CN101024203A - High-performance light catalyst loating solution and preparing method - Google Patents

Abstract

This invention discloses a high-performance light accelerant coating solution and manufacturing methods. This invention is a manufacturing method of using light accelerant to disperse solution and colloidal inorganic oxides Sol light accelerant solution. Its key technology is in room temperature conditions the inorganic oxide particles coating on the light accelerant particle surface to prevent the organ base material in the light accelerant effect to induce decomposition of base material or coating film, furthest advanced the decomposition and solution storage stability of high Painting Solution to hazardous substances. Manufacturing methods include: 1) the created mixed sol solution stage after stringing light accelerant dispersed solution and colloidal inorganic oxide solution, 2) add distilled water or carbon alcohol in the mixture, regulating the content of the mixture solid phase, 3) adding acid or base into above solution, adjusting the pH value stage.

Description

High-performance light catalyst loating solution and manufacture method thereof

Technical field

The present invention is the invention of the manufacture method of relevant light catalyst loating solution.Specifically, it is part coating nano inorganic oxide particle simply on the photocatalyst particle surface under normal temperature condition, prevent that effectively application from crossing the organic substrate of photocatalyst (fiber, plastic cement etc.) and being decomposed by the coated film of photocatalyst, make coated film when durability strengthens, improve manufacture method most effectively the light catalyst loating solution of harmful substance resolution ratio.

Background technology

Photocatalyst is the material that shows catalyst performance under the effect of light.The illuminated light to a certain degree of photocatalyst, electronics from the band guide that is situated between charged from, conduction band generates electronics, and that the band that is situated between forms the hole is right, thereby produces strong reducing power and oxidability.Be that illumination is mapped on the photocatalyst substance, become electronics and hole right in the particle internal ionization, and electronics of separating and hole subtend photocatalyst particle surface move, and with moisture and oxygen reaction on every side, form strong oxidability.Particularly because electronics that ionization generated and hole pair and substance reactions such as water, oxygen, generate active OH-and negative oxygen ion, so be easy to these organic structural deteriorations are decomposed, thereby reach the purpose of decomposing various harmful chemicals and stink substance.

The research of photocatalyst mainly concentrates on the photocatalyst of pulverulence and mixes the product (Republic of Korea patent 10-0185179) of formation with other materials, but this product is because problems such as the caused stability of precipitation reduction have been subjected to a lot of restrictions in practical process.

After, the photocatalyst powder is mainly used in the dispersion liquid of making the suspension form.Though imagination photocatalyst dispersion liquid mixes with organic materials such as fiber, plastic cement or application after formation film decomposing harmful substances, but because the effect of photocatalyst, in with harmful substance in the environment and polluter decomposition, also decomposed organic substrate bodies such as fiber, plastic cement, used just very difficult.

The 9-239277 of Japan Patent office patent has been put down in writing the photocatalyst dipping body that floods non-Photoactive compounds such as silicon, aluminium, pick on the surface of titanium dioxide.Thisly handle with non-Photoactive compounds such as silicon, aluminium, pick and the method for flooding at titanium dioxide surface, be originally in cosmetics or pigment field for the catalyst activity that reduces titanium dioxide to be the method that purpose develops, can contain reaction between titanium dioxide and the organic substances such as fiber, plastic cement with the method, but also reduce significantly as the decomposition of photocatalyst simultaneously thereupon.In addition, this titanium dioxide is made antibiotic, mildew-resistant photocatalyst, because of mushroom is not easy attached to the photocatalyst film coated surface, thereby make the effect of photocatalyst be not easy performance, efficient reduces, the low inferior problems of durability will occur.In addition, even proposed to preventing the decomposition of base material, other application layers of first application one deck, again in the method for its external coating photocatalyst, but this needs twice application, and cost and engineering operational ton risen significantly.

Present light catalyst loating market is just needing a kind ofly also to keep excellent in performance applicable to various materials, long-term use, and coated film self also has the hardening at subcritical temerature type light catalyst loating material of durability.

Summary of the invention

The technical issues that need to address of the present invention are to disclose a kind of high-performance light catalyst loating solution and manufacture method thereof, to overcome the above-mentioned defective that prior art exists.

The manufacture method of light catalyst loating solution provided by the invention comprises the steps:

(1) the photocatalyst dispersion soln of dispersion step manufacturing and colloid inorganic oxide solution stir the step that mixed sols is made in the back;

(2) in above-mentioned mixed solution, add alcohol or distilled water, the step of regulating the solid content of mixed solution;

(3) add acid or alkali in the solution that contains solid constituent of above-mentioned adjusting, regulating pH value is the step of principal character.

