CN1382521A - Metal composite titanium dioxide nano particle and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of nanomaterials, and in particular relates to metal composite titanium dioxide nanoparticles with the functions of antibacterial, mildewproof, deodorizing, degrading organic pollutants, and decomposing harmful gases, as well as its preparation method and application. Using titanium tetrachloride as raw material, it is prepared by hydrothermal method. The method comprises the following steps: (1) preparing an aqueous solution of titanium tetrachloride; (2) adding 0.1 to 30 parts of a transition metal salt to 10 to 50 parts of the aqueous solution of titanium tetrachloride in step (1) and dissolving it in 95 to 100 parts of A solution generated in ionized water, the transition metal salt can be complexed by a complexing agent; stirring, constant temperature at 50-400 ° C; (3) washing, centrifugal sedimentation, to obtain a metal compound with a particle size of 3-50 nanometers Titanium dioxide nanoparticles; wherein, the metal accounts for 0.005-5 parts by weight, and the titanium dioxide accounts for 95-100 parts by weight. It is used to prepare architectural ceramics and coatings with antibacterial, mildew-proof, and pollutant-decomposing functions.

Description

Metal composite titanium dioxide nanoparticles and its preparation method and use

Technical field

The invention belongs to the technical field of nanometer materials, and in particular relates to metal composite titanium dioxide nanoparticles with the functions of antibacterial, mildewproof, deodorizing, degrading organic pollutants and decomposing harmful gases, as well as its preparation method and application.

Background technique

At present, the use of titanium dioxide photocatalysts for environmental purification has attracted widespread attention, and a lot of research work has been carried out on the preparation of titanium dioxide photocatalysts, the improvement of photocatalytic activity, and the immobilization of photocatalysts. Reports in this regard can be found on page 2180 of Volume 8 of "Chemical Materials" in 1996 (Vinodgopal, K.; Bedja, I., Kamat, P.V., Chem.Mater., 1996, 8, 2180) and "Journal of Physical Chemistry" 1994, Vol. 98, p. 13669 (Choi, W., Termin, A., Hoffmann, M.R., J. Phys. Chem., 1994, 98, 13669), etc. In order to prepare a titanium dioxide nanoparticle film with photocatalytic function, titanium alkoxide is generally used as a precursor, and a stable titanium dioxide sol is prepared by a sol-gel method, and then the titanium dioxide sol is loaded on a certain substrate. The report in this respect can be referred to " nature " magazine 1997 the 388th volume 431 pages (Wang, R., Hashimoto, K., Fujishima, A., Nature, 1997,388,431), " new chemistry magazine " 1996 20 Volume 233 (Sitkiewiitz, S., Heller, A., New J.Chem., 1996, 20, 233) and "Environmental Science and Technology" 1998, Volume 32, page 726 (Sunada, K., Kikuchi, Y. , Hashimoto, K., Fujishima, A., Eviron. Sci. Techno., 1998, 32, 726) and the like. For example, using titanium alkoxide as a raw material, titanium dioxide nanoparticles prepared by a sol-gel method are carried on the glass surface to prepare self-cleaning glass. However, there are few reports on the preparation of self-cleaning ceramics prepared by loading titania nanoparticles on the ceramic surface. Secondly, improving the photocatalytic activity of titanium dioxide nanoparticles also plays a very important role. Carrying out metal ion doping to titanium dioxide nanoparticles is one of the effective means to improve its photocatalytic efficiency, the reports in this respect can be found in "Chemical Reviews", page 735 of volume 95 in 1995 (Linsbigler, L.A., Lu G.Q., Yates, J.Y.) ; At the same time, because titanium dioxide is a semiconductor with a large band gap, high energy is required to excite titanium dioxide nanoparticles. Therefore, in order to exhibit high photocatalytic efficiency and antibacterial efficiency, the intensity of ultraviolet light for exciting titanium dioxide nanoparticles is required to be high. However, the intensity of ultraviolet rays from sunlight in nature is very small. Even outdoors, the intensity of ultraviolet light can only reach about 1 mW/cm2, and the intensity of ultraviolet light indoors is even smaller, and its quantity is only microwatts/cm2. This aspect is described in Fujishima, "Principles and Applications of Titanium Dioxide Photocatalysts" (Fujishima, A., Hashimoto, K., Watanabe, T., TiO2 Photocatalysis Fundamentals and Applications). Therefore, the development of titanium dioxide nanoparticles with self-cleaning functions such as antibacterial, anti-mildew, deodorization, degradation of organic pollutants, and decomposition of harmful gases under low ultraviolet light intensity will have more realistic application value.

