WO2007026796A1 - Photocatalyst - Google Patents

Abstract

Disclosed is a photocatalyst which is improved in light absorption capability for the visible light region and thus exhibits sufficiently high photocatalytic performance even in an environment with less ultraviolet light. Specifically disclosed is a photocatalyst containing a nitrogen atom-containing titanium oxide or a sulfur atom-containing titanium oxide and an iron (III) compound, wherein the iron (III) compound is held on the surface of the photocatalyst. Also disclosed are a photocatalyst composition, a building material for interiors, a coating material, a synthetic resin molded body and a fiber respectively using such a photocatalyst; a use of such a photocatalyst; and a method for decomposing a harmful substance.

Description

 Technical field

 The present invention relates to a photocatalyst, a photocatalyst composition using the same, an interior building material, a paint, a synthetic resin composition, a fiber, a method for using the photocatalyst, and a method for decomposing a harmful substance.

 Background art

 [0002] It is known that when titanium dioxide is irradiated with ultraviolet rays, the titanium dioxide exhibits a photocatalytic action. The photocatalytic action of strong diacid titanium is considered as a causative substance of, for example, Sicknosaurus syndrome, and is used for decomposition of compounds such as formaldehyde and toluene. However, the titanium dioxide has a drawback that it can not be used because it absorbs only a part of ultraviolet energy contained in natural light when the photocatalytic action is exhibited.

 [0003] Therefore, at present, attempts have been made to impart a property of absorbing visible light to titanium dioxide by doping nitrogen dioxide or sulfur atom into titanium dioxide (for example, patent documents). 1 and Patent Document 2).

 [0004] However, even when the titanium dioxide introduced with the nitrogen atom described in Patent Document 1 and the titanium dioxide with the sulfur atom introduced in Patent Document 2 are used, for example, In an environment using light such as an indoor fluorescent lamp, there is a drawback that sufficient photocatalytic action, for example, photocatalytic action sufficient to prevent the occurrence of sick house syndrome cannot be obtained.

 Patent Document 1: Japanese Patent Laid-Open No. 2001-205094

 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-143032

 Disclosure of the invention

 Problems to be solved by the invention

[0005] In one aspect of the present invention, the ability to absorb light in the visible light region is enhanced, and high photocatalytic activity is achieved even in an environment with little ultraviolet light, for example, in an environment with light such as an indoor fluorescent lamp. The present invention relates to providing a photocatalyst that can sufficiently exert its application. The present invention is the other side In terms of the aspect, the present invention relates to providing a method for producing the photocatalyst, which can be obtained by a simple operation in a shorter time than the efficiency. In still another aspect, the present invention relates to providing a photocatalyst composition capable of sufficiently exhibiting the photocatalytic action with higher versatility. In yet another aspect, the present invention can sufficiently exhibit a high photocatalytic action even in the environment that has been difficult to use in the past, can be used in various places, and is a toxic substance. The present invention relates to providing an interior building material that can achieve at least one of, for example, that it can be decomposed with high efficiency, such as prevention of sick house syndrome and allergy to chemical substances. The present invention

In still another aspect, the photocatalytic action can be sufficiently exerted even in a place where the use form is limited such as a narrow space, and the target of application of the photocatalytic action, for example, a substance (substance to be oxidatively decomposed) ( For example, a coating composition that can achieve at least one of the functions of easily and efficiently decomposing a harmful substance in the air, an attached pollutant, etc.) with high efficiency is provided. About that. According to another aspect of the present invention, the photocatalytic action can be exhibited, and a target to which the photocatalytic action is applied, for example, a substance that is subject to acidolysis (for example, a harmful substance in the air or an attached pollutant). At least the ability to easily and efficiently demonstrate the ability to decompose with high efficiency

The present invention relates to providing a synthetic resin molding that can achieve one. In still another aspect, the present invention relates to providing a fiber that can exhibit the photocatalytic action, and can be used, for example, in the manufacture of clothing that can exhibit a deodorizing function and the like. According to another aspect of the present invention, the photocatalytic action can be exerted even in the environment that has been difficult to use in the past, such as automobile-related members, office supplies, daily necessities, inside and outside of a house. It can reduce bad odors, sebum stains, dust accumulation, adhesion of pollutants, adhesion of bacteria, etc. generated in public goods and electrical equipment, etc., and environment can be improved easily and efficiently. The present invention relates to providing a method of using a photocatalyst that can achieve at least one of the above. In still another aspect, the present invention is capable of exerting the photocatalytic action even in the environment that has been difficult to use conventionally, for example, harmful substances that cause sick house syndrome such as formaldehyde That can be efficiently decomposed, and that the environment can be easily and efficiently improved. It is an object to provide a method for decomposing harmful substances. Other problems of the present invention are also apparent from the description of the present specification.

Means for solving the problem

 That is, the gist of the present invention is as follows.

 [1] A photocatalyst comprising a nitrogen atom-containing titanium oxide and an iron (III) compound, and holding the iron (III) compound on the surface of the crystal of the nitrogen atom-containing titanium oxide.

[2] The photocatalyst according to the above [1], wherein the iron (III) compound is a γ-type iron (III) compound,

[3] The photocatalyst according to the above [2], wherein the γ-type iron (III) compound is γ-FeO (OH),

[4] A photocatalyst obtained by immersing a nitrogen atom-containing titanium oxide in a solution in which an iron (III) compound is dissolved, thereby supporting the iron (ΠΙ) compound on the nitrogen atom-containing titanium oxide,

 [5] The above-mentioned [4], wherein the product obtained by supporting an iron (III) compound on a nitrogen atom-containing titanium oxide is further reduced, and then the obtained product is acidified The photocatalyst,

 [6] A photocatalyst containing a sulfur atom-containing titanium oxide and an iron (III) compound, and holding the iron (III) compound on the surface of the crystal of the sulfur atom-containing titanium oxide.

[7] The photocatalyst according to the above [6], wherein the iron (III) compound is a γ-type iron (III) compound,

[8] The photocatalyst according to the above [7], wherein the γ-type iron (III) compound is γ-FeO (OH),

[9] A photocatalyst obtained by immersing a sulfur atom-containing titanium oxide in a solution in which an iron (III) compound is dissolved, thereby supporting the iron (III) compound on the sulfur atom-containing titanium oxide. ,

 [10] The above [9], wherein the product obtained by loading the iron (III) compound on the sulfur atom-containing titanium oxide is further reduced, and then the obtained product is acidified. The photocatalyst,

 [11] A photocatalyst characterized by immersing a nitrogen atom-containing titanium oxide in a solution in which an iron (III) compound is dissolved, thereby supporting the iron (III) compound on the nitrogen atom-containing titanium oxide. Manufacturing method,

[12] Production obtained by supporting an iron (III) compound on the nitrogen atom-containing titanium oxide The method for producing a photocatalyst according to the above [11], wherein the product is further reduced, and then the resulting product is oxidized.

 [13] A photocatalyst characterized by immersing a sulfur atom-containing titanium oxide in a solution in which an iron (III) compound is dissolved, thereby supporting the iron (原子) compound on the sulfur atom-containing titanium oxide. Manufacturing method,

 [14] The production of the photocatalyst according to the above [13], wherein the product obtained by supporting the iron atom (III) compound on the sulfur atom-containing titanium oxide is further reduced, and then the obtained product is oxidized. Method,

 [15] The photocatalyst composition comprising the photocatalyst according to any one of [1] to [10],

 [16] The photocatalyst composition according to the above [15], which further contains an adsorbent and Z or a porous agent,

 [17] The photocatalyst according to any one of [1] to [10] above, and a building material, and on the surface of the building material, the photocatalyst and the photocatalyst contained in the photocatalyst composition are misaligned! A building material for interiors that retains a layer containing

 [18] A paint composition comprising the photocatalyst paint according to any one of [1] to [10],

 [19] A synthetic resin molded article obtained by blending the photocatalyst according to any one of [1] to [10] and a synthetic resin,

 [20] A fiber comprising the photocatalyst according to any one of [1] to [10] and a fiber component, wherein the photocatalyst is held by the fiber component,

 [21] The photocatalyst according to any one of [1] to [10] is irradiated with light to activate the photocatalyst, thereby deodorizing action, sebum dirt decomposition action, dust removal action A method of using a photocatalyst, characterized by causing at least one selected from the group consisting of a degrading action of a pollutant and an antibacterial activity

[22] A harmful substance characterized in that the photocatalyst according to any one of [1] to [10] is irradiated with light to activate the photocatalyst, thereby decomposing a harmful substance in the air. A method of decomposing substances, and [23] The method for decomposing a harmful substance according to [22], wherein the harmful substance is formaldehyde or toluene,

 About.

