensional characteristics, be subjected to the restriction of membrane electrode units activity area, be difficult to increase substantially degradation rate technically, practical application is subjected to certain limitation and (sees document: " water treatment " (Water Research), 1997,31 (3): 675).
People such as Wu Hejin expand to three-dimensional system with two-dimensional system, promptly by means of the notion of stereo electrod, use three-dimensional TiO
2Stereo electrod replaces plate electrode, allows reaction solution pass through by particulate state TiO
2The photoelectricity assembly catalyze bed system that photocatalyst and anode send electroplax to form, to strengthen the light-catalyzed reaction process that realizes that electric field is assisted, be referred to as photoelectricity assembly catalyze or enhancement type electric field and assist photochemical catalysis (being called for short EEAPC, EnhancedElectro-Assisted Photocatalysis).In fact, the competition of charge transfer is to influence one of key factor of photochemical catalysis quantum yield between heavy combination of the light induced electron of photocatalyst and photohole and interface, and the increase of interfacial charge transfer rate constant will cause the increase of light-catalyzed reaction quantum yield.For the ordinary light catalyzed reaction, the molecular oxygen of catalyst surface absorption is accepted light induced electron and is become O
- 2, in the flash photolysis experiment, be proved to be slowly rapid, make in the competition of interfacial charge, to be in a disadvantageous position.And when existing highfield around the photocatalyst, can realize effectively limiting the heavily combination of light induced electron and photohole by the directed interfacial migration of light induced electron, thereby improve the light-catalyzed reaction quantum yield.People such as Wu Hejin research finds that also under identical reaction conditions, the degradation rate of phenol is respectively 10% and 33.6% in electrolytic reaction and the light-catalyzed reaction, and the degradation rate of phenol is 82.8% in the photoelectricity assembly catalyze process, has the obvious synergistic effect.Producing this synergistic major cause is, anodic bias can reduce the heavily combination of light induced electron and photohole effectively, and the brine electrolysis reaction also can provide oxygen source for light-catalyzed reaction effectively.Lab scale experiment to the actual industrial wastewater treatment shows that ordinary light catalysis COD (chemical oxygen demand (COD)) clearance is 10%, and percent of decolourization is 20%; Under electric field acted on separately, the clearance of COD was 18%, and percent of decolourization is 15%; Under the effect of EEAPC, the clearance of COD can be up to 80%, and percent of decolourization is 90% and (sees document: " catalysis journal ", 2000,21 (9): 399-403).
Above-mentioned electric field is assisted light-catalyzed reaction, is cost with the consumed power, though have certain advantage in some special uses or special occasions, if it is not use this technological development usual production,, still actual as the function of purifying indoor air building materials etc.
Tourmalinite (Tourmaline) is a kind of cyclosilicate crystal mineral by elements such as elementary composition moisture, fluorine such as Al, Na, Ca, Mg, B and Fe.It is rich in volatiles boron and water, belongs to pneumatogenic mineral mostly, and fecund is in pegmatite and pneumatoilitc solution mineral deposit.The chemical ingredients of tourmalinite mineral is very complicated, and its general formula can be expressed as XY
3Z
6Si
6O
18(BO
3)
3W
4, in the formula, X=Na, Ca, K, mouth (room), Y=Mg
2+, Fe
2+, Mn
2+, Al, Fe
3+, Mn
3+, Li, Z=Al, Fe
3+, Cr
3+, Mg, W=OH, F, O.X, Y, the different colors that can influence tourmalinite of the atom of Z three positions or ionic species.Clung to the absolute direction that time (Barton) found the tourmalinite structure in 1969, promptly the drift angle Sauerstoffatom of silicon-oxy tetrahedron points to same direction in the tourmalinite structure---the positive pole (analogouspole) of tourmalinite, determined that the spacer of tourmalinite belongs to trigonal system, C
3v 5--R3m group.So tourmalinite is the heteropolarity mineral, the c axle is the three-fold symmetry axle, does not have the symmetry axis and the plane of symmetry perpendicular to the c axle, does not also have symmetrical center.19th-century finds that tourmalinite exists piezoelectricity and pyroelectric effect along the c axle.Japan's scholar storehouse pool (T.Kubo) utilizes the cupric ion adsorption experiment to prove the existence of tourmalinite spontaneous electrode in late 1980s.Electrostatic attraction and repulsion, existing of eelctric dipole that doctor Ji Zhijiang, professor Liang Jinsheng utilize the bombardment imaging technique of scanning electron microscope and electronic probe electron beam directly to observe tourmaline particle (are seen document " ChinesePhysics ", 2003,12 (2): 222-225).Tourmalinite self has permanent electrode, can be looked at as a pair of electric dipole, and the strength of electric field of electrode is approximately 10
7V/m.Electrostatic field can be calculated as follows along with weakening rapidly away from the center: Er=(2/3) E
0(a/r)
3, a is the tourmaline particles radius, r is the distance apart from the center.Hence one can see that, has 10 in tourmalinite surface thickness tens micrometer ranges
7(maximum)～10
4Therefore the high electric field of V/m has very strong attract electrons ability.
