CN101254461B - Composite photocatalyst, production method and combination containing same - Google Patents
Composite photocatalyst, production method and combination containing same Download PDFInfo
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- CN101254461B CN101254461B CN2008100855273A CN200810085527A CN101254461B CN 101254461 B CN101254461 B CN 101254461B CN 2008100855273 A CN2008100855273 A CN 2008100855273A CN 200810085527 A CN200810085527 A CN 200810085527A CN 101254461 B CN101254461 B CN 101254461B
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Abstract
The invention provides a composite photocatalyst which contains a photocatalyst coated with inorganic particles on the surface, wherein the content of inorganic particles is 3-70% by weight of the total solid content. The inventive composite photocatalyst is excellent in super-hydrophilicity, duration, antibacterial activity, deodorant effect and safety. The invention also provides a manufacturing method and compositions thereof.
Description
Technical field
The present invention relates to a kind of composite photo-catalyst, its method for making and contain its composition.
Background technology
Photochemical catalyst has the function of absorption light with excitation electron, thereby has light-catalysed performance.Photocatalyst material is after light excites, and then activate airborne aqueous vapor molecule or oxygen molecule and form hydroxyl free radical or negative oxygen ion, carry out redox, to decompose the pollutant in the environment, can use and remove in the air or pollutants in waste water, also can suppress to be attached to the bacterium on surface, reach antibiotic effect.
With titanium dioxide (TiO
2) as photochemical catalyst to carry out light-catalyzed reaction, start from photochemical catalyst electrode decomposition water that the Akira Fujishima of Tokyo Univ Japan in 1972 and K.Honda professor delivered to produce the result of study of hydrogen and oxygen, from then on open the gate of photochemical catalyst electrochemical reaction research.In nineteen ninety-five, after professor Fujishima delivers the Superhydrophilic and super-hydrophobicity achievement in research of photochemical catalyst once again, photocatalyst applications more expands self-cleaning functions such as anti-minute surface hazes or skin prevents dust to, human habitat is improved producing significant impact.
The photochemical catalyst product is generally nano particle, nano particle must be fixed in substrate surface.But often density is bad, causes particle to peel off, and produces dust, if suck human body, is a major injury to lung, and if be adhered on the skin, more can cause pore to stop up.In addition, the oxidation characteristic of photochemical catalyst also can directly cause the deterioration of base material, and especially organic class base material is as the cloth material.General solution to these problems is to embed an inorganic layer between base material and photochemical catalyst, but described method processed complex height.
For avoiding photochemical catalyst to cause the base material oxidation; industry mostly adopts composite photo-catalyst at present; promptly form protection in photocatalyst surface; for example No. 539579 bulletin of TaiWan, China patent discloses; utilizing has become the titanium dioxide powder of crystalline state to carry out finishing; but the shortcoming of described method is modification of surfaces (being difficult for powder disperses) uniformly, and causes particle excessive, influences the activity of photochemical catalyst.The another kind of method of protecting in photocatalyst surface formation is for utilizing sol-gal process; as United States Patent (USP) the 6th, 653, No. the 592824th, No. 356 or TaiWan, China patent disclose; the titanium dioxide and the silica of collosol state are disperseed, form crystallization with the high-temperature calcination more than 600 ℃ again.The shortcoming of the method is the initiation material costliness, and needs to use a large amount of organic solvents, easily causes environmental pollution, and high-temperature calcination can cause particle aggregation in addition, influences the effect of photochemical catalyst.
For improveing above-mentioned shortcoming, this case the inventor find through broad research, utilize Hydrolyze method to make photochemical catalyst, and add inorganic particles during the course, can obtain the composite photo-catalyst of anatase phase at low temperatures, both can keep the original function of photochemical catalyst, and can not cause the base material oxidation Decomposition again, and can effectively overcome above-mentioned shortcoming.
Summary of the invention
Main purpose of the present invention is to provide a kind of composite photo-catalyst, and it comprises the photochemical catalyst of surperficial coated inorganic particulate, and wherein said inorganic particles content is counted 3～70 weight % with the total solid component content.