 The invention's effect

 [0007] According to the photocatalyst of the present invention, the ability to absorb light in the visible light region is enhanced, and the photocatalytic activity is high even in an environment with little ultraviolet light, for example, in an environment with light such as an indoor fluorescent lamp. Produces an excellent effect of sufficiently exhibiting the above.

[0008] According to the method for producing a photocatalyst of the present invention, there is an excellent effect that the photocatalyst of the present invention can be obtained by a simple operation in a shorter time than efficiency.

According to the photocatalyst composition of the present invention, if the photocatalytic action can be sufficiently exerted with higher versatility, an excellent effect is exhibited.

[0010] According to the interior building material of the present invention, it is possible to sufficiently exhibit a high photocatalytic action even in the environment that has been difficult to use conventionally, and to be used in various places. It is possible to achieve at least one of being capable of decomposing toxic substances with high efficiency, for example, being able to prevent sickino, us syndrome and allergy to allergies, etc. Has an effect.

 [0011] According to the coating composition of the present invention, the photocatalytic action can be sufficiently exerted even in a place where the usage form such as a narrow space is limited. Achieving at least one of the functions of easily and efficiently decomposing substances subject to oxidative decomposition (for example, harmful substances in the air and attached pollutants) with high efficiency There is an excellent effect of being able to.

[0012] According to the synthetic resin molded body of the present invention, the photocatalytic action can be exerted, and the target of application of the photocatalytic action, for example, a substance subject to oxidative decomposition (for example, harmful substances in the air or attached contamination) High substance)!ヽ It has an excellent effect that it can achieve at least one of the functions that can be efficiently and efficiently exhibited.

[0013] According to the fiber of the present invention, the photocatalytic action can be exhibited, and for example, it is possible to produce an apparel, wallpaper, cloth wall surface, etc. that can exhibit a deodorizing function and the like. To do.

 [0014] According to the method of using the photocatalyst of the present invention, the photocatalytic action can be exhibited even in the environment that has been difficult to use in the past, such as automobile-related members, office supplies, and daily necessities. It can reduce bad odors, sebum dirt, dust accumulation, adhesion of pollutants, adhesion of germs, etc. generated inside and outside the house, public goods, electrical equipment, etc., and improve the environment easily and efficiently. It has an excellent effect of being able to achieve at least one of things that can be achieved.

 [0015] According to the method for decomposing a harmful substance of the present invention, the photocatalytic action can be exerted even in the environment that has been difficult to use in the past, for example, a sick house syndrome such as formaldehyde. It is possible to achieve at least one of being able to efficiently decompose the harmful substances that cause it and to improve the environment easily and efficiently! .

 Brief Description of Drawings

 [0016] FIG. 1 shows sulfur atom-containing titanium dioxide, iron-containing sulfur atom-containing titanium dioxide, and reduced ferrous iron-containing sulfur atom obtained by reducing the iron-containing sulfur atom-containing titanium dioxide. It is a figure which shows the X-ray diffraction pattern of each titanium dioxide.

 FIG. 2 shows nitrogen atom-containing titanium dioxide, iron-containing nitrogen atom-containing titanium dioxide, and reduced ferrous-containing nitrogen atom-containing diacid obtained by reducing the iron-containing nitrogen atom-containing titanium dioxide. It is a figure which shows the result of having investigated the photocatalyst effect | action by each of the soot titanium. The light intensity values in the figure are values when UV-35 (manufactured by Kenko Co., Ltd.), which is a colored glass filter, is used. In the figure, the black bar indicates the amount of 2-propanol decomposition, and the white bar indicates the amount of acetone produced.

FIG. 3 is obtained by reducing anatase-type sulfur atom-containing titanium dioxide, iron-containing sulfur atom-containing titanium dioxide (anatase type), and iron-containing sulfur atom-containing titanium dioxide (anatase type). It is a figure which shows the result of having investigated the photocatalytic action by each reduced ferrous iron containing sulfur atom containing titanium dioxide. In addition, the value of the light intensity in the figure is a value when a color glass filter UV-35 (manufactured by Kenko Co., Ltd.) is used. In the figure, the black bar indicates the amount of 2-pronool V-decomposition, and the white bar indicates the amount of acetone produced. [FIG. 4] FIG. 4 shows the results of examining the photocatalytic action of the rutile-type sulfur atom-containing titanium dioxide produced using iron sulfate and the rutile-type sulfur atom-containing titanium dioxide produced using iron chloride. FIG. In addition, the value of the light intensity in the figure is a value when a color glass filter UV-35 (manufactured by Kenko Co., Ltd.) is used. In the figure, the black bar indicates the amount of 2-pronool V-decomposition, and the white bar indicates the amount of acetone produced.

 [FIG. 5] FIG. 5 is a graph showing the results of examining the amount of carbon dioxide produced by the decomposition of acetaldehyde by a photocatalyst. Panel (A) shows the result in the case of iron-containing nitrogen atom-containing titanium dioxide, and panel () shows the result in the case of reduced iron-containing nitrogen atom-containing titanium dioxide. In the figure, circles indicate the results in the case of nitrogen atom-containing titanium dioxide, and squares indicate iron-containing nitrogen atoms-containing titanium dioxide or iron oxide carrying 3.0% by weight of iron (III) compound. As a result of the case of iron-containing nitrogen atom-containing titanium dioxide, the triangle mark shows the case of iron-containing nitrogen atom-containing titanium dioxide or reduced ferrous iron-containing nitrogen atom-containing titanium dioxide carrying 1.0% by weight of iron (III) compound. The results are shown.

 [FIG. 6] FIG. 6 is a graph showing the results of measuring the ESR ^ vector of a photocatalyst [iron-containing nitrogen atom-containing titanium dioxide supported with 1.0% by weight of an iron (III) compound]. . In the figure, the dotted line shows the ESR spectrum of the photocatalyst before light irradiation, the solid line shows the ESR vector of the photocatalyst after light irradiation for 5 minutes, and the thick line shows the ESR vector of the photocatalyst after light irradiation for 20 minutes.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0017] In one aspect, the present invention contains a nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide and an iron (III) compound, and the nitrogen atom-containing titanium dioxide or the sulfur atom-containing diacid. The present invention relates to a photocatalyst (Embodiment 1) in which the iron (III) compound is held on the surface of a titanium crystal.

[0018] Hereinafter, in the present specification, "the nitrogen atom-containing titanium dioxide and the iron (III) compound are contained, and the iron (III) compound is formed on the surface of the nitrogen atom-containing titanium dioxide crystal". The “retained photocatalyst” is also referred to as “nitrogen atom-containing photocatalyst”. Further, in the present specification, “a photocatalyst containing a sulfur atom-containing titanium dioxide and an iron (IV) compound and holding the iron (III) compound on the surface of the crystal of the sulfur atom-containing titanium dioxide” Is also referred to as "sulfur atom-containing photocatalyst" [0019] Further, in this specification, "nitrogen atom-containing diacid-titanium" means that a nitrogen atom exists in at least one of the positions where oxygen atoms originally exist in the crystal of diacid-titanium. A state in which at least one of all oxygen atoms contained in the crystal is replaced by a nitrogen atom, a nitrogen atom is present in at least one of the positions where a titanium atom originally exists in a titanium dioxide crystal. Any state existing, that is, a state in which at least one of all titanium atoms contained in the crystal is replaced by a nitrogen atom, and a state in which a nitrogen atom is S-doped between crystal lattices in the crystal. It is intended to encompass concepts. Further, in this specification, “sulfur atom-containing titanium dioxide” means a state in which a sulfur atom is present in at least one position where an oxygen atom is originally present in a crystal of titanium dioxide. A state in which at least one of all oxygen atoms contained in the crystal is substituted with a sulfur atom, a state in which a sulfur atom is present in at least one position where a titanium atom originally exists in a crystal of titanium dioxide, that is, Including a concept in which at least one of all titanium atoms contained in the crystal is substituted with a sulfur atom, and a state in which a sulfur atom is doped between crystal lattices in the crystal. Intended. Here, the “at least one” may be a number that can maintain a crystal structure exhibiting a photocatalytic function. When substituting oxygen atoms with nitrogen atoms, the content power of nitrogen atoms in the titanium dioxide crystal is preferably about 2 atomic%. When replacing titanium atoms with sulfur atoms, the content of sulfur atoms in the titanium dioxide crystals

Preferably, the upper limit is about 3 atomic%.

