WO2004110620A1 - Photocatalyst composition and manufacturing method thereof - Google Patents

Photocatalyst composition and manufacturing method thereof

Info

Publication number
WO2004110620A1
WO2004110620A1 PCT/KR2003/002044 KR0302044W WO2004110620A1 WO 2004110620 A1 WO2004110620 A1 WO 2004110620A1 KR 0302044 W KR0302044 W KR 0302044W WO 2004110620 A1 WO2004110620 A1 WO 2004110620A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
photocatalyst
test
sol
invention
present
Prior art date
Application number
PCT/KR2003/002044
Other languages
French (fr)
Inventor
Cheong-Sik Jeong
Original Assignee
Cpc Co., Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • B01J35/004Photocatalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • B01J37/0244Coatings comprising several layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057Selenium or tellurium; Compounds thereof
    • B01J27/0573Selenium; Compounds thereof

Abstract

The present invention is about optical catalyst composite and the manufacturing method thereof, it can be characterized by the following process. After making sol using selenuim(Se) metal, that can be used together with optical catalyst or Se sol can be used in primer which promotes viscosity of the surface in the 1st layer, anatase type optical catalyst sol is coated on the 2nd layer.

Description

PHOTOCATALYST COMPOSITION AND MANUFACTURING

METHOD THEREOF

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a photocatalyst composition and a preparing method thereof which have an excellent photocatalyst function even in a natural light and indoor light.

2. Description of the Background Art

When a light having energy above band gap is irradiated to a metallic material having a semiconductor property, oxidation and reduction reactions occur in surrounding organic compounds. Here, a photocatalyst material having a property of semiconductor is referred to as a photocatalyst agent.

For obtaining the above photocatalyst, there is a method in which a photocatalyst is carried on a substrate using a refractory binding agent by adapting a high molecule as a supporter. Another method is characterized in which a photocatalyst powder is adhered to a substrate of a fluorine group polymer or a silicon polymer and silicon sol of an inorganic group by binder. And, there is a method in which a photocatalyst is obtained from a metallic oxide sol as a carrier of a photocatalyst powder. Recently, an applicable range of the photocatalyst is sharply increased. Namely, the above photocatalyst is adapted in home, office and various industrial fields. The use of the photocatalyst is rapidly spread. Photocatalyst is used for decomposition of harmful substances to a human body and bad smells. It is also used for prevention of sliding in a public bath room, removal of smell component, purification of indoor air, removal of bad smell in the interior of a vehicle, or prevention of bacteria propagation in a food factory, etc. However, it is needed to implement the properties that photocatalyst particles are strongly adhered on a substrate, maintaining an inherent function of the photocatalyst and a long time efficacy of the same.

In the case that an organic high molecule is adapted as a supporter of a photocatalyst, a semiconductor photocatalyst may receive a certain energy level above the energy of the band gap, so that the organic materials may be continuously and gradually oxidized and decomposed. Therefore, the efficacy of the same is very short, and it is impossible to implement a desired effect, so that a consumer is not satisfied.

In addition, when rutile type photocatalyst or anatase type photocatalyst is coated on a substrate by spray or brush method using an organic group as a binder and inorganic silicon group polymer as a supporter and dried thereon, a certain crack may occur due to the binding of particles during a drying process or the surface of the catalyst may be rough. SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a photocatalyst composition and a manufacturing method thereof which overcome the problems encountered in the conventional art.

It is another object of the present invention to provide a photocatalyst composition and a manufacturing method thereof which are capable of implementing a strong adhering force on the surface of a substrate without damaging the particles of a photocatalyst and the inherent functions of a photocatalyst.

It is another object of the present invention to provide a photocatalyst composition and a manufacturing method thereof which are capable of implementing a long time efficacy of the photocatalyst. To achieve the above objects, there is provided a method for preparing a photocatalyst composition which is characterized in that a sol is prepared using a selenium(Se) metal and is co-used with a photocatalyst or a selenium sol is adapted as a primer for enhancing an adhering force on a surface of a first layer, and an anatase type photocatalyst sol is coated on a second layer. In the present invention, it is possible to implement a uniform thin film coating process having a desired adherence without crystallization by a titanium dioxide and a crack during a drying process.

A certain layer is separated by neutralization using an alkali property contained in NaOH, KOH, NaHCo3, ammonia water, etc. in a titanium aqueous solution like TiCI4 as a layer separation agent of a photocatalyst sol adapted in the present invention.

Here, a separated supernatant has a base component. The supernatant is washed multiple times using distilled water thus discarding a base. The distilled water is added 1 or 3 times based on the volume of a precipitated agent, and a solid value is obtained based on the added amount of the distilled water. Here,

HNO3 solution is slowly added by 1 ,000ppm(0.1%) and is strongly agitated by high-speed agitator for 30 minutes thus obtaining pH of 1-2. In order to adjust color and pH of neutrality, NaOH, KOH, NaHCO3, or ammonia water may be added in an aqueous solution within a range of 0.2% thus obtaining a neutral pH of 7-8.