The present invention can increase the step that the step of adding photocatalyst powder and solvent or dispersant is made the photocatalyst dispersion soln before above-mentioned steps (1).

The present invention comprises the above-mentioned solution that regulates pH value, can increase the step that the step of adding metal mixed is made the photocatalyst dispersion soln again, i.e. the 4th step;

Photocatalyst powder of the present invention comprises titania powder.

The above-mentioned colloid inorganic oxide colloidal sol of the present invention comprises the cataloid inorganic oxide sol.

The present invention can be added with the organic silane compound adhesive in above-mentioned steps (1).

The present invention comprises produced light catalyst loating solution of above stage.

Describe the present invention in detail according to appended pattern.Appended pattern is in order to narrate example of the present invention, with the example more than 1 formation of the present invention and effect to be described at least according to this pattern.

In addition, technical thought of the present invention and its formation and effect not only are confined to this example, and the scope of technical thought of the present invention also is not limited to appended pattern.In addition, by the same inscape of appended pattern, in this patent, can use unified symbol as far as possible.

The method that the present invention makes light catalyst loating solution is a photocatalyst particle surface part application colloid inorganic oxide particle simply under normal temperature condition, photocatalyst is not having organic substrates such as fiber, plastic cement on the basis of decomposing, show quite outstanding catalyst performance, therefore be not subjected to the restriction of base material.The invention provides a kind of field outstanding light catalyst loating solution of performance very widely that uses.

Adopt the manufacture method of light catalyst loating solution of the present invention, formed and partly be coated with the colloid inorganic oxide particle surface double electrical layers that is contained in the photocatalyst particle surface, thereby obtained the fabulous light catalyst loating solution of a kind of storage stability.

Adopt the manufacture method of light catalyst loating solution of the present invention, surface at employed colloid inorganic oxide colloidal sol, by MOH (M:Si, Zr, Al, Deng) and OH-constitute, so, can keep the light catalyst loating solution of Superhydrophilic and organic matter characterization of adsorption for a long time even a kind of irradiation that does not have light can be provided.

Adopt the manufacture method of light catalyst loating solution of the present invention,, add acid again or alkali is regulated pH value, the light catalyst loating solution that provides a kind of pH value to regulate according to environment for use at the last stage that mixed solution is made.

Adopt the manufacture method of light catalyst loating solution of the present invention, after the manufacturing of final mixed solution, add metal ion and metal oxide regulator solution, provide a kind of and strengthened light catalyst loating solution antibiotic, sterilizing ability with the simplest engineering.

Light catalyst loating solution through the present invention's manufacturing, it is part coating nano inorganic oxide particle simply on the surface of photocatalyst under normal temperature condition, prevent that effectively application from crossing the organic substrate of photocatalyst (fiber, plastic cement etc.) and being decomposed by the coated film of photocatalyst, and when the durability that makes coated film strengthens, improve resolution ratio to harmful substance.

Description of drawings

Fig. 1 is a programme diagram of making light catalyst loating solution according to the present invention.

Fig. 2 is for being the illustraton of model of example withTiO 2 particles and cataloid.

Fig. 3 is the illustraton of model of coated film of the application of Fig. 2.

Fig. 4 is the schematic diagram of surface charge state

Fig. 5 is the schematic diagram of surface charge state.

Fig. 6 is the schematic diagram of surface charge state.

Fig. 7 utilizes comparative example 1 and 2 and the solution of 1 li manufacturing of example, is coated with the durability evaluation result who is contained in the sample that obtains on the fiber of forming with organic substance.

The specific embodiment

Referring to Fig. 1, method of the present invention comprises thatdispersion step 1, mixedsolution manufacturing process 2, solid component content are regulatedoperation 3, pH value is regulatedoperation 4, additive mixedprocesses 5;

Saiddispersion step 1 is the photocatalyst powder of 1～40 unit of weight is arranged intotal amount 100 unit of weights and to be mixed together as other components of solvent and dispersant, use the pearl or the sphere of 0.1～3mm diameter, in revolution is 100～2000rpm scope, milled 0.5～48 hour;

The pH value (hydrogen ion concentration) of the dispersion liquid of the above-mentioned dispersion engineering of process manufacturing it would be desirable 10～12 in 1～14 scope.The mean size of photocatalyst particle is 1～1000nm in the dispersion liquid, it would be desirable 40～100nm.The photocatalyst powder also can use the titanium oxide dispersion of selling on the market.Above-mentioned photocatalyst powder and dispersion liquid have not only comprised titanium dioxide, and comprise WO₃, ZnO₃, SiC, SnO₃, ZrO₂, V₂O₅Deng the total material that is used in the manufacturing photocatalyst.Can use two or more mixture of powders as required.