Contents of Invention

One of the objectives of the present invention is to provide a metal composite titanium dioxide nano-particle that has self-cleaning functions such as antibacterial, anti-mildew, deodorization, degradation of organic pollutants, and decomposition of harmful gases under low ultraviolet light intensity.

Another object of the present invention is to provide a metal-composite nano-titanium dioxide doped with different metals by a hydrothermal method with a simpler process, using the metal inorganic salt-titanium tetrachloride, which is cheaper and easier to obtain than metal alkoxides, as a raw material. particle method.

Another object of the present invention is to use the sol containing the metal composite titanium dioxide nanoparticles of the present invention to prepare chemical products such as ceramic products and coatings with self-cleaning function, so that the self-cleaning products prepared have very high photodegradation efficiency, even in It has high antibacterial efficiency and good anti-mildew effect under natural indoor light or low ultraviolet light intensity.

The purpose of the present invention is achieved by the following technical solutions:

The composition and content of metal composite titanium dioxide nanoparticles of the present invention are:

Metal ion 0.005～5 parts by weight

Titanium dioxide 95-100 parts by weight

The metals are transition metals such as iron, nickel, platinum, iridium, palladium, silver, zinc or copper.

The particle diameter of the metal composite titanium dioxide nanoparticles is 3-50 nanometers, preferably 3-10 nanometers.

The preparation method of the metal composite titanium dioxide nano-particles of the present invention is as follows: titanium tetrachloride is used as a raw material and prepared by a hydrothermal method. The method comprises the following steps, and the amounts involved are in parts by weight:

(1) Dissolve 15 to 65 parts of titanium tetrachloride in 35 to 85 parts of ice water and stir evenly to obtain a transparent and clear titanium tetrachloride aqueous solution;

(2) Under rapid stirring, add 0.1 to 30 parts of transition metal salt in 95 to 100 parts of deionized water to 10 to 50 parts of titanium tetrachloride aqueous solution in step (1). It can be complexed by a complexing agent; stir, then add deionized water, stir evenly, transfer the above solution to a medium pressure kettle, and keep the temperature at 50-400°C;

(3) cooling naturally, washing with deionized water, and centrifuging and settling, collecting the obtained filter cake to obtain a metal composite titanium dioxide nanoparticle powder; at the same time collecting the supernatant obtained in the centrifugal washing process to obtain a metal composite titanium dioxide nanoparticle sol.

The step (2) further adds 30 to 85 parts of deionized water before constant temperature.

The step (2) is constant temperature for 0.5-7 hours.

Said salts are transition metal chlorides or metal nitrates, such as ferric chloride, silver nitrate, copper nitrate and the like.

The complexing agent is ammonia water, oxalate, thiosulfate or thiocyanate and the like.

The metal composite titanium dioxide nano particle sol prepared by the invention is mainly composed of the metal composite titanium dioxide nano particle and water. The weight percentage of metal composite titanium dioxide nanoparticles is 0.03-0.5%. .

By changing the type of metal ions in the added transition metal salt, titanium dioxide nanoparticles composited with different metal ions can be obtained, and the particle diameter is about 3-50 nanometers.

Changing the existing form of metal ions in the solution, such as adding a metal salt solution complexed by a complexing agent, can produce metal composite titanium dioxide nanoparticles with a particle size of about 3 to 10 nanometers, including a part of the particle size of 10 to 50 nanometers. Nano-Metal Composite Titanium Dioxide Nanoparticles.