The obtained material is heated at above 100°C for more than 30 minutes, and then the crystal titanium dioxide sol of the anatase type is obtained. The photocatalyst is coated on a ceramic and is dried and heated to 400°C. As a result, the titanium dioxide of the anatase type is obtained.

At this time, the titanium dioxide sol of the anatase type has a grain diameter of below 5-20nm, and pH is 7-8, and the outer appearance is white transparent color.

As a component of the binder adapted in the present invention, there are Se, Co, CeO3, Ta2O5, RuO2, InPb, MoS3, MoS2, SaO2, Zno, SrTiO3, CdS, CdO, CaP, TiO2, SiO2, SiC, Ca, Fe, Mn, Mg, etc. Among the above components, a transparent selenium sol has an excellent adherence on the surface. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The preferred embodiments and references of the present invention will be described in detail. The scope of the present invention is not limited to the following examples.

[Example 1] Preparation of titania sol

In a high speed agitator, a distilled water of 10,000ml was added to 99% TiCI4 of 500ml(Junsei) at a ratio of 20:1 , maintaining a temperature at 0°C through

3°C, and 40% solution of NaOH(supplied by Yongjin chemical corporation) was added, neutralized to pH of 6-7 and the layer was separated. The water residing in the upper layer of the solution was discarded. Supernatant was fully washed with silver nitrate solution of 1mol until chlorine contained in the supernatant was not detected thus obtaining 2,000ml of gel.

The resultant solution was diluted with nitric acid (70%) supplied by Dongyang chemical corporation, and a solid value was freely controlled based on the ratio of the diluted nitric solution, thus obtaining a stable aqueous dispersion of about 5,000ml which has at least 10% of solid value.

[Example 2] Preparation of inorganic binder

A distilled water of 30ml was added to a solution of a nitric acid (70% ) of 100 ml supplied by Dongyang chemical corporation thus preparing diluted HNO3 solution. Se of 13g was added to diluted HNO3. The resultant solution was neutralized with KOH (30%) solution supplied by Duksan chemical corporation, and pH was adjusted to 8-9. The pH was fixed at 7.5-8 using lactic acid for preventing a layer separation, and the solid value was adjusted using distilled water. It was preferred that the solid component does not exceed 3% of the solid content of photocatalyst when it is used as a binder for a photocatalyst according to the present invention.

[Example 3] Preparation of photocatalyst composition The inorganic binder prepared by the example 2 was mixed with a photocatalyst and was heated at below 100°C within 10 minutes thus preparing an anatase type titanium dioxide. The photocatalyst sol of transparent white color was obtained.

[Experimental example 1]

The decomposition force test for the organic materials of the photocatalyst sol of the example 3 including the inorganic binder was implemented based on the following methods. A cubic box was formed by plastic material in size of 2m3. A 2OW UV fluorescent light was attached to each rectangular corner of the box. A bad smell gas (for example, ammonia, SOx, NOx, etc.) of 2,000ppm was injected into the box one time for every one minute for 24 hours totally 1 ,440 times using a pump. Photocatalyst sol containing inorganic binder was injected for 1 minute by 10CC using an air spray gun by a compressor for removing particles of the bad smell gas. Thereafter, a smell removing ability was checked one time for every hour.

As a result of the above processes for researching and checking the efficiency of the removal of the bad smell gas, photocatalyst sol containing inorganic binder was proved to be capable of decomposing organic materials completely only in 1 minute.

[Experimental example 2]

The decrease rate of the bacteria was checked with respect to the strain 1 of Staphylococcus aureus having an initial number of bacteria of 1.3x106 after 24 hours based on FC-TM-20 in the antimicrobial susceptibility test. As a result of the check, an extinction ability of 99.9% was obtained. In addition, the decrease rate of the bacteria was checked with respect to the strain 2 of the Escherichia coli having an initial number of bacteria of 1.5x104 after 24 hours based on the same manner. As a result of the check, an extinction ability of 99.9% was obtained.

[Experimental example 3]

A photocatalyst sol was adjusted to solid value of 1 % using distilled water and was fully diluted and sprayed on a transparent glass test sample having a dimension of 10cmx5.5cmx5cm using a spray, so that a coating layer having a thickness of 1μm~2μm was formed thereon. Thereafter, an adhering strength test was performed with respect to the resultant coating layer under a natural environment at a room temperature through 200°C. [Adhering strength test 1]

A photocatalyst having water was placed indoor at a room temperature of 150C for 2 hours. The water contained in the photocatalyst was fully evaporated. It was visually checked that a rainbow was outputted from a glass test sample coated with a photocatalyst, viewing the same in a lateral direction. In addition, the strength of the glass test sample coated with the photocatalyst was tested using a 4H pencil. As a result of the test, there was not any scratch on the glass test sample.

[Adhering strength test 2]

The above glass test sample was coated using a spray at a room temperature, and water contained in the glass test sample was evaporated at a temperature of 500C. The strength of the glass test sample coated with a photocatalyst was tested using a 4H pencil. As a result of the test, there was not any scratch on the glass test sample.