Above-mentioned colloid inorganic oxide colloidal sol can use silica gel, the cataloid of market sale, also can use a lot of inorganic oxide sols such as silica, aluminium, but the surface of inorganic oxide particle must form the electric double layer structure.

The pH value of above-mentioned colloid inorganic oxide colloidal sol is 3～5 scopes, and wherein the mean size of cataloid particle is 10～40nm, and is configured to the most desirable with the electric double layer that forms the al-khary ion.In addition, can use the mixture of two or more variety classes colloid inorganic oxide colloidal sols as required.

In the mixedsolution manufacturing process 2 below, be to be 1～40% the dispersion soln and the colloid inorganic oxide colloidal sol ofsolid content 1～40% with the solid content that above-mentioneddispersion step 1 is made, mixed in 1: 9～9: 1 according to the solid constituent ratio, stir with 300～1500rpm rotating speed at normal temperatures and made in 10～30 minutes, best solid constituent ratio is 4: 6～6: 4.At this moment, the mean size of photocatalyst particle is optimum is bigger 2～20 times than the particle mean size of colloid inorganic oxide colloidal sol.When needs guarantee the transparency, be 40～90nm with the mean size of photocatalyst particle, SiO₂Particle size is that 10～20nm is optimum;

In addition, in the above-mentioned mixed solution that adds bronsted lowry acids and bases bronsted lowry, optionally add acid or alkali mixed solution, at normal temperature and be no more than under 60 ℃ of states and stirred 1～6 hour as the organic silane compound of binder.Above-mentioned organic silane compound bonding agent comprises MTMS; ethyl trimethoxy silane; the vinyl methyl-monosilane; the vinyl ethylsilane; right type methyl dextrorotation methoxy silane; right type methyl dextrorotation Ethoxysilane; vinyl methyl three dextrorotation methoxy silane; vinyl methyl three dextrorotation Ethoxysilanes; phenyltrimethoxysila,e; tetrem acidylate Ethoxysilane; the ethoxyl methyl vinyl silanes; the butoxy trimethyl silane; butyl trimethoxy silane; right type phenyl ethoxy vinyl silanes; methyl three isopropoxy silane; methyl triacetoxysilane; tetrem acidylate phenoxy group silane; tetrem acidylate propoxyl group silane; in the vinyl silane triisopropoxide more than a kind.

In solid constituent is regulatedoperation 3, the alcohol of above-mentioned mixed solution or mixedsolution 100 unit of weights of having added bonding agent and carbon containing 1～4 or distilledwater 50～500 unit of weights are mixed regulate solid constituent.

In pH value is regulatedoperation 4, added acid in the solution of solid constituent or alkali is regulated pH value regulating, make a kind of final light catalyst loating solution;

In addition, be additive mixedprocesses 5 at last, sterilization, antibacterial functions in order to improve above-mentioned final solution optionally add metal ion and metal oxide, and mix with solution state.Metallic addition comprises and is not limited to silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), mixes 0.05～10 unit of weight and make in final lightcatalyst loating solution 100 unit of weights.

Application product as example of the present invention can be used in materials such as glass, metal, pottery, also can be used on wall paper, shutter, fiber, timber indoor products such as (furniture) and the medical product and on the outdoor architecture material.When particularly on the septum pellucidum soundboard of making by plastic materials such as acrylic acid, Merlon, using, do not need the just directly application of other coating agents of precoating.Its range of application is very widely as can be seen.In addition, its solution can be used with plastic cement or other organic material mixing aftershapings.

The shape of the particle of above-mentioned application solution and the illustraton of model of coated film are example withTiO 2 particles and cataloid, as shown in Figures 2 and 3.Among Fig. 2,8 represent the particle of silica, and 9 represent the particle of titanium dioxide, and the particle size of titanium dioxide is 40～100nm, and the particle size of silica is 10～40nm.Among Fig. 3,10 represent base material.

By Fig. 2 and Fig. 3 as can be seen, TiO₂SiO on the particle surface₂Particle is not all to cover top but part is coated with top loading.Fig. 3 is the illustraton of model of the coated film of application; the base material that is coated, even organic substrates such as fiber, plastic cement, because the silica of application has the effect of diaphragm on the surface of photocatalyst; so photocatalyst does not contact with the organic substrate surface, can prevent the decomposition of base material.