The sol containing the metal composite titanium dioxide nanoparticles of the present invention can be used to prepare architectural coatings, pigments, fibers or resins with functions of antibacterial, mildew proof, deodorizing and decomposing pollutants.

The specific method is as follows: in parts by weight: 5-50 parts of sol containing metal composite titanium dioxide nanoparticles are added to 50-95 parts of paint, pigment or resin raw materials, and mixed evenly.

The sol containing the metal composite titanium dioxide nanoparticles of the invention can be used to prepare building ceramics and daily sanitary ceramics with the functions of antibacterial, mildew proof, deodorizing and decomposing pollutants.

The specific method is, in parts by weight: (1) add 20 to 100 parts of the sol containing metal composite titanium dioxide nanoparticles into deionized water and stir evenly; (2) spray on the sintered ceramic products, dry or (1) Spray on bisque-fired ceramic products and dry; (3) Sinter in a muffle furnace at a constant temperature of 300-1300°C for 10 minutes to 10 hours, and cool naturally.

The metal composite titanium dioxide nanoparticles of the invention can be used to prepare indoor and outdoor wall coatings with the functions of antibacterial, deodorizing and air purification.

The specific method is as follows: in parts by weight: uniformly mix 0.1-10 parts of metal composite titanium dioxide nanoparticles with 90-100 parts of paint.

Compared with titanium dioxide prepared by conventional methods, the metal composite titanium dioxide nanoparticles prepared by the present invention have the following advantages:

1. The raw materials used are cheap and easy to get:

The metal composite titanium dioxide nanoparticles prepared by the invention use the inorganic salt of titanium, titanium tetrachloride, as the main raw material, and the raw material used is much cheaper than the metal alkoxide used by the sol-gel method, and the raw material is easy to obtain.

2. The preparation method is simple and easy:

When the present invention adopts the hydrothermal method to prepare metal composite titanium dioxide nanoparticles, each component can be added sequentially, without complicated addition and preparation process, and at the same time, it does not need to adjust the pH value compared with the general preparation method.

3. The prepared metal composite titanium dioxide nanoparticles have a more uniform particle size and almost no particle agglomeration:

The metal composite titanium dioxide nanoparticles prepared by the method of the present invention, as shown in Figure 1, have a particle diameter of about 10-50 nanometers, good monodispersity, and almost no aggregated large particles.

4. Metal composite titanium dioxide nanoparticles with different catalytic activities and sizes can be obtained simply by changing the type and form of the transition metal salt added to the titanium tetrachloride solution.

When the metal ions in the transition metal salt solution added to the titanium tetrachloride solution changed from free ions to complex ions, the prepared metal composite titanium dioxide nanoparticles showed different catalytic activities. As shown in accompanying drawing 1,2, the shape and the size of particle have also changed, when adding the complex compound of transition metal salt, as shown in accompanying drawing 2, the particle diameter of most of the metal composite titanium dioxide nanoparticles prepared is about 3 to 10 nanometers.

5. High catalytic activity:

Metal composite titanium dioxide nanoparticles of the present invention, as shown in accompanying drawing 3, have very high photocatalytic activity; With the optical function film that the sol preparation containing metal composite titanium dioxide nanoparticles of the present invention, as shown in accompanying drawing 4, also have High photocatalytic activity.

6. High antibacterial efficiency:

As shown in accompanying drawing 5, under indoor natural light condition, the photofunctional film prepared with the sol containing the metal composite titanium dioxide nanoparticle prepared by the present invention has shown quite high antibacterial effect; Under lower ultraviolet light intensity, Compared with the photofunctional film prepared by the titanium dioxide sol prepared by the general method, the antibacterial effect is also remarkable.

7. Compared with the nano-titanium dioxide sol prepared by the conventional sol-gel method, it is more stable:

The sol containing the metal composite titanium dioxide nanoparticles of the present invention is still very stable after being placed at room temperature for several months.

8. The sol containing metal composite titania nanoparticles of the present invention can be used to improve traditional ceramic products and can give it new functions:

As shown in accompanying drawings 4 and 5, the ceramic product sprayed with the sol containing metal composite titanium dioxide nanoparticles of the present invention has the functions of degrading pollutants, antibacterial, anti-mildew, and decomposing harmful gases.