Theoretical investigation and the lot of experiments progressively deep to tourmalinite prove, it has natural electric polarity, pyroelectricity, piezoelectricity, radiation wavelength 4～14 μ m far infrared rays performances and discharges anionic property, should have the wide development application prospect in health environment-friendly material field.China's tourmalinite resource is very abundant, in Hebei, ground such as Xinjiang, the Inner Mongol and Yunnan all found a large amount of tourmalinite resources, has the good prospect of marketing and competitive edge.
No. 6267944 patents of the U.S. provide a kind of preparation method who contains the titanium deoxid film of tourmalinite and magnetic mineral material.The main preparation material and the proportioning of the described TiO 2 sol of this method are: and titanium colloidal sol (PTX, 0.85wt%), silicon sol (1-5%), capsicin (0.01-15%), magnetite (10-40%), tourmalinite (0.5-15%).Its main preparation technology is: silicon sol, capsicin, magnetite, tourmalinite are mixed, with the deionized water dilution, mix with titanium colloidal sol then, heat under greater than 80 ℃ situation.Utilize the prepared titanic oxide material of this method to prepare titanium film on various base materials, gained titanium film has certain antibacterial and mouldproof and the organic function of photocatalysis Decomposition.But this method desired raw material kind is more, and expensive raw material usage quantity such as tourmalinite is big, and titanium colloidal sol and silicon sol are purchased by market, and restricted bigger, cost is higher.Titanium content is low in the film, mainly is at using under the more weak condition of light source, relatively the organic ability of photocatalysis Decomposition a little less than.Tourmalinite powder content height in the film causes the film stability poor.In addition, antiseptic-germicide capsicin used in this colloidal sol is an organic antibacterial agent, and the life-span is shorter, and product efficacy can not be lasting.
Summary of the invention
At the deficiencies in the prior art, the technical problem that the present invention mainly solves provides a kind of low cost, multi-functional, and functional stable, tourmalinite/titanium dioxide complex sol that the life-span is long when being on active service; A kind of preparation method of this colloidal sol is provided simultaneously, and this method technology is simple, and use equipment is few, and is with low cost; Also provided simultaneously the main application of this colloidal sol, be about to described tourmalinite/titanium dioxide complex sol doubly, made coating liquid with dehydrated alcohol dilution 1-20; Directly adopt conventional film coating method such as dipping lifts, spraying easily, at base material or product surface plated films such as the metal of different shape, pottery, glass; Can also with described tourmalinite/titanium dioxide complex sol doubly make spray coating liquor with dehydrated alcohol dilution 1-20; Directly be sprayed at the surfaces externally and internally of top ceiling and construction wall, all kinds of vehicles, give it and purify air, discharge negative ion and multiple function such as radiation infrared.
The technical scheme that the present invention solves the complex sol technical problem is: design a kind of tourmalinite/titanium dioxide complex sol, its raw material and the mass fraction that feeds intake are:
Titanium salt 5-15%;
Dehydrated alcohol 60-88%;
Organic acid 3-13%;
Mineral acid 2-15%;
Deionized water 0.5-1.5%;
Tourmalinite 0.001-3%, described titanium salt are meant any in butyl (tetra) titanate, metatitanic acid methyl esters, titanium tetrachloride, the titanyl sulfate; Described organic acid is meant any in acetic acid, oxalic acid, formic acid, the Phenylsulfonic acid; Described mineral acid is meant any in the vitriol oil, concentrated nitric acid, the concentrated hydrochloric acid; Described tourmalinite is meant one or more in iron tourmaline, elbaite, the dravite.