The surface charge of Fig. 4 displaylight catalyst particle 1 trend cloudy 3 is charged, and Fig. 5 is a charged pattern on the surface ofinorganic oxide particle 2, and particle surface trend cloudy 4 is charged, andtrend sun 5 is charged on every side, demonstrates the structure that forms electric doublelayer.Photocatalyst particle 1 andinorganic oxide particle 2 mix, and stir at normal temperatures, and the surface is because of the difference of energy, and inorganic oxide particle has formed the shape of Fig. 6 attached to the surface of photocatalyst particle.The inorganic oxide particle of application on this moment photocatalyst particle surface, because the charged electric double layer of inorganic oxide surface trend sun, produce repulsive force betweensun 6 and thesun 7, partly be coated with and installed, and all do not cover the surface of photocatalyst, so the excellent in performance of photocatalyst just can be kept well.

Shown in Figure 6, the colloid inorganic oxide particle of photocatalyst surface top application has been owing to formed electric double layer, thereby makes the greatly dispersed of photocatalyst, improved the storage stability of solution thereupon.The present invention explains detailedly by following comparative example and example, but not only is confined to this example.

Comparative example 1

By disperseing the solution of engineering manufacturing: nascent particle mean size is 5～10, is Detitanium-ore-type photocatalyst powder 20g and distilled water 74g and the dispersion 6g of 30～60 μ m after the cohesion, mills 24 hours with the scandium oxide ball of 0.3mm and 1mm diameter.At this moment, pH (hydrionic concentration) is 10.2.

Comparative example 2

What colloid inorganic oxide colloidal sol was selected is the cataloid of selling on the market.Its solid component content is 20%, and pH value (hydrogen ion concentration) is 4, because the existence of Na+ ion forms double electrical layers.

Embodiment 1

The cataloid of thesolid content 20% that the dispersion soln of thesolid content 20% that above-mentioned comparative example 1 is made and above-mentioned comparative example 2 are selected, with 1: 1 ratio of solid constituent at normal temperatures, 800rpm speed mixed 30 minutes.After the stirring distilled water or ethanol are added in the mixed solution, regulate solid content to 4%, the pH value of this moment is 8.Regulate pH value to 7 with 10% salpeter solution, make the neutral solution of photocatalyst.

Embodiment 2

The dispersion soln of above-mentioned example 1 and cataloid mix in 7: 3 ratio, implement with quadrat method according to the described of above-mentioned example 1, make pH value and be 7 photocatalyst neutral solution.

Embodiment 3

The dispersion soln of above-mentioned example 1 and cataloid mix in 3: 7 ratio, implement according to the narration method of above-mentioned example 1, make pH value and be 7 photocatalyst neutral solution.

Embodiment 4

The dispersion soln of above-mentioned example 1 and cataloid mix in 1: 1 ratio, implement according to the narration method of above-mentioned example 1, and the pH value of final solution is regulated with 10% salpeter solution, make pH value and be 2 photocatalyst acid solution.

Embodiment 5

The dispersion soln of above-mentioned example 1 and cataloid mix in 1: 1 ratio to be made, and implements according to the narration method of above-mentioned example 1, and the pH value of final solution is regulated with 4% ammonia spirit, makes pH value and be 10 photocatalyst alkaline solution.

Table 1 is the solution of comparative example 1,2 and example 1～5 manufacturing, has carried out the signal table that the benzene rate is estimated that removes of stability and application sample.The stability of (example 1-5) its solution was very outstanding when as can be seen from Table 1, relatively cataloid mixed with comparative example 1.Also very good by its stability of solution (example 1,4,5) that method of the present invention is made under the situation that pH value changes.Utilize various solution applications sample survey its remove the benzene rate, after two hours, except comparative example 2, all reach more than 95%, the problem that does not have the photocatalyst performance to reduce, and when mixing 50% photocatalyst, the adsorption capacity of cataloid is stronger, and the performance of photocatalyst is also better.Comparative example 2 is not there being photocatalyst when only having used cataloid, and about 30 minutes to 2 hours, embody 30% the benzene rate of removing, confirmed only to have absorption property.

Table 1

	Comparative example 1	Comparative example 2	Example 1	Example 2	Example 3	Example 4	Example 5
								Stability of solution	Bad	Very outstanding	Very outstanding	Outstanding	Very outstanding	Very outstanding	Very outstanding
Remove the benzene rate behind the 2hr	97％	31％	100％	100％	91％	100％	100％

(1) stability of solution: the solution of making is observed after placing certain hour in 60 ℃ of baking ovens.