9. The metal-composite titanium dioxide nanoparticles prepared by the present invention are added to traditional coatings in an appropriate proportion, so that they have the green and environmental protection functions of degrading pollutants, antibacterial, anti-mildew, and decomposing harmful gases. As shown in Figure 6, after a certain amount of metal composite titanium dioxide nanoparticles of the present invention is added to the paint, the paint also shows a considerable antibacterial effect under natural light conditions indoors.

10. The metal composite titanium dioxide nanoparticles prepared in the present invention can be mixed with resin masterbatches, fibers, etc. in an appropriate proportion to prepare products with similar functions.

Description of drawings

Fig. 1. the transmission electron micrograph of the metal composite titania nanoparticle prepared in embodiment 2;

Fig. 2. the transmission electron micrograph of the metal composite titania nanoparticle prepared in embodiment 6;

Fig. 3. the photocatalytic degradation of metal composite titanium dioxide nanoparticles prepared in embodiment 3 contains the aqueous solution of azo dye methyl orange, and the absorption spectrum of residual methyl orange changes with the illumination time;

Fig. 4. Self-cleaning ceramic chip photocatalytic degradation azo dye methyl orange in embodiment 10, the absorption spectrum of residual methyl orange changes with illumination time;

Fig. 5. the antibacterial effect of the self-cleaning ceramic sheet prepared in embodiment 11 under indoor natural light conditions;

Figure 6. The antibacterial effect of the metal composite titanium dioxide nanoparticle modified coating prepared in Example 13 under natural light indoors.

Detailed ways

Example 1

Take 22 parts by weight of titanium tetrachloride and dissolve it in 78 parts by weight of ice water, and stir evenly to obtain a transparent and clear aqueous solution of titanium tetrachloride; under rapid stirring, add 20 parts by weight to the aqueous solution of titanium tetrachloride of 40 parts by weight 1 part of ferric chloride dissolved in 99 parts by weight of deionized water generated solution, after continuous stirring for several minutes, after adding 40 parts by weight of deionized water, stir evenly, transfer to polytetrafluoroethylene as In a lined medium pressure autoclave, keep the temperature at 150°C for 2 hours, and cool down to room temperature naturally. The precipitate is centrifuged and washed, and the supernatant and the lower layer of filter cake are collected respectively to obtain iron ion composite titanium dioxide nanoparticles and iron ion composite titanium dioxide nanoparticle sol with a particle size of about 10 to 50 nanometers. The iron ion composite titanium dioxide nanoparticle is composed of iron ion and titanium dioxide, and the percentage of iron ion is 1.89; the iron ion composite titanium dioxide nanoparticle sol is mainly composed of iron composite titanium dioxide nanoparticle and water, and the percentage of nanoparticle is 0.1 .

Example 2

Dissolve 60 parts by weight of titanium tetrachloride in 40 parts by weight of ice water and stir evenly to obtain a transparent and clear aqueous solution of titanium tetrachloride; under rapid stirring, add 10 parts by weight of The solution generated by dissolving 1 part of copper nitrate in 99 parts by weight of deionized water was continuously stirred for several minutes, and then 76 parts by weight of deionized water was added, stirred evenly, and transferred to a high-pressure tank lined with polytetrafluoroethylene. In the kettle, keep the temperature at 100°C for 4 hours, then cool down to room temperature naturally. The precipitate is centrifuged and washed, and the supernatant and the lower filter cake are collected respectively to obtain copper ion composite titanium dioxide nanoparticles and copper ion composite titanium dioxide nanoparticle sol with a particle size of about 10 to 50 nanometers. The copper ion composite titanium dioxide nanoparticles are composed of copper ions and titanium dioxide, and the percentage of copper ions is 0.97; the copper ion composite titanium dioxide nanoparticle sol is mainly composed of copper composite titanium dioxide nanoparticles and water, and the percentage of nanoparticles is 0.07 .