In the present invention, in the case of the “sulfur atom-containing titanium dioxide”, a sulfur atom is present in at least one position where the titanium atom originally exists in the crystal of titanium dioxide. Prefer what is in the state to do.

[0021] Furthermore, in this specification, "iron (III) compound" means a compound derived from trivalent iron. In this specification, an iron (III) compound held on the surface of a crystal of nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide may be referred to as a “surface iron (III) compound”.

The photocatalyst of the present invention has one major feature in that an iron (III) compound is held on the surface of a crystal of nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide. But Thus, according to the photocatalyst of the present invention, visible light can be absorbed with higher efficiency than nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide. In addition, according to the photocatalyst of the present invention, the charge separation efficiency is increased, thereby significantly improving the photocatalytic activity. Therefore, according to the photocatalyst of the present invention, the photocatalytic action by nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide that exhibits the ability to absorb light in the visible light region, although it is not sufficient for its original use, and trivalent iron Combined with the electron retention effect by ions, there is light in the environment where there is little ultraviolet light, for example, indoor fluorescent lamps, etc., where it has been difficult to exert the photocatalytic action of titanium dioxide. Even under the environment, it exhibits an excellent effect of being able to sufficiently exhibit an extremely high photocatalytic action.

 [0023] The photocatalyst of the present invention has, for example, a nitrogen atom-containing titanium dioxide or sulfur in which the surface may be inactivated due to distortion of the crystal lattice or deficiency of a titanium atom or an oxygen atom, resulting in an inactivated site. Atom-containing titanium dioxide carries trivalent iron ions with small ion radius! For this reason, the photocatalyst of the present invention can efficiently perform the filling of inactive sites, and thus can exhibit higher performance as a photocatalyst.

 In the present specification, “visible light” means light having a wavelength of 400 nm to 800 nm.

 [0025] When the photocatalyst of the present invention is a nitrogen atom-containing photocatalyst, the amount of the iron (III) compound on the surface of the nitrogen atom-containing titanium dioxide crystal is selected from the viewpoint of sufficiently absorbing visible light. Photocatalytic action in an environment with little ultraviolet rays, with an amount of 0.00107 g (0.05 wt%) or more, preferably 0.00429 g (0.2 wt%) or more, relative to lg of titanium dioxide. From the viewpoint of efficiently exhibiting the above, it is desirable that the amount be 0.442916 g (20 wt%) or less, preferably 0.221458 g (10 wt%) or less.

[0026] On the other hand, when the photocatalyst of the present invention is a sulfur atom-containing photocatalyst and contains rutile-type titanium diacid titanium, the iron (III) compound on the surface of the sulfur atom-containing titanium dioxide crystal the amount is, from the viewpoint of performing a sufficient absorption of visible light, for sulfur atom-containing dioxide titanium lg, 0. 00052g (0. 03 weight _^0/0) or more, preferably ί or, 0. 00174g (0. 1 From the viewpoint of efficiently exhibiting photocatalytic action in an environment with little ultraviolet light, it is 0.14066 g (10 wt%) or less, preferably 0.112184 g (7 wt%) or less. The amount is desirable. The photocatalyst of the present invention is a sulfur atom-containing light. In the case where the catalyst contains anatase-type titanium dioxide and titanium dioxide, from the viewpoint of sufficient absorption of visible light, it is 0.00022 g (0.07 wt%) or more with respect to titanium dioxide lg. Preferably, the amount is not less than 0.300522 g (0.3 wt%), and from the viewpoint of exerting a sufficient photocatalytic action even in an environment with little ultraviolet light, 0.34813 g (20 wt%) or less, preferably 0.17406 ₈ (10% by weight) or less is desirable.

[0027] The surface iron (III) compound is preferably a γ-type iron (III) compound from the viewpoint of allowing the photocatalyst to absorb visible light with higher efficiency. The surface iron (III) compound may be a compound derived from trivalent iron, and examples thereof include iron (III) hydroxide and iron (III) oxide. Specifically, examples of the surface iron (III) compound include FeO (OH) and Fe 2 O. In particular, high photocatalytic performance in an environment with little ultraviolet light

twenty three

 From the viewpoint of sufficiently exerting the application, the surface iron (III) compound is preferably FeO (OH).

— FeO (OH) is more preferable.

[0028] In the photocatalyst of the present invention, the dispersion state of the iron (III) compound on the surface of the crystal of nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide may be substantially agglomerated. desirable. The dispersion state of the surface iron (III) compound can be evaluated by, for example, observation under an electron microscope.

The surface iron (III) compound in the photocatalyst of the present invention is analyzed using, for example, an X-ray diffractometer (for example, but not limited to, manufactured by JEOL Ltd., trade name: JDX-3500K, etc.). Can be confirmed.

 [0030] The photocatalyst of the present invention is obtained by immersing a nitrogen atom-containing titanium dioxide or a sulfur atom-containing titanium dioxide in a solution (for example, an iron nitrate aqueous solution, an iron chloride aqueous solution, an iron sulfate aqueous solution, etc.) in which an iron (IV) compound is dissolved. Thereby, the iron (III) compound is supported on the nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide.

Therefore, according to another aspect of the present invention, a nitrogen atom-containing titanium oxide is immersed in a solution in which an iron (III) compound is dissolved. A photocatalyst obtained by loading a compound; and a sulfur atom-containing titanium oxide are immersed in a solution in which an iron (II I) compound is dissolved, whereby iron (III) is added to the sulfur atom-containing titanium oxide. A photocatalyst obtained by loading a compound (embodiment 2). Also, In still another aspect of the present invention, the nitrogen atom-containing titanium dioxide is immersed in a solution in which the iron (III) compound is dissolved, and the iron (III) compound is supported on the nitrogen atom-containing titanium dioxide. A method for producing a photocatalyst; and a sulfur atom-containing titanium oxide is immersed in a solution in which an iron (III) compound is dissolved, whereby iron (III) is added to the sulfur atom-containing titanium oxide.

III) The present invention relates to a method for producing a photocatalyst characterized by supporting a compound.

[0032] The photocatalyst according to the embodiment has one major characteristic in that a solution in which an iron (III) compound is dissolved is used in the production. Therefore, in the photocatalyst of the embodiment, the time required for stirring during production is substantially shortened in comparison with the case where a solution in which a compound derived from divalent iron is dissolved in producing the photocatalyst, and This is advantageous in that the light irradiation operation during production can be substantially omitted. Therefore, the photocatalyst of the present invention can be produced by a simple operation.

 [0033] Further, in the photocatalyst of the embodiment, a nitrogen atom-containing titanium dioxide-containing titanium dioxide or sulfur atom-containing titanium dioxide is immersed in a solution in which an iron (ΠΙ) compound is dissolved. In addition, the iron (III) compound is supported on the nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide. Therefore, according to the photocatalyst of the embodiment, it is possible to absorb more light in the visible light region, and extremely high photocatalyst even in an environment using visible light, for example, light such as an indoor fluorescent lamp. It exhibits an excellent effect that it can fully exert its action.

 [0034] As the iron (III) compound used in the solution, when the photocatalytic action is exhibited by the nitrogen atom-containing titanium dioxide-containing titanium dioxide or sulfur atom-containing titanium dioxide, the light absorbing ability in the visible light region is further improved. If it is a compound, it is preferable that it is a compound having high solubility in water. The iron (III) compound is not particularly limited, and examples thereof include Fe (SO), Fe (NO), FeCl, FeBr, Fe (C10), and the like. Above all, this departure

2 4 3 3 3 3 3 4 3

 In the description, the Fe (NO 2) and FeCl are nitrogen atom-containing titanium dioxide or sulfur source.

 3 3 3

 Since the nitrate ion or salt ion that can be generated after supporting the iron (in) compound on the titanium-containing titanium dioxide becomes salt hydrogen, hydrochloric acid, or nitric acid, it can be easily removed, and the crystal of the photocatalyst It is suitable in that the remaining inside can be suppressed. Therefore, said

When Fe (NO) and FeCl are used, the resulting photocatalyst exhibits sufficient photocatalytic activity. And can be manufactured by a simple operation.