[Adhering strength test 3]

The glass test sample was coated using a spray at a room temperature, and water contained in the glass test sample was evaporated for 5 minutes at a temperature of 500C and was heated for 10 minutes at a temperature of 1000C.

The strength of the glass test sample coated with the photocatalyst was tested using a 4H pencil. As a result of the test, there was not any scratch on the glass test sample. In order to test the adherence of the photocatalyst on the surface, the strength of the glass test sample coated with the photocatalyst was tested using a 4H pencil. As a result of the test, there was not any scratch on the surface of the same. In addition, the glass test sample coated with the photocatalyst was rubbed 50 times with a common towel using a neutral detergent having a density of 1 ,000ppm for performing an adhesive force test on the surface. As a result of the test, it was possible to obtain the same result as the original state.

[Experimental example 4] In order to perform a storing property test with respect to a photocatalyst sol having an inorganic binder, the photocatalyst sol was inputted into an ample bottle having a volume of 100CC by 50CC and was frozen in a freezing room of a common environment for 24 hours at -50C. A resultant sol was placed at a room temperature for 3 hours. Thereafter, the state of the recoupling of the nano-size particles was visually checked. The conventional local products and conventional Japanese products each having pH value of 7-8 were frozen or defrozen. As a result of the above process, when the particles were recoupled, the products were damaged, so that there was not any value as a product. However, in the case of the products according to the present invention, when it was frozen and defrozen multiple times, it was possible to visually check no changes in the products. Therefore, even when the products according to the present invention are frozen by mistake during the transportation of the products, there will be no problems in the products. Hence, it is possible to sell and use the products without any damages.

As described above, in the preparing method of the present invention, it is possible to prepare a photocatalyst composition having a good adhering property, spreading property, durability, cold-resistant property, etc. when coating on a surface of a thing without decreasing an inherent function of a photocatalyst.

As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described examples are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.

Claims

What was claimed is:
1. A photocatalyst composition characterized in that said photocataiyst composition consists of a selenium(Se) sol and a titanium dioxide(TiO2).
2. The composition of claim 1 , wherein in said selenium sol is used as a primer layer and an titanium dioxide of anatase type is coated on an upper layer.
3. The composition of claim 1 , wherein the amount of said solid selenium is below 3% of the solid titanium dioxide photocatalyst.
4. A prepartion method of a photocatalyst composition characterized in that said photocatalyst composition is prepared in such a manner that a selenium is formed in a sol type and is mixed with a titania(TiO2) sol, and a resultant mixture is heated for 10 - 60 minutes at 100°C.
PCT/KR2003/002044 2003-06-13 2003-10-02 Photocatalyst composition and manufacturing method thereof WO2004110620A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR10-2003-0038339 2003-06-13
KR20030038339A KR20040107315A (en) 2003-06-13 2003-06-13 photocatalyst composition and manufacturing method thereof

Publications (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100443164C (en) 2006-12-08 2008-12-17 南京大学 Mesoporous titania meterial containing selenium and its prepn process
CN100453165C (en) 2006-06-02 2009-01-21 安徽大学 Nanometer titanium dioxide/selenium dioxide composition and its prepn. method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759948A (en) * 1994-02-07 1998-06-02 Ishihara Sangyo Kaisha Ltd. Titanium oxide for photocatalyst and method of producing the same
US6107241A (en) * 1996-03-29 2000-08-22 Tao Inc. Photocatalytic body and method for making same
US6106955A (en) * 1997-01-14 2000-08-22 Takenaka Corporation Metal material having photocatalytic activity and method of manufacturing the same
US6387446B1 (en) * 1998-10-01 2002-05-14 Fraun-Hofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Method for depositing titanium oxide layers using soluble powders
US6576589B1 (en) * 1999-09-20 2003-06-10 Lg Electronics Inc. Method for making anatase type titanium dioxide photocatalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759948A (en) * 1994-02-07 1998-06-02 Ishihara Sangyo Kaisha Ltd. Titanium oxide for photocatalyst and method of producing the same
US6107241A (en) * 1996-03-29 2000-08-22 Tao Inc. Photocatalytic body and method for making same
US6429169B1 (en) * 1996-03-29 2002-08-06 Saga-Ken Photocatalytic body and method for making same
US6106955A (en) * 1997-01-14 2000-08-22 Takenaka Corporation Metal material having photocatalytic activity and method of manufacturing the same
US6387446B1 (en) * 1998-10-01 2002-05-14 Fraun-Hofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Method for depositing titanium oxide layers using soluble powders
US6576589B1 (en) * 1999-09-20 2003-06-10 Lg Electronics Inc. Method for making anatase type titanium dioxide photocatalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100453165C (en) 2006-06-02 2009-01-21 安徽大学 Nanometer titanium dioxide/selenium dioxide composition and its prepn. method
CN100443164C (en) 2006-12-08 2008-12-17 南京大学 Mesoporous titania meterial containing selenium and its prepn process

Also Published As

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