Example 3

Dissolve 22 parts by weight of titanium tetrachloride in 78 parts by weight of ice water and stir evenly to obtain an aqueous solution of titanium tetrachloride; under vigorous stirring, add 1 part by weight of 5 parts by weight to the aqueous solution of titanium tetrachloride of 45 parts by weight The solution generated by dissolving silver nitrate in 99 parts by weight of deionized water, after continuing to stir for several minutes, added 50 parts of deionized water to it, stirred evenly, and transferred it to a medium-pressure kettle lined with polytetrafluoroethylene , kept at 250°C for 1 hour, and cooled to room temperature naturally. The precipitate is centrifuged and washed, and the supernatant and the lower filter cake are collected respectively to obtain silver ion composite titanium dioxide nanoparticles and silver ion composite titanium dioxide nanoparticle sol with a particle size of about 10 to 50 nanometers. The silver ion composite titanium dioxide nanoparticle is composed of silver ion and titanium dioxide, and the percentage of silver ion is 0.63; the silver ion composite titanium dioxide nanoparticle sol is mainly composed of silver composite titanium dioxide nanoparticle and water, and the percentage of nanoparticle is 0.12.

Example 4

Dissolve 35 parts by weight of titanium tetrachloride in 65 parts by weight of ice water and stir evenly to obtain an aqueous solution of titanium tetrachloride; under vigorous stirring, add 5 parts by weight of 0.5 parts by weight to the aqueous solution of 30 parts by weight of titanium tetrachloride The solution generated by dissolving ammonium chloroiridate in 95 parts by weight of deionized water was continuously stirred for several minutes, and then 69.5 parts of deionized water was added thereto, stirred evenly, and then transferred into a medium-pressure tank lined with polytetrafluoroethylene. In the kettle, keep the temperature at 180°C for 1 hour, then cool down to room temperature naturally. The precipitate is centrifuged and washed, and the supernatant and the lower filter cake are collected respectively to obtain iridium ion-composite titanium dioxide nanoparticles and iridium ion-composite titanium dioxide nanoparticle sol with a particle size of about 10 to 50 nanometers. The iridium ion composite titanium dioxide nanoparticles are composed of iridium ions and titanium dioxide, and the percentage of iridium ions is 0.23; the iridium ion composite titanium dioxide nanoparticle sol is mainly composed of iridium composite titanium dioxide nanoparticles and water, and the percentage of nanoparticles is 0.2 .

Example 5

Dissolve 50 parts by weight of titanium tetrachloride in 50 parts by weight of ice water and stir evenly to obtain a transparent and clear aqueous solution of titanium tetrachloride; under rapid stirring, add 19 parts by weight of The solution generated by dissolving 5 parts of ammonia and silver nitrate in 95 parts by weight of deionized water, after continuing to stir for several minutes, added 61 parts of deionized water, stirred evenly, and transferred it into polytetrafluoroethylene. In a lined medium autoclave, keep the temperature at 120°C for 3 hours, then cool down to room temperature naturally. The precipitate is centrifuged and washed, and the supernatant and the lower filter cake are collected respectively to obtain silver ion composite titanium dioxide nanoparticles and silver ion composite titanium dioxide nanoparticle sol with a particle size of about 3 to 50 nanometers. The composite particles are composed of silver ions and titanium dioxide, and the percentage content of silver ions is 0.012; the silver ion composite titanium dioxide nano particle sol is mainly composed of silver composite titanium dioxide nanoparticles and water, and the percentage content of nano particles is 0.09.