[0035] The content of the iron (III) compound in the solution may be set according to the amount of the surface iron (soot) compound supported on the nitrogen atom-containing titanium dioxide or the sulfur atom-containing titanium dioxide.

 [0036] The solution is, for example, a powder substance containing an iron (III) compound such as FeCl in an appropriate solvent.

 Three

 Is dissolved to ionize the iron (III) compound and then the trivalent iron ions are dispersed. The solvent is not particularly limited as long as it can ionize iron. Examples thereof include water.

 [0037] When the nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide is immersed in a solution in which the iron (III) compound is dissolved, for example, using a stirrer, the nitrogen atom-containing titanium dioxide or sulfur atom What is necessary is just to stir the mixture of containing titanium dioxide and this iron (soot) compound. The time required for stirring is not particularly limited, but from the viewpoint of supporting the surface iron (III) compound sufficient to exert the photocatalytic action on the nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide-titanium, 2 Is not less than 10 hours, preferably 5 hours, and is sufficient for supporting the surface iron (III) compound on the nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide. The following). The time required for vigorous stirring is markedly reduced compared to the case of using a solution in which a compound derived from divalent iron is dissolved, which is advantageous in terms of shortening the time required for production.

 [0038] Further, the photocatalyst of the embodiment which is powerful is the above-mentioned nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide from the viewpoint of exerting a higher photocatalytic action in an environment with less ultraviolet rays. It is preferable that the product obtained by loading the iron (III) compound is further reduced, and then the obtained product is acidified.

 [0039] The action of the photocatalyst of the present invention is not particularly limited, but for example, it is evaluated by a 2-propanol decomposition measurement method shown in Examples described later.

 [0040] The method for producing the photocatalyst of the present invention includes, for example,

(A) Nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide crystals are immersed in a solution in which the iron (III) compound is dissolved, and the nitrogen atom-containing titanium dioxide or sulfur A step of supporting an iron (m) compound on atom-containing titanium dioxide, and

 (B) washing the product obtained in the step (A) with an appropriate solution;

 It can be done by.

 [0041] In the step (A), as the solution in which the iron (III) compound is dissolved, for example, FeCl or

 Three

Fe (NO), etc. dissolves and has a property of exhibiting acidity after releasing trivalent iron ions.

3 3

 When liquid is used, iron (

III) After loading the compound, in the step (B), from the viewpoint of efficiently proceeding the oxidation reaction, a product having iron (iiiM compound supported on nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide is prepared. By washing with a basic substance such as ammonia, neutralizing, and further washing with water etc., salt and nitrate ions can be easily and sufficiently removed and the photocatalytic activity is maximized. Can be demonstrated.

 [0042] In the method for producing a photocatalyst of the present invention, from the viewpoint of further improving the photocatalytic action in an environment where there is visible light, for example, light from an indoor fluorescent lamp or the like, the nitrogen atom-containing titanium dioxide or sulfur atom-containing material is used. It is preferable to further reduce the product obtained by supporting the iron (IV) compound on titanium dioxide, and then acidify the obtained product.

 [0043] The reduction of the product obtained by loading the iron atom (III) compound on the nitrogen atom-containing titanium dioxide or sulfur atom-containing titanium dioxide can be performed under conditions that give electrons to the product. More specifically, the reduction is not particularly limited, and examples thereof include sodium borohydride, lithium borohydride, lithium aluminum hydride, hydrogen sulfide, hydrogen iodide, hydrogen, carbon monoxide. , Sulfur dioxide, sulfite, sodium sulfide, sodium polysulfide, ammonium sulfide, alkali metals, magnesium, calcium, aluminum, zinc, aldehyde compounds, formic acid, oxalic acid, etc. sell. In the reduction, for example, when sodium borohydride is used, the amount of sodium borohydride is desirably an amount that is at least 10 times the number of moles of the surface iron (III) compound supported on the product. . Thereafter, the obtained product may be washed using, for example, ion exchange water.

[0044] The acid of the product obtained after the reduction may be artificially performed while maintaining the conditions for depriving electrons from a strong product that may be performed with natural acid. The oxidation is Although not particularly limited, for example, permanganate, chromic acid, nitric acid, halogen, peroxide, peroxoacid salt, oxyacid salt, and other oxidizing agents (eg, nitrobenzene, iodine compounds) are used. It can be performed by a method or the like.

 [0045] In another aspect, the present invention relates to a photocatalyst composition containing the photocatalyst of the present invention. The photocatalyst composition of the present invention may further contain an adsorbent and Z or a porous agent in addition to the photocatalyst. Moreover, the photocatalyst composition of the present invention may further contain various solvents, various carriers and the like as long as the effects of the present invention are not hindered. According to the photocatalyst composition of the present invention, the photocatalytic action can be sufficiently exhibited with higher versatility.

 [0046] When the photocatalyst composition of the present invention further contains an adsorbent, the photocatalyst composition or a substance to be oxidatively decomposed is adsorbed by the adsorbent in the vicinity thereof. This photocatalyst composition is preferable in that a substance to be oxidatively decomposed by the photocatalyst can be efficiently decomposed. In addition, when the photocatalyst composition of the present invention further includes a porous agent, the surface area capable of adsorbing a substance to be oxidatively decomposed is increased. It is preferable in that the target of photocatalysis can be efficiently decomposed, for example, the substance that is subject to acidolysis by the photocatalyst. Further, when the photocatalyst composition of the present invention further contains an adsorbent and a porous agent, according to the photocatalyst composition, an object of application of photocatalysis, for example, an object of oxidation decomposition by a photocatalyst. Can be decomposed more efficiently.

 [0047] Examples of the adsorbent include activated carbon, silica gel, zeolite, artificial zeolite, synthetic zeolite, bentonite, apatite, sepiolite, montmorillonite, talc and the like. The adsorbents may be used alone or in combination of two or more.

 [0048] Further, examples of the porous agent include porous materials, diatomaceous earth, diatom shale, palygorskite (for example, trade name: attapulgite, etc.) among those mentioned as the adsorbent such as activated carbon. . The porous agent may be used alone or in combination of two or more.

[0049] Further, in the present invention, the photocatalyst of the present invention is added to the adsorbent and Z or the porous agent. The photocatalyst may be coated on the adsorbent and Z or the porous agent, which may support the photocatalyst. Furthermore, in the present invention, the photocatalyst of the present invention and the adsorbent and Z or porous agent may be dispersed in a binder and arranged in a matrix!

 [0050] The photocatalyst composition of the present invention may be mixed with the photocatalyst composition of the present invention as long as it exhibits the photocatalytic action, even if it reacts with the photocatalyst of the present invention to produce a compound. .

 [0051] The present invention includes products using the photocatalyst and uses thereof.

 [0052] In still another aspect, the present invention relates to an interior building material containing the photocatalyst of the present invention and a building material, and holding a layer containing the photocatalyst on the surface of the building material.

 [0053] Since the interior building material of the present invention contains the photocatalyst of the present invention, according to the interior building material of the present invention, an excellent effect of exhibiting a high photocatalytic action even in an environment with little ultraviolet light. Demonstrate. Therefore, by coating the photocatalyst of the present invention on the building material and supporting it near the surface of the base material, the interior building material can be easily provided with high photocatalytic activity energy. According to the interior building material, indoor harmful substances can be decomposed with high efficiency, for example, sick house syndrome and chemical substance allergy can be prevented.

 [0054] Further, since the interior building material of the present invention holds the layer containing the photocatalyst of the present invention on the surface of the building material, the interior building material of the present invention is difficult to use conventionally. Even under such circumstances, it can fully exert its high photocatalytic activity, can be used in various places, decomposes harmful substances with high efficiency, and sick house syndrome, chemical substance allergy, etc. Can be prevented.

 [0055] The interior building material of the present invention supports the photocatalyst of the present invention on the surface of various building materials including, for example, wall materials, wallpaper, ceiling materials, ceiling boards, floor materials, curtains, shelf materials, and the like. It can be obtained by carrying it on an air filter.

[0056] As a method of supporting the photocatalyst of the present invention on an interior building material, the photocatalyst is dispersed in a paint and coated on the surface of the building material. When the interior building material is a resin molded product, a surface is formed. In general, there are various existing supporting methods such as blending into a layer. The amount of the photocatalyst contained in the interior building material of the present invention may be an amount sufficient to exert the photocatalytic action. [0057] From the viewpoint of obtaining sufficient durability of the interior building material, a part of the photocatalyst may be masked with a substance that is not substantially affected by the photocatalytic action, such as silica.