The technical scheme that the present invention solves described method and technology problem is: stirring 1-2h mixes with the dehydrated alcohol of titanium salt, organic acid, tourmalinite and half described mass fraction of described mass fraction in elder generation, then in the intensively stirred while, the mixing solutions of the dehydrated alcohol of the deionized water of the described mass fraction of dropping and second half described mass fraction in gained suspension, the dropping time is 0.5-1h, thereafter continue to stir 2-4h, the mineral acid that adds described mass fraction at last, continuously stirring 0.5-1h can make described tourmalinite/titanium dioxide complex sol again.
The present invention is with the natural forceful electric power polarity and the TiO of tourmalinite
2The photochemical catalysis strong oxidizing property organically combine, utilizing the natural highfield of tourmalinite securely will be by uviolizing TiO
2Film and excite the light induced electron of generation to catch, thus the compound again of light induced electron and photohole avoided, improve the utilization ratio of photohole, also promptly improved light-catalyzed reaction efficient greatly, give tourmalinite/TiO
2The photochemical catalytic oxidation ability that laminated film is superpower.
Compared with prior art, do not have magnetic in the prescription of tourmalinite of the present invention/titanium dioxide complex sol, tourmalinite content is less, economic formula, and product function is stable lasting, and prolong work-ing life; The inventive method not only preparation technology is simple, use equipment is few, with low cost, and in film, can form the microporous hollow spherical structure of titanium dioxide, improve film to organic capacity of decomposition, simultaneously also provide more photocatalytic activity position, promptly utilized self electric field of tourmalinite to catch the light induced electron of titanium dioxide, avoid the compound again of photoproduction hole and electronics, thereby increased photocatalytic activity; Product of the present invention directly and of many uses indirectly, adaptability is strong, with the traditional technology method compatibility, industrialization is used does not have obstacle; In addition, the tourmalinite among the present invention/titanium dioxide complex sol also has infrared radiation, discharges negative ion, reduces and multiple function such as activated water molecular grouping, has realized the health environment-friendly multifunctional all of tourmalinite/composite titania material.
Description of drawings
Fig. 1 is tourmalinite/TiO of the present invention
2A kind of embodiment 8 of complex sol is at the scanning electron microscopy analysis photo of copper primary surface plated film; Hollow ball among the figure bunch tourmaline particle and surperficial TiO by bunch inside
2Hollow ball constitutes;
Fig. 2 is tourmalinite/TiO of the present invention
2The scanning electron microscopy analysis photo on a kind of embodiment 1 of complex sol tourmaline particle surface in copper primary surface plated film; Figure hollow core spherical structure consists of TiO
2
Fig. 3 is tourmalinite/TiO of the present invention
2The scanning electron microscopy analysis photo on a kind of embodiment 1 of complex sol tourmaline particle surface in the glass-based surface coating;
Fig. 4 is tourmalinite/TiO of the present invention
2A kind of embodiment 1 of complex sol and the general T iO that does not contain tourmalinite
2Colloidal sol is at the plated film of the copper primary surface photocatalytic degradation rate curve to tropeolin-D; Curve 1--TiO
2Film; Curve 2--tourmalinite/TiO
2Laminated film.
Embodiment
Further specify the present invention below in conjunction with embodiment and accompanying drawing thereof:
Tourmalinite/TiO of the present invention
2The raw material of complex sol and the mass fraction that feeds intake are: titanium salt: 5-15%; Dehydrated alcohol 60-88%; Organic acid 3-13%; Mineral acid 2-15%; Deionized water 0.5-1.5%; Tourmalinite 0.001-3%; Described titanium salt can be in organic titanate and the inorganic titanium salt any, any in titanium ethanolate, butyl (tetra) titanate, metatitanic acid methyl esters, titanium tetrachloride, the titanyl sulfate etc. for example, the first-selected butyl (tetra) titanate of the embodiment of the invention; Described organic acid can be any in acetic acid, oxalic acid, formic acid, the Phenylsulfonic acid etc., the first-selected acetic acid of the embodiment of the invention; Described mineral acid can be any in the vitriol oil, concentrated nitric acid, the concentrated hydrochloric acid etc., the first-selected concentrated hydrochloric acid of the embodiment of the invention; Described tourmalinite can be one or more in iron tourmaline, elbaite, the dravite etc.; The embodiment of the invention first-selected iron tourmaline, i.e. natural black tourmalinite.