Example 6

Dissolve 22 parts by weight of titanium tetrachloride in 78 parts by weight of ice water and stir evenly to obtain an aqueous solution of titanium tetrachloride; under vigorous stirring, add 8 parts by weight of 25 parts by weight to the aqueous solution of titanium tetrachloride of 40 parts by weight A solution formed by dissolving ammonia-complexed copper nitrate in 92 parts by weight of deionized water, after continuing to stir for several minutes, then adding 35 parts of deionized water, stirring evenly, and transferring it to a medium-pressure autoclave lined with polytetrafluoroethylene , kept at 350°C for 0.5 hours, and cooled to room temperature naturally. Centrifuge and wash the precipitate, collect the supernatant and the lower filter cake respectively, and obtain copper ion composite titanium dioxide nanoparticles and copper ion composite titanium dioxide nanoparticle sol with a particle size of about 3 to 50 nanometers. The nanoparticles are composed of copper ions and titanium dioxide. , the percentage content of copper ions is 0.1; the sol of copper ion composite titanium dioxide nanoparticles is mainly composed of copper composite titanium dioxide nanoparticles and water, and the percentage content of nanoparticles is about 0.3.

Example 7

Dissolve 35 parts by weight of titanium tetrachloride in 65 parts by weight of ice water and stir evenly to obtain an aqueous solution of titanium tetrachloride; under vigorous stirring, add 1 part by weight of 3 parts by weight to the aqueous solution of titanium tetrachloride of 23 parts by weight A solution formed by dissolving ammonia-complexed silver nitrate in 99 parts by weight of deionized water, after continuing to stir for several minutes, adding 74 parts of deionized water, stirring evenly, and transferring it to a medium-pressure kettle lined with polytetrafluoroethylene , kept at 350°C for 5 hours, and cooled to room temperature naturally. The precipitate is centrifuged and washed, and the supernatant and the lower filter cake are collected respectively to obtain silver ion composite titanium dioxide nanoparticles and silver ion composite titanium dioxide nanoparticle sol with a particle size of about 3 to 50 nanometers. The composite particles are composed of silver ions and titanium dioxide, and the percentage content of silver ions is 0.15; the silver ion composite titanium dioxide nano particle sol is mainly composed of silver composite titanium dioxide nanoparticles and water, and the percentage content of nano particles is 0.15.

Example 8

Dissolve 22 parts by weight of titanium tetrachloride in 78 parts by weight of ice water and stir evenly to obtain an aqueous solution of titanium tetrachloride; under vigorous stirring, add 0.2 parts by weight of 0.5 parts by weight to the aqueous solution of titanium tetrachloride of 45 parts by weight The solution generated by dissolving ferric chloride in 99.8 parts by weight of deionized water was continuously stirred for several minutes, then added 54.5 parts of deionized water, stirred evenly, and transferred to a medium-pressure kettle lined with polytetrafluoroethylene , kept at 150°C for 2 hours, and cooled to room temperature naturally. Centrifuge and wash the precipitate, collect the supernatant and the lower filter cake respectively, and obtain iron ion composite titanium dioxide nanoparticles and iron ion composite titanium dioxide nanoparticle sol with a particle size of about 10 to 50 nanometers. The composite particles are composed of iron ions and titanium dioxide. , the percentage content of iron ions is 0.008; the sol of iron ion composite titanium dioxide nanoparticles is mainly composed of iron composite titanium dioxide nanoparticles and water, and the percentage content of nanoparticles is 0.1. Example 9

Dissolve 22 parts by weight of titanium tetrachloride in 78 parts by weight of ice water and stir evenly to obtain an aqueous solution of titanium tetrachloride; under vigorous stirring, add 3 parts by weight of Potassium thiocyanate-complexed silver nitrate is dissolved in 97 parts by weight of deionized water to form a solution. After continuous stirring for several minutes, add 35 parts of deionized water, stir evenly, and transfer it into the polytetrafluoroethylene lining In a medium autoclave, the temperature was kept at 120°C for 6 hours, and then naturally cooled to room temperature. The precipitate is centrifuged and washed, and the supernatant and the lower filter cake are collected respectively to obtain silver ion composite titanium dioxide nanoparticles and silver ion composite titanium dioxide nanoparticle sol with a particle size of about 3 to 50 nanometers. The composite particles are composed of silver ions and titanium dioxide, and the percentage of silver ions is 0.19; the silver ion composite titanium dioxide nano particle sol is mainly composed of silver composite titanium dioxide nanoparticles and water, and the percentage of nano particles is 0.1.