 [0058] In still another aspect, the present invention relates to a coating composition comprising the photocatalyst of the present invention and a paint.

 [0059] Since the coating composition of the present invention contains the photocatalyst of the present invention! / According to the coating composition of the present invention, the coating composition of the present invention can be used even in places where usage forms such as narrow spaces are limited. By applying the coating composition, the photocatalytic action can be sufficiently exerted. That is, according to the coating material of the present invention, the photocatalyst compounded only by applying the coating material can be held near the surface of the object to be applied, and the high activity energy by the photocatalyst is applied to the object to be applied. And to easily provide a function for efficiently decomposing a target to which photocatalysis is applied, for example, a substance subject to oxidative decomposition (for example, harmful substances in the air or attached pollutants). Can do. Therefore, according to the coating composition of the present invention, a target to which photocatalysis is applied, for example, a substance that is subject to oxidative decomposition (for example, harmful substances in the air, attached pollutants, etc.) can be decomposed with high efficiency. Functions can be demonstrated easily and efficiently.

 [0060] The coating composition of the present invention can be obtained by dispersing and blending the photocatalyst of the present invention in a liquid coating material or a powder coating material.

[0061] The paint is not particularly limited. For example, silicone resin, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetratetrasilane, which is a tetrafunctional substance of tetraalkoxysilane compound. Butoxysilane, etc .; three functional substances of alkoxysilane compounds: alkoxysilanes, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrilip Roxoxysilane, etc .; Fluorine-based resin, such as force-inner-type fluorinated resin, Lumiflon-type fluorinated resin; Cement-based materials, such as hydraulic lime, Portland cement, alumina cement, mixed cement Cement, lime, gypsum, etc. Hard cement, etc .; Acetate-based resin, vinyl acetate-acrylic resin, ethylene acetate-based resin, acrylic styrene resin, acrylic resin, epoxy resin, alkyd resin, acrylic alkyd resin Water-based synthetic emulsion paint such as fat I can get lost. Among these, from the viewpoint of easy handling, the paint is preferably based on a silicone resin. The paints may be used alone or in combination of two or more.

[0062] According to the coating composition of the present invention, it can be applied to, for example, a wood board board, a gypsum board, a rock wall, a calcium oxalate board, a cloth bag fiber, etc. to form an interior building material. wear.

 [0063] The amount of the photocatalyst in the coating composition of the present invention should be an amount sufficient to exert the photocatalytic action.

 [0064] In another aspect, the present invention relates to a synthetic resin molded product obtained by blending the photocatalyst of the present invention and a synthetic resin.

 [0065] Since the synthetic resin molded body of the present invention is blended with the photocatalyst of the present invention, according to the synthetic resin molded body of the present invention, the photocatalytic action can be exhibited, and the target of application of the photocatalytic action, for example, It is possible to easily and efficiently exert a function of decomposing a substance (for example, harmful substances in the air or adhering pollutants, etc.) subject to oxidative decomposition with high efficiency.

 [0066] Further, since the synthetic resin molded article of the present invention can be manufactured in a form according to the use, the synthetic resin molded article of the present invention has a higher photocatalytic action by the photocatalyst of the present invention. It becomes possible to use it.

 [0067] The synthetic resin molded article of the present invention can be obtained, for example, by mixing a photocatalyst with a synthetic resin in a pre-cured state, a softened state, or a molten state, or adhering it to the vicinity of the surface. As a result, the photocatalyst of the present invention can be held near the surface of the synthetic resin molding, and the photocatalytic action can be easily and efficiently exhibited with higher versatility.

[0068] The synthetic resin may be a thermosetting resin or a thermoplastic resin. Specific examples of the synthetic resin include polyethylene resin, polypropylene resin, polystyrene resin, polyacetate resin, polychlorinated resin, polysalt vinylidene resin, polycarbonate resin, Polyethylene terephthalate resin, Polybutylene terephthalate resin, Polyethylene naphthalate resin, Polyphenylene sulfide resin, Polyamide resin, Polyurethane resin, Polymethacrylate resin, Polyacrylonitrile resin, Atari Mouth-tolyl / butadiene / styrene copolymer (ABS resin), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), phenol resin, melamine resin, formaldehyde Examples include resin, urea resin, unsaturated polyester resin, epoxy resin, natural rubber and its derivatives. The synthetic resins may be used alone or in combination of two or more.

 [0069] The synthetic resin molded body of the present invention may be used as long as it does not interfere with the object of the present invention, even if it reacts with a photocatalyst and Z or a synthetic resin.

 [0070] From the viewpoint of sufficiently obtaining the durability of the synthetic resin molded article, a part of the photocatalyst may be masked with a substance that is not substantially affected by the photocatalytic action, such as silica.

 [0071] In still another aspect, the present invention relates to a fiber characterized by containing the photocatalyst of the present invention and a fiber component, wherein the photocatalyst is held by the fiber component.

 [0072] Since the fiber of the present invention is a fiber component of the photocatalyst of the present invention, the fiber of the present invention can exhibit the photocatalytic action.

 [0073] In the fiber of the present invention, the photocatalyst of the present invention may be supported on the surface of the fiber component which may be kneaded into the fiber component during production. From the viewpoint of sufficiently maintaining the strength of the fiber, a part of the photocatalyst may be masked with a substance that is not substantially affected by the photocatalytic action, such as silica.

 [0074] Examples of the fiber component include cotton, hemp, wool, silk, cellulose fiber, acetate fiber, polyester fiber, acrylic fiber, vinyl synthetic fiber, polypropylene fiber, glass fiber, metal fiber, and carbon fiber. Etc.

 [0075] In yet another aspect of the present invention, the photocatalyst of the present invention is irradiated with light to activate the photocatalyst, thereby deodorizing action, sebum dirt decomposition action, dust removal action, The present invention relates to a method for using a photocatalyst characterized by causing at least one selected from the group consisting of a decomposition action of pollutants and an antibacterial activity.

[0076] According to the method of using the photocatalyst of the present invention, since the photocatalyst of the present invention is used, the photocatalytic action is efficiently and easily exhibited even in the environment that has been difficult to use. Can be made. Further, according to the method of using the photocatalyst of the present invention, the photocatalyst of the present invention is irradiated with light to activate the photocatalyst, and the photocatalyst is retained. Deodorizing action, sebum dirt decomposing action, dust removing action, pollutant decomposing action, antibacterial activity, etc. can be exerted at or near the surface or object where the photocatalyst is supported. . Therefore, according to the method of using the photocatalyst of the present invention, bad odors, sebum dirt, dust accumulation, pollutants generated in automobile-related parts, office supplies, daily necessities, inside / outside houses, public goods parts, electrical equipment, etc. Adhesion, adhesion of germs, etc. can be reduced, and the environment can be improved easily and efficiently.

 [0077] In the method of using the photocatalyst of the present invention, the photocatalyst is activated by irradiating artificially a stronger irradiation dose of visible light or the like, which may be performed by light from an ordinary indoor fluorescent lamp or the like. May be.

 [0078] Applications for deodorizing by the method of using the photocatalyst of the present invention include a meter display board for automobile-related members, a glass inner surface, interior lining, sheets, a storage shelf for office supplies, partitions, slippers, daily life Equipment socks, suits, cold clothes, uniforms, shirts, underwear, kimonos, trash cans, towels, wigs, hats, house kites, ceilings, shoeboxes, closets, pillows, duvets, blankets, filters, fans, lights Umbrellas, blinds, carpets, sheets, pet huts, bird cages, tatami mats, bran, shoji, pet toilets, foliage plants, shoe covers, curtains, wallpaper, painted walls, toilet surroundings, toilet lids, public goods Applications include advertising, air purifiers for smoking of electrical equipment, air conditioner filters, OA equipment, AV equipment, fan heaters, kotatsu, air purifiers, and vacuum cleaners. By applying the method of using the photocatalyst of the present invention to the above-mentioned application, as a result of irradiating the photocatalyst with light, for example, a substance causing a bad odor is decomposed by oxidative decomposition.