Another object of the present invention is to provide a kind of composition that is used to prepare the method for above-mentioned composite photo-catalyst and comprises described composite photo-catalyst.
Description of drawings
On behalf of the present invention, Fig. 1 utilize the titanium tetrachloride hydrolysis legal system to be equipped with the composite photocatalyst agent method of anatase phase.
The specific embodiment
Composite photo-catalyst of the present invention comprises the photochemical catalyst of surperficial coated inorganic particulate, and described inorganic particles content is counted 3～70 weight % with the total solid component content.
Photochemical catalyst used in the present invention is that the those skilled in the art is known, for example titanium dioxide, zinc oxide, strontium titanates (SrTiO
3) or its mixture, be preferred wherein to environment or the more harmless titanium dioxide of human body.With regard to the catalyst performance viewpoint, the titanium dioxide that contains the anatase crystallization and be Main Ingredients and Appearance is preferred.In addition, the particle size of titanium dioxide is preferably 1 to 50 nanometer (nanometer nm), is preferably 5nm to 30nm.If titanium dioxide is less than 1nm, it is difficult to produce and is impracticable so, if but greater than 50nm, the photochemical catalyst effect will significantly reduce so.Because the oxidation characteristic of photochemical catalyst easily causes the base material deterioration, especially organic class base material so the present invention uses inorganic particles to come the cladding titanium dioxide surface, directly contacts with base material to avoid photochemical catalyst.
The inorganic particles that can be used among the present invention there is no particular restriction, and it for example is selected from the group that silica, aluminium oxide, cadmium sulfide, zirconia, calcium phosphate, calcium oxide and its mixture are formed, and is preferably silica.According to of the present invention one preferred specific embodiment, composite photo-catalyst of the present invention comprises the titanium dioxide optical catalyst of surperficial coated silica, and the content of wherein said silica is counted 10～30 weight % with the total solid component content.In this preferred specific embodiment, composite photo-catalyst utilization of the present invention has porous coated with silica titanium dioxide surface, make direct contact substrate of titania molecule, and the stink molecule can diffuse into and is adsorbed in titanium dioxide surface in the hole, and carry out photocatalysis Decomposition.
The present invention is characterized in that utilizing the titanium tetrachloride hydrolysis method to obtain the intermediate product titanium sulfate in addition about a kind of manufacture method of composite photo-catalyst, adds silica afterwards again, obtains the titanium dioxide composite photocatalyst of anatase phase at low temperatures.The inventive method can avoid using the high-temperature calcination step in the conventional processing procedure.
(as shown in Figure 1) according to an advantageous embodiment of the invention, the manufacture method of composite photo-catalyst of the present invention comprises following steps:
(a) utilize the titanium tetrachloride hydrolysis method to obtain the white gels hydrate;
(b) in reactor, the concentrated sulfuric acid is added in the gained hydrate, stirred 10～50 minutes, obtain titanium sulfate solution;
(c) silica is added in the above-mentioned titanium sulfate solution, fully mix, stirred 0.5～2 hour down in normal temperature;
(d) be warmed up to 80-100 ℃, under fixed temperature, reacted 4～7 hours; With
(e) splash into 4～6M sodium hydrate aqueous solution, filter then, wash and at room temperature dry, can obtain the composite titanium dioxide photocatalyst powder.
The silica of step in the processing procedure of the present invention (c) there is no particular restriction, and it can be powder form, aqueous solution form or colloidal form, and its particle diameter is preferably 10nm between the 30nm.
The above-mentioned processing procedure gained of the present invention composite photo-catalyst powder has about 50～500m
2The surface area of/g.
The present invention provides a kind of composition in addition, and it comprises above-mentioned composite photo-catalyst and solvent.
Photochemical catalyst content in the present composition is counted 1～70 weight % with composition total weight, is preferably 3～30 weight %.When the content of photochemical catalyst during, photochemical catalyst usefulness deficiency less than 1 weight %, if but surpass 70 weight %, so dispersed can sharp fall.The pH value scope of the present composition should be controlled between 1～5.