Tourmalinite/TiO of the present invention
2Complex sol raw material titanium salt, organic acid and mineral acid, why first-selected butyl (tetra) titanate, acetic acid and concentrated hydrochloric acid, be because butyl (tetra) titanate is compared hydrolysis with other titanium salts severe degree relatively a little less than, easier control helps realizing industrial applications; And acetic acid can close with the butyl (tetra) titanate huge legendary turtle, generates more stable huge legendary turtle and closes macromolecular mass, control hydrolysis speed; Concentrated hydrochloric acid is to TiO
2Micelle has the effect of dispergation, not only can be used for controlling TiO
2The size of micelle can also improve TiO
2The stability of colloidal sol.Tourmalinite/TiO of the present invention
2Complex sol raw material tourmalinite is first-selected iron tourmaline why, and promptly the natural black tourmalinite is that the ability of radiation red line far away is stronger because iron tourmaline has stronger piezoelectricity and pyroelectricity, and this external source is comparatively extensive, also helps realizing industrial applications.
The described raw material and the quality optimization umber that feeds intake of being further characterized in that of the present invention is: titanium salt 8-12%; Dehydrated alcohol 70-81%; Organic acid 5-9%; Mineral acid 5-10%; Deionized water 0.7-1.2%; Tourmalinite 0.01-1%.
Tourmalinite/TiO of the present invention
2The further feature of complex sol is that also described material component tourmalinite is that its purity is not less than 9O% (weight ratio) through the tourmalinite of purification and superfine grinding, and median size is not more than 5 μ m.This design is for can be better and TiO
2Colloidal sol is mutually compound, and stronger natural permanent electric field is provided, and improves the ability of infrared radiation and generation negative aeroion, and adds bigger serface.
Tourmalinite/TiO of the present invention
2The mass fraction that complex sol feeds intake be through to photochemical catalysis, radiation infrared, generate function such as negative ion, and performances such as stability, dissolved adhesiveness, micelle granularity are carried out synthetic study and are designed definite.Tourmalinite/TiO of the present invention
2In the complex sol main raw material: the mass fraction that feeds intake of titanium salt is designed to 5-15%, when its less than 5% the time because titanium content is lower, can influence the photochemical catalysis effect in the application process, reduce and the complex function effect of tourmalinite; Otherwise when surpassing 15%, the glue process is not easy control, simultaneously also can be too much because of titanium, and cause product in application process, to ftracture easily, and, influenced product infrared radiation and the ability that produces negative ion because of the blocked up titanium film of tourmalinite surface coverage.The mass fraction that feeds intake of tourmalinite is designed to 0.001-3%, actual application value and raw materials cost have mainly been considered, when the mass fraction that feeds intake of tourmalinite is lower than 0.001%, can influence in actual application the photochemical catalysis, the ability of radiation infrared and generation negative ion of film; When tourmalinite feeds intake mass fraction when surpassing 3%, on the one hand, to tourmalinite/TiO
2The film-forming properties of complex sol film and stability all can have a negative impact, and the injected volume of excessive tourmalinite can not produce very big effect to the function that improves laminated film on the other hand, can therefore increase raw materials cost on the contrary, and be uneconomical.
Tourmalinite/TiO of the present invention
2The preparation method of complex sol is characterised in that: stirring 1-2h mixes with the dehydrated alcohol of titanium salt, organic acid, tourmalinite and half described mass fraction of described mass fraction in elder generation, then in the intensively stirred while, the mixing solutions of the dehydrated alcohol of the deionized water of the described mass fraction of dropping and second half described mass fraction in gained suspension, the dropping time is 0.5-1h, thereafter continue to stir 2-4h, the mineral acid that adds described mass fraction at last, continuously stirring 0.5-1h can make described tourmalinite/TiO again
2Complex sol.
Tourmalinite/TiO of the present invention
2The complex sol purposes is further characterized in that, with described tourmalinite/TiO
2Complex sol with dehydrated alcohol dilution 1-20 is doubly made coating liquid; Directly adopt conventional film coating method such as dipping lifts, spraying plated film on material such as metal, pottery, glass or product surface then, thereafter seasoning is to surface drying, under 250-800 ℃ of constant temperature, toast 2-4h again, can obtain firm function plated film at described material or product.This method can be used for preparing to be had purifying air, discharges negative ion and the decoration ceramic tile of infrared radiation, the filtering material of the usefulness that purifies air etc.; Also can make different substrate materials can activated water, reduce the water dispenser water activated mesh of water clusters etc.; Can also with described tourmalinite/titanium dioxide complex sol doubly make spray coating liquor with dehydrated alcohol dilution 1-20; Spray coating liquor directly is sprayed at the surfaces externally and internally of top ceiling and construction wall, all kinds of vehicles, gives it and purify air, discharge negative ion and multiple function such as radiation infrared.