 [0079] In addition, the use of the photocatalyst of the present invention for the decomposition of sebum stains includes meter display plates for automobile-related members, glass inner surfaces, handles, top surfaces and edges of office supplies desks, keyboards, telephones, Glasses for daily use, wigs, hats, handrails for house parts, chairs, display surfaces for display devices, frame for glasses, handrails for public goods, hanging leather in cars, OA equipment for electrical equipment, AV equipment, TV, laundry Application to machine etc. is mentioned. By applying the method of using the photocatalyst of the present invention to the above application, for example, sebum soil that is an organic substance is decomposed by an oxidative decomposition action as a result of irradiating the photocatalyst with light.

Furthermore, as an application for removing dust by the method of using the photocatalyst of the present invention, an automobile Applications include air conditioner fans for related components, display for office supplies, fan for notebook computers, hard disk surfaces, umbrellas for lighting lamps for building components, and blinds. By applying the method of using the photocatalyst of the present invention to the above-mentioned application, as a result of light being irradiated to the photocatalyst, for example, organic substances contained in dust are decomposed by oxidative decomposition action, and the dust is removed from the applied product Easily detached.

 [0081] The use of the photocatalyst of the present invention for decomposing pollutants includes license plates for automobile-related members, lights, door mirrors, cord surfaces of office supplies, microwave hoods for household items, water tanks, Bicycles, pools, umbrellas, house floors, tiles, air-con fans, sinks, fans, tables, bran, shoji, windows, smoking for electrical equipment Air purifiers, stereos, fan heaters, washing machines, rice cookers Application to dryers, dishwashers, etc. By applying the method of using the photocatalyst of the present invention to the above-mentioned application, as a result of the photocatalyst being irradiated with light, for example, organic substances contained in these contaminants that mainly adhere to the outer surface and cause contamination Is decomposed by the oxidative decomposition action so that the pollutant is easily detached, and the hydrophilicity of the photocatalyst is expressed so that the pollutant can be easily washed and washed away.

 [0082] The use of the antibacterial method according to the method of using the photocatalyst of the present invention includes sheets of automobile-related parts, telephones for office supplies, partitions, slippers, socks for daily necessities, cups, suits, winter clothes, uniforms. , Shirts, underwear, kimonos, aquariums, pools, trash cans, towels, wigs, hats, bath covers, glasses frames, wheelchairs, canes, house kites, rice cakes, pillows, futons, blankets, fans, sinks Umbrellas, blinds, sheets, pet huts, bird cages, tatami mats, pet toilets, wallpaper, painted walls, toilet surroundings, toilet lids, air conditioner filters for electrical equipment, washing machines, kotatsu, dishwashers, air Application to a cleaner, a vacuum cleaner, etc. is mentioned. By applying the method of using the photocatalyst of the present invention to the above-mentioned application, as a result of light being applied to the photocatalyst, for example, various bacteria adhering to the acid-decomposing action are killed or weakened and an antibacterial action is exhibited Is done.

[0083] In yet another aspect of the present invention, the photocatalyst of the present invention is irradiated with light to activate the photocatalyst, thereby decomposing a harmful substance in the air. It relates to the decomposition method. In the method for decomposing harmful substances of the present invention, the photocatalyst of the present invention is used. Therefore, according to the method for decomposing a harmful substance of the present invention, the photocatalytic action can be exhibited even in the environment that has been difficult to use conventionally, and a thick house such as formaldehyde is used. It can efficiently decompose harmful substances that cause the syndrome, and can improve the environment easily and efficiently.

 [0084] The method for decomposing toxic substances of the present invention can also be applied to decomposing toxic substances on an industrial scale. When the method for decomposing toxic substances of the present invention is applied to decomposing toxic substances on an industrial scale, the above-mentioned photocatalytic action can be exerted with a simple facility such as a conventional fluorescent lamp, and the capital investment is small. In addition, it is possible to decompose harmful substances efficiently with low operating costs.

 [0085] Examples of harmful substances to which the method for decomposing harmful substances of the present invention is applied include, for example, acetonitrile, phenolcarb, formaldehyde, toluene, xylene, paradichlorobenzene, ethylbenzene, styrene, chloropyrifos, di-phthalate. -Butyl, tetradecane, di-2-ethylhexyl phthalate, diazinon and the like. In particular, the method for decomposing harmful substances of the present invention exhibits an excellent effect of being able to decompose toluene, which has been difficult to decompose efficiently, and further improving the environment.

 [0086] In the hazardous substance decomposition method of the present invention, the photocatalyst can be activated by the same method as described above.

 Example

 [0087] Hereinafter, the present invention will be described in detail with reference to examples and the like, but the present invention is not limited to the powerful examples.

 [0088] (Production Example 1)

 (1) Preparation of nitrogen atom-containing titanium dioxide

Anatase-type titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: ST-01) and urea were mixed at a ratio of 1: 4 (molar ratio). The obtained mixture was fired in an electric furnace at a firing temperature of 400 ° C., 500 ° C. or 600 ° C. for 3 hours. The baked product was filtered and washed with ion-exchanged water. The washing and filtration were repeated as described above until the pH of the filtrate reached 7. Thereafter, the obtained powder was vacuum-dried at 60 ° C. Then get The decomposition of 2-propanol by the obtained powder was measured by the method shown in (2) below.

 [0089] (2) Degradation measurement method of 2-propanol

 5 ml of 50 mM 2-propanol acetonitrile solution and lOOmg of the sample to be measured were placed in a Pyrex glass test tube. The test tube was sealed with a silicon double cap. Next, the test tube was subjected to ultrasonic treatment (conditions: 60 W, 47 kHz, 5 minutes), and the sample to be measured was well dispersed to obtain a sample. Thereafter, the sample in the test tube was irradiated with light for 1 hour, and a decomposition reaction of 2-propanol with a photocatalyst was performed. During the light irradiation, a 500 W xenon lamp (manufactured by Usio Electric Co., Ltd., trade name: SX UL500XQ) was used as a light source. Also, as a colored glass filter, a product name: UV-35 (manufactured by Kenko Co., Ltd.) or a product name: Y-42 (manufactured by Kenko Co., Ltd.) is inserted between the light source and the sample, The wavelength was adjusted.

 [0090] After completion of the reaction, the sample was subjected to centrifugation to separate the sample to be measured and the solution component.

Thereafter, the solution components were subjected to gas chromatography, and the amount of 2-propanol reduced and the amount of acetone produced were measured. The measurement conditions of the gas chromatography were: injection temperature: 250 ° C, detection temperature: 270 ° C, cooling temperature: 70 ° C, nitrogen gas pressure: 0.5 kgZcm ² , hydrogen gas pressure: 0.7 kgZcm ² , air pressure: 0. 5kgZcm ^2, use column: DB- WAX (trade name, J & W Scientific Inc. Co., Ltd.) was.

 [0091] As a result, it was found that the powdery force 2-propanol calcined at 400 ° C was best decomposed. Therefore, hereinafter, the powder fired at 400 ° C was used as nitrogen atom-containing titanium dioxide.

 [0092] (Production Example 2)

 In Production Example 1, each of the rutile-type diacid titanium [Tika Co., Ltd., trade name: MT-150A] and anatase-type diacid titanium [Ishihara Sangyo Co., Ltd., trade name: ST-01] Sulfur atom-containing titanium dioxide was prepared in the same manner except that it was used, thiourea was used instead of urea, and the calcination temperature was 400 ° C.

[0093] (Production Example 3)

 Preparation of photocatalyst (iron-containing nitrogen atom-containing titanium dioxide)

As iron (ΠΙ) compound supported on nitrogen atom-containing titanium dioxide, iron sulfate (ΠΙ) · hydrated The product (manufactured by Sigma Aldrich, catalog number: 30771-8) 0.00634 g, 0.03219 g, 0.0437 g, 0.193121 g or 0.332187 g was dissolved in 300 ml of ion-exchanged water.

 For example, the amount of the iron (III) sulfate N hydrate is represented by the following formula:

3.00 (g) X [47.87 (g / mol) /79.87 (g / mol)] XNX [55.85 (g / mol)] — ¹ X 0.5 X 399.9 (g / mol) [where N is a nitrogen atom (Indicates the amount of iron (III) compound supported on titanium dioxide (weight% Z 100))

 Calculated by Thus, 0.1 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt% or 5 wt% of iron (III) compound is supported on the nitrogen atom-containing titanium dioxide I let you.