The contained solvent of the present composition is water and/or organic solvent.Be preferably hydrophilic organic solvent in the organic solvent, for example methyl alcohol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol (DEG), glycerine, acetone, MEK, ethyl acetate and its mixture etc.
The present composition can optionally comprise those skilled in the art's known additives.For example, metallics such as silver or copper can be added, or, metals such as palladium or platinum can be added for improving the catalytic activity of photochemical catalyst for improving bactericidal effect.This class additive level is about 10～10000ppm in composition total weight.
Following examples are used for the present invention is further specified, but are not in order to limit the scope of the invention.Modification that any those skilled in the art can reach easily and change all are included in the scope of the disclosure of this case specification and the claims of enclosing.
Embodiment
If following examples and comparative example do not have special declaration (weight %) all by weight percentage.
Embodiment 1
Get the titanium tetrachloride solution of 3.9M 200ml, thin up is 2000ml to cumulative volume, splash into the ammoniacal liquor of 500ml (5M), the white titanium dioxide hydrates utilization that produces is filtered, with 200ml deionized water washing three times, remove excessive moisture, can obtain the titanium hydroxide hydrate [TiO (OH) of white gels
2].
The concentrated sulfuric acid (18M) of 60ml is added in the above-mentioned hydrate, stirred 30 minutes, obtain a transparent clarification titanium sulfate solution, titanium sulfate solution is placed reactor, be warmed up to 100 ℃, reacted 5 hours.The SiO that in the titanium sulfate that is obtained, adds 25 grams
2The aqueous solution (20%), normal temperature stirred 1 hour down.
Splash into 700ml (5M) sodium hydrate aqueous solution, filter, washing and under drying at room temperature, can obtain white powder, detect through XRD and FE-SEM, white powder is the Detitanium-ore-type photochemical catalyst, and particle diameter is 15-19nm.
The octahedrite type titanium dioxide photocatalyst of gained is added in the acrylic resin (Enternal-6134, resin solid content=45%) adding proportion TiO
2: resin=3: 7, add a little nitric acid the pH value is adjusted between the 1-2, dispersed with stirring is coated on the glass plate to make with 50 micron thickness and is filmed, and carries out weather resistance test (utilizing the weather-proof accelerated testing cabinet of QUV, Q-panel company).The result is as shown in table 1 below for the test gained.
Be placed on the initial stage concentration of being equipped with filming and be in 5 liters of four jiaos of bags of acetaldehyde of 120ppm, it is shone 0.88mW/cm with black light
2The ultraviolet light of intensity 365nm wavelength shone after 100 hours, measured the concentration of acetaldehyde with detector tube.The result is as shown in table 2 below for the test gained.
Embodiment 2
Repeat the step of embodiment 1, but use the SiO of 50 grams instead
2The aqueous solution (20%).Test gained result is shown in following table 1 and table 2.
Comparative example 1
Get the titanium tetrachloride solution of 3.9M 200ml, thin up is 2000ml to cumulative volume, splashes into the ammoniacal liquor of 500ml (5M), the white titanium dioxide hydrates utilization that produces is filtered, with 200ml deionized water washing three times, remove excessive moisture, can obtain the titanium hydroxide hydrate of white gels.
The concentrated sulfuric acid (18M) of 60ml is added in the above-mentioned hydrate, stirred 30 minutes, obtain a transparent clarification titanium sulfate solution, titanium sulfate solution is placed reactor, be warmed up to 100 ℃, reacted 5 hours.
Splash into 700ml (5M) sodium hydrate aqueous solution, filter, washing and under drying at room temperature, can obtain white powder, detect through XRD and FE-SEM, white powder is the Detitanium-ore-type photochemical catalyst, and particle diameter is 15-19nm.
The octahedrite type titanium dioxide photocatalyst of gained is added acrylic resin (Enternal-6134, solid content=45%) in, adding proportion is TiO2: resin=3: 7, adding a small amount of nitric acid is adjusted into the pH value between the 1-2, dispersed with stirring, coat on the glass plate to make with 50 micron thickness and film, carry out weather resistance test (utilizing the weather-proof accelerated testing cabinet of QUV, Q-panel company).The result is as shown in table 1 below for the test gained.