Provide specific embodiments of the invention below:
Embodiment 1:
With 0.2g iron tourmaline (median size is that 1.2 μ m, purity are 96.3%), the 10g tetrabutyl titanate, 38g dehydrated alcohol and 7g acetic acid mix and continuously stirring 1h, then in the intensively stirred while, the mixing solutions of 38g dehydrated alcohol and 1.0g deionized water slowly is added drop-wise in the above-mentioned suspension, about 30min dropwises, continue to stir 2h again, add the 8g concentrated hydrochloric acid at last, after continuing to stir 1h, can obtain tourmalinite/TiO of the present invention
2Complex sol.
Tourmalinite/the TiO that makes with aforesaid method
2The complex sol stable performance, sealed storage was never degenerated in 1 year, viscosity about 30s, multiple traditional plated film or spraying method such as be convenient to adopt that spraying, spin coating, dipping lift.
Embodiment 2:
With 0.001g iron tourmaline (median size is that 1.2 μ m, purity are 99.0%), the 5g tetrabutyl titanate, 40g dehydrated alcohol and 7g acetic acid mix and continuously stirring 1h, then in the intensively stirred while, the mixing solutions of 40g dehydrated alcohol and 0.6g deionized water slowly is added drop-wise in the above-mentioned suspension, about 30min dropwises, continue to stir 2h again, add the 6g concentrated hydrochloric acid at last, after continuing to stir 1h, can obtain tourmalinite/TiO of the present invention
2Complex sol.
Tourmalinite/the TiO that makes with aforesaid method
2The complex sol stable performance, sealed storage was never degenerated in 1 year, viscosity about 40s, multiple traditional plated film or spraying method such as be convenient to adopt that spraying, spin coating, dipping lift.
Embodiment 3:
With 0.1g elbaite (median size is that 5 μ m, purity are 96.0%), the 10g tetrabutyl titanate, 38g dehydrated alcohol and 7g acetic acid mix and continuously stirring 1h, then in the intensively stirred while, the mixing solutions of 38g dehydrated alcohol and 1.2g deionized water slowly is added drop-wise in the above-mentioned suspension, about 30min dropwises, continue to stir 2h again, add the 10g concentrated hydrochloric acid at last, after continuing to stir 1h, can obtain tourmalinite/TiO of the present invention
2Complex sol.
Tourmalinite/the TiO that makes with aforesaid method
2The complex sol stable performance, sealed storage was never degenerated in 1 year, viscosity about 40s, multiple traditional plated film or spraying method such as be convenient to adopt that spraying, spin coating, dipping lift.
Embodiment 4:
With 0.2g dravite (median size is that 6.3 μ m, purity are 96.3%), the 12g tetrabutyl titanate, 39g dehydrated alcohol and 10g acetic acid mix and continuously stirring 1.5h, then in the intensively stirred while, the mixing solutions of 39g dehydrated alcohol and 1.3g deionized water slowly is added drop-wise in the above-mentioned suspension, about 50min dropwises, continue to stir 3h again, add the 8g concentrated hydrochloric acid at last, after continuing to stir 1h, can obtain tourmalinite/TiO of the present invention
2Complex sol.
Embodiment 5:
With 0.5g lithium dravite (median size is that 1.2 μ m, purity are 99%), the 14g tetrabutyl titanate, 41g dehydrated alcohol and 12g acetic acid mix and continuously stirring 1.5h, then in the intensively stirred while, the mixing solutions of 41g dehydrated alcohol and 1.2g deionized water slowly is added drop-wise in the above-mentioned suspension, about 50min dropwises, continue to stir 3h again, add the 14g concentrated hydrochloric acid at last, after continuing to stir 1h, can obtain tourmalinite/TiO of the present invention
2Complex sol.
Embodiment 6:
With 2g iron tourmaline (maximum particle diameter 1.2 μ m, purity are 95%), the 14g tetrabutyl titanate, 42g dehydrated alcohol and 12g acetic acid mix and continuously stirring 1.5h, then in the intensively stirred while, the mixing solutions of 42g dehydrated alcohol and 1.2g deionized water slowly is added drop-wise in the above-mentioned suspension, about 50min dropwises, continue to stir 3h again, add the 14g concentrated hydrochloric acid at last, after continuing to stir 1h, can obtain tourmalinite/TiO of the present invention
2Complex sol.