Very outstanding: as to place not unusual more than 20 days.

Outstanding: as 10-20 variable color between day, to solidify, precipitate formation.

Generally: 5-10 variable color between day, solidify, precipitate formation.

Bad: as variable color between 5 days, to solidify, precipitate formation.

(2) resolution ratio of gaseous organic substance: with the concentration of gas check pipe method measurement benzene (acetaldehyde), the method for measurement as described below.

-Japanese photocatalyst experimental method // (calendar year 2001 degree version), gasbag A method is estimated.

-ready application sample ultraviolet ray (1mW/cm²) shine and carried out pre-treatment in 3 hours.

Fill air in the-3L tedlar sack, inject approximately 100ppm of benzene (acetaldehyde), in the dark placed 30 minutes after evenly mixing.

-5L tedlar sack cuts one side, with the application sample of pre-treatment, seals after extracting the air in the sack again out.

Benzene (acetaldehyde) in-3L tedlar sack is sent in the 5L tedlar sack of sample, in thedark places 30 minutes.

-2 groups of samples preparing with above method, each comfortable bright condition (ultraviolet ray: 1mW/cm²) and dark condition (dark place) estimate after placing.

-(0 hour) in the early stage, 0.5 hour, 1 hour, 2 hour time, utilize gas check pipe method, internal gas as sample, is confirmed the scale value of gas, calculate the benzene rate of removing.

-except that benzene rate=(dark condition mean value-Ming condition mean value)/dark condition mean value * 100

Fig. 7 utilizes comparative example 1 and 2 and the solution of 1 li manufacturing of example, is coated with and is contained in the sample that obtains on the fiber of forming with organic substance, for the durability of confirmatory sample, estimated sample and removed the result of benzene rate after 50 hours in 1 hour in the ultraviolet lamp irradiation.

The situation of the photocatalyst sample of application comparative example 1: remove the benzene rate and have only 41% to the ultraviolet ray irradiation in the time of 50 hours from 89% of the initial stage, performance has reduced more than 50%.Ultraviolet ray irradiation application sample is in the time of 30 hours, and it removes the benzene rate and sharply descends.

The situation of the cataloid sample of application comparative example 2: remove the benzene rate and be reduced to 30% to the ultraviolet ray irradiation after 50 hours from 31% of the initial stage.

The solution that application mixes with the photocatalyst of example 1 and 1: 1 ratio of cataloid is as the situation of sample: the initial stage removes the benzene rate and reaches 96%, and the ultraviolet ray irradiation is after 50 hours, it removes the benzene rate and has also reached 95%, do not occur base material itself being produced the phenomenon appearance of decomposing, and kept the very outstanding performance of photocatalyst because of the effect of photocatalyst.

Claims (8)

1. photocatalyst solution manufacture method of utilizing photocatalyst dispersion soln and colloid inorganic oxide colloidal sol.

2. method according to claim 1 is characterized in that, the manufacture method of high-performance light catalyst loating solution comprises following steps:

(1) photocatalyst dispersion soln and colloid inorganic oxide colloidal sol stir the step that mixed solution is made in the back;

(2) in above-mentioned mixed solution, add alcohol or distilled water, the step of regulating the mixed solution solid content;

(3) in having regulated the above-mentioned solution of solid content, add the step that acid or alkali are regulated the mixed solution pH value.

3. method according to claim 2 is characterized in that, comprises the manufacture method of the high functionality light catalyst loating solution made from the next stage:

In step (1) before, comprise that photocatalyst powder, solvent and dispersant make the step of photocatalyst dispersion soln.

4. method according to claim 2 is characterized in that, comprises the manufacture method of the high-performance light catalyst loating solution made from the next stage: in the solution of above-mentioned adjusted pH value, add metallic addition.

5. according to claim 2,3 or 4 described methods, it is characterized in that said photocatalyst powder comprises the high-performance light catalyst loating solution manufacture method of titania powder.

6. according to claim 2,3 or 4 described methods, it is characterized in that said colloid inorganic oxide colloidal sol comprises the high-performance light catalyst loating solution manufacture method of silica inorganic oxide sol.

7. according to claim 2,3 or 4 described methods, it is characterized in that step (1) stage is added with the high-performance light catalyst loating solution manufacture method of organic silane compound adhesive.

8. the high functionality light catalyst loating solution that method according to claim 1 produces.

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