Be placed on the initial stage concentration of being equipped with filming and be in 5 liters of four jiaos of bags of acetaldehyde of 120ppm, it is shone 0.88mW/cm with black light
2The ultraviolet light of intensity 365nm wavelength shines the concentration of measuring acetaldehyde after 100 hours with detector tube.The result is as shown in table 2 below for the test gained.
Comparative example 2
Repeat the step of embodiment 1, but in the Detitanium-ore-type photochemical catalyst of white powder, add the SiO of 50 grams in addition
2The aqueous solution (20%).Test gained result is shown in following table 1 and table 2.
Comparative example 3
Repeat the step of embodiment 1, but with SiO
2The aqueous solution (20%) changes 200 grams into.Test gained result is shown in following table 1 and table 2.
(table 1): weatherability test
| ? | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| The anti-efflorescence time | 450-550hr? | 800-900hr? | ＜100hr? | ＜100hr? | 1200-1500hr? |
(table 2): acetaldehyde deodorization test [residual rate]
The result of comparing embodiment 1 and comparative example 3 and embodiment 2 and comparative example 3 as can be known, composite photo-catalyst is coated with in the rete, dioxide-containing silica is many more, the anti-efflorescence time is long more, promptly base material is difficult for oxidation more.But excessive finishing reduces photocatalyst activity on the contrary, thereby reduces deodorizing effect
The result of comparing embodiment 1 and comparative example 1 and embodiment 2 and comparative example 1 modifies if photochemical catalyst has silica to do the surface as can be known, easy efflorescence, and do not have silica to assist absorbing and deodorizing thing, photocatalyst deodorization DeGrain.
The result of comparing embodiment 2 and comparative example 2 if only utilize physical absorption, carries out the finishing of titanium dioxide with silica as can be known, easily coats inhomogeneously, causes titanium dioxide still may directly contact with base material, causes oxidation.
Claims (9)
1. composite photo-catalyst, its titanium dioxide and described composite photo-catalyst that comprises surperficial coated inorganic particulate has 50～500m
2The surface area of/g, wherein said inorganic particles content is counted 10～30 weight % with the total solid component content, and described titanium dioxide is the anatase crystallization.
2. composite photo-catalyst according to claim 1, wherein said inorganic particles is selected from the group that silica, aluminium oxide, cadmium sulfide, zirconia, calcium phosphate, calcium oxide and its mixture are formed.
3. composite photo-catalyst according to claim 1, wherein said inorganic particles are silica.
4. composite photo-catalyst according to claim 3, wherein titanium dioxide optical catalyst has the particle diameter of 1nm to 50nm.
5. composite photo-catalyst according to claim 4, wherein titanium dioxide optical catalyst has the particle diameter of 5nm to 30nm.
6. composition, it comprises composite photo-catalyst according to claim 1 and solvent, and the content of wherein said composite photo-catalyst is in composition total weight, between 1～70 weight %.
7. composition according to claim 6, wherein said solvent are water and/or hydrophilic organic solvent.
8. composition according to claim 6, the content of wherein said composite photo-catalyst in composition total weight between 3～30 weight %.
9. composition according to claim 6, the pH value scope of wherein said composition is 1～5.
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| TWI618578B (en) * | 2015-05-15 | 2018-03-21 | 莎哈利本化學有限公司 | Powdered titanium oxide, processes for preparing the same and the use thereof |
| CN105727997A (en) * | 2016-01-29 | 2016-07-06 | 上海师范大学 | Cadmium sulfide/sodium titanate supported type compound visible-light-driven photocatalyst and preparation method and application thereof |
| CN111790418B (en) * | 2019-04-08 | 2023-05-26 | 国家纳米科学中心 | Calcium-titanium composite material and preparation method and application thereof |
| CN114618537B (en) * | 2022-04-10 | 2023-05-26 | 贵州大学 | Red phosphorus/strontium titanate heterojunction photocatalyst, and preparation method and application thereof |
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| CN1407029A (en) * | 2001-08-27 | 2003-04-02 | 上海大学 | Preparation of nano-silicon/titanium composite particles |
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