Example 10

Take 80 parts of the iridium ion composite titanium dioxide sol solution obtained in Example 4, add 20 parts of deionized water under electromagnetic stirring, and spray it on the finished ceramic sheet. After drying at room temperature, sinter at low temperature, and repeat the film coating process several times. After keeping the temperature at 600°C for 5 hours, it was cooled naturally. Ceramic products with antibacterial and pollutant-degrading functions are obtained.

Example 11

Take 50 parts of the silver ion composite titanium dioxide sol solution obtained in Example 7, add 50 parts of deionized water under electromagnetic stirring, spray it on the finished ceramic sheet, after drying at room temperature, sinter at low temperature, repeat several times after the film coating process, muffle furnace After keeping the temperature at 400°C for 2 hours, it was cooled naturally. Ceramic products with antibacterial and pollutant-degrading functions are obtained.

Example 12

Take 0.5 part of silver ion composite titanium dioxide nanoparticles obtained in Example 7, uniformly disperse in 99.5 parts of interior wall paint, and dry at room temperature. A coating with the functions of antibacterial, antifungal, deodorizing, and degrading pollutants is obtained.

Example 13

Take 5 parts of copper ion composite titanium dioxide nanoparticles obtained in Example 2, uniformly disperse in 95 parts of exterior wall paint, and dry at room temperature. A coating with the functions of antibacterial, antifungal, deodorizing, and degrading pollutants is obtained.

Claims (11)

1. metal composite titanium dioxide nano particle, it is characterized in that: the composition of this metal composite titanium dioxide nano particle and content are:

Metal ion 0.005～5 weight portion

Titanium dioxide 95～100 weight portions.

2. metal composite titanium dioxide nano particle as claimed in claim 1 is characterized in that: described metal is iron, nickel, platinum, iridium, palladium, silver, zinc or copper transition metal.

3. metal composite titanium dioxide nano particle as claimed in claim 1 is characterized in that: the particle diameter of described metal composite titanium dioxide nano particle is 3～50 nanometers.

4. as claim 1 or 2 any described metal composite titanium dioxide nano particles, it is characterized in that: the particle diameter of described metal composite titanium dioxide nano particle is 3～10 nanometers.

5. as the preparation method of the described metal composite titanium dioxide nano particle of claim 1-4, it is characterized in that: this method may further comprise the steps, and related amount is in parts by weight:

(1) gets 15～65 parts of titanium tetrachlorides and be dissolved in 35～85 portions of frozen water, stir, obtain titanium tetrachloride aqueous solution;

(2) under stirring fast, add 0.1～30 part of transition metal salt in the titanium tetrachloride aqueous solution of 10～50 parts of steps (1) and be dissolved in the solution that generates in 95～100 parts the deionized water, this transition metal salt can be by the complexing agent complexing; Stir constant temperature under 50～400 ℃ of temperature;

(3) deionized water washing after the centrifugal sedimentation, is collected the gained filter cake, obtains the metal composite titanium dioxide nano particle powder; Collect the supernatant liquor that obtains in the centrifuge washing process simultaneously, obtain metal composite titanium dioxide nano particle colloidal sol.

6. method as claimed in claim 5 is characterized in that: described step (2) further added 30～85 parts of deionized waters before constant temperature.

7. method as claimed in claim 5 is characterized in that: described step (2) constant temperature 0.5～7 hour.

8. method as claimed in claim 5 is characterized in that: described complexing agent is ammoniacal liquor, oxalates, thiosulfate or rhodanate.

9. method as claimed in claim 5 is characterized in that: described salt is transition metal chlorate or transition metal nitrate.

10. as claim 5 or 9 any described methods, it is characterized in that: described transition metal is iron, nickel, platinum, iridium, palladium, silver, zinc or copper.

11. the purposes as the described metal composite titanium dioxide nano particle of claim 1-4 is characterized in that: be used to prepare have antibiotic, mildew-resistant, architectural pottery, daily-use sanitary pottery, building coating, pigment, plastics and the fiber or the resin of deodorizing, decomposing pollutant function.

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