 [0094] To the obtained aqueous solution, 3 g of nitrogen atom-containing titanium dioxide obtained in (1) of Production Example 1 was added, and then the resulting mixture was stirred. After 2 hours, the supernatant was collected, and the amount of iron ions in the supernatant was quantified. In addition, the powder was washed with ion-exchanged water until the waste liquid power after washing became H7. The amount of iron ions in the waste liquid after washing was also quantified. The washed powder was vacuum-dried at 60 ° C. to obtain a photocatalyst (iron-containing nitrogen atom-containing titanium dioxide).

 [0095] (Production Example 4)

 Preparation of photocatalyst (reduced ferrous iron-containing nitrogen atom-containing titanium dioxide)

 Photocatalyst (iron-containing nitrogen atom-containing titanium dioxide) lg obtained in Production Example 3, 30 g of water, and sodium borohydride corresponding to a 10-fold molar amount of the iron (III) compound adsorbed on the powder. The resulting mixture was allowed to stir for 2 hours. Thereafter, the obtained product was washed with ion-exchanged water until the waste liquid strength after washing became H7. The washed powder was vacuum dried at 60 ° C. to obtain a photocatalyst (reduced iron-containing nitrogen atom-containing titanium dioxide).

 [0096] (Production Example 5)

 Preparation of photocatalyst (iron-containing sulfur atom-containing titanium dioxide)

To 100 ml of water, the salted pig iron (III) 0.0174g, 0.087g or 0.174g was added. The obtained mixture was stirred to prepare an aqueous solution in which trivalent iron ions were dissolved in an aqueous solvent. The sulfur atom-containing titanium dioxide lg obtained in Production Example 2 is immersed in the aqueous solution. Soaked. The resulting mixture was stirred with a stir bar for 1 hour. Next, the obtained product was subjected to suction filtration, and the powder was separated by filtration. The obtained powder was neutralized by washing with 1N aqueous ammonia. Further, the suction filtration and washing with ion exchange water were repeated twice. The obtained product was vacuum-dried at 60 ° C. to obtain a 1%, 5%, or 10% by weight iron (III) compound-introduced photocatalyst (iron-containing sulfur atom-containing titanium dioxide).

[0097] (Production Example 6)

 Preparation of photocatalyst (reduced ferrous iron-containing sulfur atom-containing titanium dioxide)

 A photocatalyst (reduced iron-containing sulfur atom-containing titanium dioxide) was prepared in the same manner as in Production Example 4.

[0098] (Comparative Example 1)

 The nitrogen atom-containing titanium dioxide obtained in Production Example 1 was used as Comparative Example 1.

[0099] (Comparative Example 2)

 The sulfur atom-containing titanium dioxide obtained in Production Example 2 was referred to as Comparative Example 2.

[0100] (Comparative Example 3)

 When introducing an iron (III) compound, iron sulfate (III) N hydrate (manufactured by Sigma-Aldrich, catalog number: 30771-8) 0.006437g, 0.332187g or 0.664373g, ion-exchanged water 300ml Dissolved in. As a result, 1 wt%, 5 wt% or 10 wt% of an iron (III) compound was supported on the nitrogen atom-containing titanium dioxide.

 [0101] To the obtained aqueous solution, 3 g of the sulfur atom-containing titanium dioxide obtained in Production Example 2 was added, and then the resulting mixture was stirred. Two hours later, the supernatant was collected, and the amount of iron ions in the supernatant was quantified. In addition, the powder was washed with ion exchanged water until the waste liquid after washing became pH7. The amount of iron ions in the waste liquid after washing was also quantified. The washed powder was vacuum-dried at 60 ° C to obtain a photocatalyst (iron-containing sulfur atom-containing titanium dioxide).

 [0102] (Test Example 1)

The X-ray diffraction patterns of the photocatalysts of Production Examples 2, 5, and 6 were analyzed. Fig. 1 shows an example of the results of using JDX-3500K, a product name of JEOL Ltd., as an X-ray diffractometer. [0103] As shown in Fig. 1, it can be seen that the photocatalyst of Production Example 6 retains γ-FeO (OH).

 [0104] (Test Example 2)

Using each photocatalyst of Production Example 3, Production Example 4 and Comparative Example 1, the photocatalytic activity was evaluated in the same manner as in the decomposition measurement of 2-propanol in (2) of Production Example 1. The light intensity of the light source was 210 mWZcm ² . The result is shown in Fig.2. In the evaluation in FIG. 2, UV-35 (manufactured by Kenichi Co., Ltd.), which is a colored glass filter, was used. In the figure, “0 wt%” indicates a comparative example.

 As a result, as shown in FIG. 2, 0.1% by weight to 3.0% by weight of the iron (III) compound is supported, and the iron-containing nitrogen atom-containing titanium dioxide is the nitrogen atom of Comparative Example 1. It can be seen that the 2-propanol decomposition activity is higher than that of the contained diacid titanium. In addition, as shown in FIG. 2, the reduced ferrous iron-containing nitrogen atom-containing titanium dioxide of Production Example 4 showed higher 2-propanol decomposition activity than the nitrogen atom-containing titanium dioxide of Comparative Example 1, and had the same amount. Compared with the iron-containing nitrogen atom-containing titanium dioxide of Production Example 3 on which an iron (III) compound is supported, it can be seen that the 2-propanol decomposition activity is remarkably high.

 [0106] Therefore, it is understood that the photocatalytic activity is remarkably improved by further reducing the iron-containing nitrogen atom-containing titanium dioxide-titanium carrying the iron (III) compound.

 [0107] (Test Example 3)

Using the photocatalysts of Production Example 5, Production Example 6, Comparative Example 2 and Comparative Example 3, the photocatalytic activity was evaluated in the same manner as the method for measuring 2-propanol decomposition in (2) of Production Example 1. A typical example of the results when using anatase-type titanium dioxide is shown in FIG. 3, and a typical example of the results when using rutile-type titanium dioxide is shown in FIG. In the evaluation in FIG. 3, the light intensity of the light source was 7.3 mWZcm ^2, and in the evaluation in FIG. 4, the light intensity of the light source was 210 mWZcm ² . In the evaluation in FIGS. 3 and 4, UV-35 (manufactured by Kenko Co., Ltd.) which is a colored glass filter was used. In the figure, “0 wt%” indicates a comparative example.

[0108] As a result, when anatase-type titanium nitric acid titanium was used, the photocatalyst of Production Example 5 (containing iron-containing sulfur atoms) was compared with the sulfur atom-containing titanium dioxide of Comparative Example 2, as shown in FIG. Titanium dioxide) shows high 2-propanol decomposing activity, and the photocatalyst of Preparation Example 6 (reduced iron-containing sulfur atom-containing titanium dioxide) shows higher 2-propanol decomposing activity. Further, the same amount of iron (III) compound is used for the photocatalyst of Production Example 5 (iron-containing sulfur atom-containing titanium dioxide) and the photocatalyst of Production Example 6 (reduced monoiron-containing sulfur atom-containing titanium dioxide). When the supported ones are compared with each other, it can be seen that the photocatalyst of Production Example 6 (reduced ferrous iron-containing sulfur atom-containing titanium dioxide) exhibits a remarkably high 2-propanol decomposition activity.

[0109] Therefore, it is understood that the photocatalytic activity is remarkably improved by introducing the iron (III) compound into the sulfur atom-containing titanium dioxide. Further, it is obvious that the photocatalytic activity can be further improved by further reducing the sulfur atom-containing titanium dioxide containing the iron (IV) compound. The same was true when rutile-type titanium dioxide was used.

 [0110] (Test Example 4)

The photocatalysts lOOmg of Production Example 3, Production Example 4 and Comparative Example 1 were spread on a petri dish having an inner diameter of 32 mm. Next, the photocatalyst on the petri dish was exposed to a black light with a light intensity of 1.5 mWZcm ² for 30 minutes to remove residual organic substances adhering to the surface of the photocatalyst.

 [0111] Acetaldehyde gasified with 125 mL of pure air sealed in a Tedlar bag 62.

 51 was collected using a gas tight syringe and injected into a Tedlar bag, thereby preparing 500 ppm cetaldehyde gas. In another tedlar bag, the petri dish containing the photocatalyst was placed and sealed. Next, 125 mL of the aldehyde gas was added to the Tedlar bag containing the photocatalyst.