Embodiment 7:
(median size is 1.2 μ m with iron tourmaline 1g, purity is 96.3%), (median size is 6.3 μ m to dravite 1.2g, purity is 96.3%), (median size is 5 μ m to elbaite 0.8g, purity is 96.0%), the 15g tetrabutyl titanate, 42g dehydrated alcohol and 12g acetic acid mix and continuously stirring 2h, then in the intensively stirred while, the mixing solutions of 42g dehydrated alcohol and 1.2g deionized water slowly is added drop-wise in the above-mentioned suspension, about 60min dropwises, continue to stir 3h again, add the 14g concentrated hydrochloric acid at last, after continuing to stir 1h, can obtain tourmalinite/TiO of the present invention
2Complex sol.
Embodiment 8:
Cutting the common red copper net of 5cm * 5cm is sample, with concentration is that 5% hydrochloric acid is removed copper oxide surface, rinse well with deionized water again, use embodiment 1 described complex sol then, adopt crystal pulling method to give described red copper net plated film, behind the plated film under 250 ℃ of constant temperature dry 3h, can obtain load electrical stone/TiO
2The red copper net of composite membrane.
Cut 2cm * 5cm simple glass sheet, use washing composition and deionized water, use embodiment 1 described complex sol then, adopt crystal pulling method to give described sheet glass plated film, at 600 ℃ of following constant temperature 3h, can obtain load electrical stone/TiO behind the plated film the glass surface washes clean
2The functional glass sheet of composite membrane.
Use tourmalinite/TiO that aforesaid method makes
2Composite membrane (referring to Fig. 1, shown in 2,3 and 4) has bigger specific surface area, and abundant reaction active site can be provided; Have stronger adsorptive power, increased organic reactant, can make reactant and TiO in its surperficial adsorptive capacity
2Contact more fully, improved the utilization ratio of reaction active site, also have the ability of higher far-infrared radiation rate and generation negative aeroion simultaneously.
Embodiment 9:
At first embodiment 2 described complex sols are carried out 5 times of dilutions with ethanol, cut common 5 * 5cm red copper net, with concentration is that 5% hydrochloric acid is removed copper oxide surface, rinse well with deionized water, in the diluent of embodiment 2 described complex sols, adopt the crystal pulling method plated film then, last 250 ℃ of following constant temperature 3h can obtain firm tourmalinite/TiO
2The red copper net of composite nanometer film plated film.
Cut 2 * 5cm simple glass sheet, use washing composition and deionized water with the glass surface washes clean, adopt the crystal pulling method plated film then in the diluent of embodiment 2 described complex sols, last 500 ℃ of constant temperature 3h can obtain load electrical stone/TiO
2The functional glass sheet of composite membrane.
Relative embodiment 8, the photocatalysis performance of this routine film a little less than, be close to 91% of embodiment 8 photo-catalysis capabilities.Other performances are close.
Embodiment 10:
At first embodiment 3 described complex sols are carried out 10 times of dilutions with ethanol, cut common 5 * 5cm red copper net, with concentration is that 5% hydrochloric acid is removed copper oxide surface, rinse well with deionized water, in the diluent of embodiment 3 described complex sols, adopt the crystal pulling method plated film then, last 300 ℃ of following constant temperature 3h can obtain the function red copper net of load electrical stone/TiO2 composite membrane.
Cut 2 * 5cm simple glass sheet, with washing composition and deionized water with the glass surface washes clean, adopt the crystal pulling method plated film then in the diluent of embodiment 3 described complex sols, last 700 ℃ of following constant temperature 3h can obtain the functional glass sheet of load electrical stone/TiO2 composite membrane.
Embodiment 11:
At first embodiment 3 described complex sols are carried out 20 times of dilutions with ethanol, cut common 5 * 5cm red copper net, with concentration is that 5% hydrochloric acid is removed copper oxide surface, rinse well with deionized water, in the diluent of embodiment 3 described complex sols, adopt the crystal pulling method plated film then, last 300 ℃ of constant temperature 3h obtain load electrical stone/TiO
2The function red copper net of composite membrane.
Cut 2 * 5cm simple glass sheet, use washing composition and deionized water with the glass surface washes clean, adopt the crystal pulling method plated film then in the diluent of embodiment 3 described complex sols, last 700 ℃ of following constant temperature 3h obtain load electrical stone/TiO
2The functional glass sheet of composite membrane.