[0112] Thereafter, the Tedlar bag containing the photocatalyst was allowed to stand in the dark until the acetonitrile concentration did not change. Next, the photocatalyst in the Tedlar bag was irradiated with light for a predetermined time, and the decomposition reaction of acetoaldehyde with the photocatalyst was performed. The light irradiation was performed using a 500 W xenon lamp (manufactured by Usio Electric Co., Ltd., trade name: SXUL500XQ) as a light source under the condition of light intensity: 13 mWZcm ² . Further, a cut-off filter [trade name: UV-35, manufactured by Kenko Co., Ltd.] was used in order to set the irradiation wavelength for the light irradiation to a wavelength of 350 nm or more. [0113] The amount of carbon dioxide produced by the decomposition of cetaldehyde was measured by gas chromatography. The gas chromatography was measured under the following conditions: injection temperature: 120 ° C, detection temperature: 150 ° C, column temperature: 100 ° C, nitrogen gas pressure: 1. Okg / cm ² , hydrogen gas pressure: 0. A packed column filled with 7 kgZcm ² , air pressure: 0.5 kgZcm ² , column used: TCP 20% Uniport R 60/80 was used, and a methanizer (product name: MT-221, manufactured by GL Science) was used. The results are shown in Fig. 5. Panel (A) shows the results in the case of iron-containing nitrogen atom-containing titanium dioxide, and panel () shows the results in the case of reduced iron-containing nitrogen atom-containing titanium dioxide. In the figure, circles indicate the results for nitrogen atom-containing titanium dioxide, and squares indicate iron-containing nitrogen atom-containing titanium dioxide or reduced ferrous iron carrying 3.0% by weight of iron (III) compound. As a result of containing nitrogen atom-containing titanium dioxide, the triangle mark indicates the case of iron-containing nitrogen atom-containing titanium dioxide or reduced ferrous iron-containing nitrogen atom-containing titanium dioxide carrying 1.0% by weight of iron (III) compound. The results are shown.

 As a result, as shown in FIG. 5, the photocatalyst of Production Example 3 (iron-containing nitrogen atom-containing titanium dioxide) is generated by decomposition of cetaldehyde as compared with the nitrogen atom-containing titanium dioxide of Comparative Example 1. A large amount of carbon dioxide and high acetaldehyde decomposition activity are shown, and it can be seen that the photocatalyst of Preparation Example 4 (reduced ferrous iron-containing nitrogen atom-containing titanium dioxide) shows higher acetaldehyde decomposition activity. . Further, the photocatalyst of Production Example 3 (iron-containing nitrogen atom-containing titanium dioxide) and the photocatalyst of Production Example 4 (reduced iron-containing nitrogen atom-containing titanium dioxide) carry the same amount of iron (III) compound. When these were compared, it can be seen that the photocatalyst of Production Example 4 (reduced iron-containing nitrogen atom-containing titanium dioxide) has a markedly high aldehyde decomposition activity.

 [0115] Therefore, it is understood that the photocatalytic activity is remarkably improved by introducing an iron (III) compound into nitrogen atom-containing titanium dioxide. In addition, it is possible to further improve the photocatalytic activity by further reducing the nitrogen atom-containing titanium dioxide-carrying iron (III) compound.

 [0116] (Test Example 5)

The ESR spectrum of the photocatalyst obtained in Production Example 3 [iron-containing nitrogen atom-containing titanium dioxide carrying 1.0% by weight of iron (III) compound] under light irradiation was measured. In addition, The ESR ^ vector was measured using an ESR ^ spectrometer (manufactured by JEOL Ltd.), measurement temperature: 77K, magnetic field: 1560G ± 250G, sweep time: 500G, 4 minutes, output: 8mW and Gain: 160 It measured on condition of this. The result is shown in FIG.

[0117] As a result, as shown in Fig. 6, a peak derived from trivalent iron ions was detected in the photocatalyst ESR ^ spectrum before light irradiation (dotted line in the figure). In the ESR vector of the photocatalyst (solid line and bold line in the figure), no peak was detected. From these results, it is suggested that in the photocatalyst, the excited electrons generated by light irradiation were trapped by the trivalent iron ions to generate divalent iron ions. From the above results, according to the iron-containing nitrogen atom-containing titanium dioxide, the excited electrons are efficiently trapped in the trivalent iron ions, and the charge separation efficiency is improved, thereby significantly increasing the photocatalytic activity. Is suggested. Industrial applicability

[0118] According to the present invention, deodorization, decomposition of sebum dirt, dust, even in an environment with little ultraviolet light, which has been difficult to apply in the past, for example, in an environment with light such as an indoor fluorescent lamp, Removal of pollutants, decomposition of pollutants, antibacterial, etc. become possible.

Claims

The scope of the claims  [I] A photocatalyst comprising a nitrogen atom-containing titanium oxide and an iron (III) compound, wherein the iron (III) compound is held on the surface of the crystal of the nitrogen atom-containing titanium oxide.  2. The photocatalyst according to claim 1, wherein the iron (III) compound is a y-type iron (III) compound. 3. The photocatalyst according to claim 2, wherein the γ-type iron (III) compound power is γ-FeO (OH). [4] A photocatalyst obtained by immersing a nitrogen atom-containing titanium oxide in a solution in which an iron (III) compound is dissolved, thereby supporting the iron (ΠΙ) compound on the nitrogen atom-containing titanium oxide. Medium.  [5] The product according to claim 4, wherein the product obtained by supporting the iron (III) compound on the nitrogen atom-containing titanium oxide is further reduced, and then the obtained product is oxidized. photocatalyst. [6] A photocatalyst comprising a sulfur atom-containing titanium oxide and an iron (III) compound, wherein the iron (III) compound is held on the surface of the crystal of the sulfur atom-containing titanium oxide. 7. The photocatalyst according to claim 6, wherein the iron (III) compound is a y-type iron (III) compound. 8. The photocatalyst according to claim 7, wherein the γ-type iron (III) compound power is γ-FeO (OH). [9] A photocatalyst obtained by immersing a sulfur atom-containing titanium oxide in a solution in which an iron (III) compound is dissolved, thereby supporting the iron (ΠΙ) compound on the sulfur atom-containing titanium oxide. Medium.  [10] The product obtained by loading an iron (III) compound on a sulfur atom-containing acid-titanium is further reduced, and then the obtained product is acidified. The photocatalyst described.  [II] Nitrogen atom-containing titanium oxide is immersed in a solution in which an iron (III) compound is dissolved, whereby the iron (ΠΙ) compound is supported on the nitrogen atom-containing titanium oxide. A method for producing a catalyst.  12. The method for producing a photocatalyst according to claim 11, wherein the product obtained by supporting the iron (III) compound on the nitrogen atom-containing titanium oxide is further reduced, and then the obtained product is oxidized. . [13] A sulfur atom-containing titanium oxide is immersed in a solution in which an iron (III) compound is dissolved, and thereby the iron (ΠΙ) compound is supported on the sulfur atom-containing titanium oxide. A method for producing a catalyst. [14] A product obtained by loading an iron (m) compound on the sulfur atom-containing titanium oxide is obtained. 14. The method for producing a photocatalyst according to claim 13, further reducing, and then oxidizing the obtained product.  [15] A photocatalyst composition comprising the photocatalyst according to any one of [1] to [10]. 16. The photocatalyst composition according to claim 15, further comprising an adsorbent and Z or a porous agent.  [17] The force of any one of claims 1 to 10, comprising the photocatalyst according to claim 1 and a building material, wherein the photocatalyst and the photocatalyst contained in the photocatalyst composition are shifted on the surface of the building material. A building material for interiors that retains a layer containing ore.  [18] A paint composition comprising the photocatalyst paint according to any one of claims 1 to 10.  [19] A synthetic resin molded article comprising the photocatalyst according to any one of claims 1 to 10 and a synthetic resin.  [20] A fiber comprising the photocatalyst according to any one of claims 1 to 10 and a fiber component, wherein the photocatalyst is held by the fiber component. [21] Any force of Claims 1 to 10 Irradiating the photocatalyst according to claim 1 with light to activate the photocatalyst, thereby deodorizing action, sebum dirt decomposition action, dust removal action, contamination A method of using a photocatalyst characterized by causing at least one selected from the group consisting of a substance decomposition action and antibacterial activity. [22] The photocatalyst according to any one of claims 1 to 10, wherein the photocatalyst is irradiated with light to activate the photocatalyst, thereby decomposing the harmful substance in the air. Disassembly method.  23. The method for decomposing a harmful substance according to claim 22, wherein the harmful substance is formaldehyde or toluene.