Embodiment 12:
At first embodiment 4 described complex sols are carried out 20 times of dilutions with ethanol, cut common 5 * 5cm red copper net, with concentration is that 5% hydrochloric acid is removed copper oxide surface, rinse well with deionized water, in the diluent of embodiment 4 described complex sols, adopt the crystal pulling method plated film then, last 300 ℃ of constant temperature 3h obtain load electrical stone/TiO
2The function red copper net of composite membrane.
Cut 2 * 5cm simple glass sheet, use washing composition and deionized water with the glass surface washes clean, adopt the crystal pulling method plated film then in the diluent of embodiment 4 described complex sols, last 700 ℃ of constant temperature 3h obtain firm tourmalinite/TiO
2The functional glass sheet of composite membrane.
Claims (7)
1. tourmalinite/titanium dioxide complex sol, its raw material and the mass fraction that feeds intake are:
Titanium salt 5-15%;
Dehydrated alcohol 60-88%;
Organic acid 3-13%;
Mineral acid 2-15%;
Deionized water 0.5-1.5%;
Electric 0.001-3%,
Described titanium salt is meant any in butyl (tetra) titanate, metatitanic acid methyl esters, titanium tetrachloride, the titanyl sulfate; Described organic acid is meant any in acetic acid, oxalic acid, formic acid, the Phenylsulfonic acid; Described mineral acid is meant any in the vitriol oil, concentrated nitric acid, the concentrated hydrochloric acid; Described tourmalinite is meant one or more in iron tourmaline, elbaite, the dravite.
2. tourmalinite according to claim 1/titanium dioxide complex sol is characterized in that the described raw material and the mass fraction that feeds intake are:
Titanium salt 8-12%;
Dehydrated alcohol 70-81%;
Organic acid 5-9%;
Mineral acid 5-10%;
Deionized water 0.7-1.2%;
Tourmalinite 0.01-1%,
Wherein, the first-selected butyl (tetra) titanate of described titanium salt; The first-selected acetic acid of organic acid; The first-selected concentrated hydrochloric acid of mineral acid; The first-selected iron tourmaline of described tourmalinite.
3. according to claim 1,2 described tourmalinite/titanium dioxide complex sols, it is characterized in that described tourmalinite is meant that its purity is not less than 90% (weight ratio) through the tourmalinite of purifying and superfine grinding is processed, median size is not more than 5 μ m.
4. according to the preparation method of the described tourmalinite of arbitrary claim among the claim 1-3/titanium dioxide complex sol, it is characterized in that: elder generation is with the titanium salt of described mass fraction, organic acid, the dehydrated alcohol of tourmalinite and half described mass fraction mixes stirring 1-2h, then in the intensively stirred while, the mixing solutions of the dehydrated alcohol of the deionized water of the described mass fraction of dropping and second half described mass fraction in gained suspension, the dropping time is 0.5-1h, continue to stir 2-4h then, the mineral acid that adds described mass fraction at last, continuously stirring 0.5-1h can make described tourmalinite/titanium dioxide complex sol again.
5. according to the purposes of claims 1,2 or 3 described tourmalinite/titanium dioxide complex sols, it is characterized in that: with described tourmalinite/titanium dioxide complex sol doubly, make coating liquid with dehydrated alcohol dilution 1-20; Directly adopt conventional film coating method such as dipping lifts, spraying plated film on material such as metal, pottery, glass or product surface then, thereafter seasoning is to surface drying, at 250-800 ℃ of constant temperature 2-4h, can obtain firm functional membrane again at described material or product surface.
6. according to the purposes of claims 5 described tourmalinite/titanium dioxide complex sols, it is characterized in that adopting ordinary methods such as spraying, spin coating, dipping lift preparations to have purifying air, discharge negative ion and radiation infrared decoration ceramic tile, the filtering material of the usefulness that purifies air, and make different substrate materials can activated water, reduce the water dispenser water activated mesh of water clusters.
7. according to another purposes of claims 1,2 or 3 described tourmalinite/titanium dioxide complex sols, it is characterized in that with described tourmalinite/titanium dioxide complex sol doubly making spray coating liquor with dehydrated alcohol dilution 1-20; Spray coating liquor directly is sprayed at the surfaces externally and internally of top ceiling and construction wall, all kinds of vehicles.
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