Titanium oxide photocatalyst having copper compounds supported thereon, and method for producing same

A copper compound support titanium oxide photocatalyst and a manufacturing method for the same

0001The present invention relates to a copper compound support titanium oxide photocatalyst which has a copper compound on the surface of titanium oxide, and a manufacturing method for the same.

0002The photocatalyst using titanium oxide is cheap, is excellent in chemical stability, has high catalyst activity, and is widely used as a photocatalyst by it being harmless to a human body etc. (for example, patent documents 1 and two references).<br />However, since titanium oxide reveals photocatalyst activity only under an ultraviolet exposure, it cannot reveal sufficient catalyst activity under the indoor light which hardly contains an ultraviolet-rays ingredient. Therefore, the visible light response type photocatalyst which reveals photocatalyst activity also under indoor light like a fluorescent light is proposed.<br />For example, in patent documents 3, the titanium dioxide which doped atoms, such as nitrogen, carbon, and sulfur, in the crystalline lattice is indicated as this visible light response type photocatalyst. In patent documents 4, it is CuO/TiO.₂(Mass % ratio) The inactivation agent of the phage virus which consists of Anatase type titanium oxide which contains copper in =1.0 - 3.5 is indicated.

<p num="0003"><patcit num="1"><text>JP,2007-51263,A</text></patcit><patcit num="2"><text>JP,2006-346651,A</text></patcit><patcit num="3"><text>JP,2004-143032,A</text></patcit><patcit num="4"><text>JP,2006-232729,A</text></patcit></p>

<p num="0004">If it is in the above-mentioned visible light response type photocatalyst, virus inactivation nature ("antiviral nature" may be called hereafter) and the further photocatalyst activity improvement are desired.<br />That is, since the visible light response type photocatalyst which doped atoms, such as nitrogen, in the crystalline lattice of titanium oxide like patent documents 3 has a limit in the doped quantity, photocatalyst activity improvement has a limit. It is lacking in virus inactivation nature.<br />Even if it is in the visible light response type photocatalyst consisting of Anatase type titanium oxide containing 2 value copper like patent documents 4, virus inactivation nature cannot fully raise photocatalyst activity, either rather than can be [ and ] enough.</p><p num="0005">The present invention is made under such a situation, and has a visible light response (performance which reveals photocatalyst activity also under indoor light like a fluorescent light), and an object of the present invention is to provide a copper compound support titanium oxide photocatalyst which is excellent in virus inactivation nature and photocatalyst activity, and a manufacturing method for the same.</p>

<p num="0006">In the copper compound support titanium oxide photocatalyst which has a copper compound on the surface of titanium oxide as a result of examining many things that this artificer should achieve the above-mentioned object, The content of a rutile type titanium dioxide uses a 1 value copper compound with a 2 value copper compound as a copper compound as titanium oxide, using what is more than 50 mol %, It found out that the copper compound support titanium oxide photocatalyst which is excellent in virus inactivation nature (antiviral nature) and photocatalyst activity could be obtained. The present invention is completed based on this knowledge.</p><p num="0007">That is, the present invention provides following [1] - [7].<br />[1] The copper compound support titanium oxide photocatalyst in which the content of a rutile type titanium dioxide has titanium oxide which is more than 50 mol %, and the 1 value copper compound and 2 value copper compound which were supported by the surface of the above-mentioned titanium oxide.<br />[2] A copper compound support titanium oxide photocatalyst given in the above [1] whose abundance ratio of the above-mentioned 1 value copper to the sum total of 1 value copper and 2 value copper is 20-70-mol %.<br />[3] The above [1] which is that in which the above-mentioned 1 value copper compound contains copper oxide (I), or a copper compound support titanium oxide photocatalyst given in [2].<br />[4] A copper compound support titanium oxide photocatalyst given in either of above-mentioned [1] - [3] which is that in which the above-mentioned 2 value copper compound contains copper hydroxide (II).<br />[5] A copper compound support titanium oxide photocatalyst given in any 1 paragraph of above-mentioned [1] - [4] from which the above-mentioned titanium oxide is obtained by a gaseous phase method.<br />[6] A manufacturing method of the copper compound support titanium oxide photocatalyst which supports a 1 value copper compound and a 2 value copper compound on the surface of titanium oxide whose content of a rutile type titanium dioxide is more than 50 mol %.<br />[7] A manufacturing method of a copper compound support titanium oxide photocatalyst given in the above [6] which includes the process of adding the reducing agent for returning 2 value copper to 1 value copper in the suspension which blended titanium oxide whose content of a rutile type titanium dioxide is more than 50 mol %, and a 2 value copper compound.<br />[8] Titanium oxide whose content of a rutile type titanium dioxide is more than 50 mol %, A manufacturing method of a copper compound support titanium oxide photocatalyst given in the above [6] including the process of carrying out light irradiation and returning some above-mentioned 2 value copper compounds to a 1 value copper compound to the catalyst precursor containing the 2 value copper compound supported by the surface of the above-mentioned titanium oxide.<br />[9] A manufacturing method of a copper compound support titanium oxide photocatalyst given in the above [8] which performs the above-mentioned light irradiation in an alcoholic content atmosphere.<br />[10] A manufacturing method of a copper compound support titanium oxide photocatalyst given in any 1 paragraph of above-mentioned [6] - [9] from which the above-mentioned titanium oxide is obtained by a gaseous phase method.</p>

<p num="0008">According to the present invention, a copper compound support titanium oxide photocatalyst which is excellent in virus inactivation nature (antiviral nature) and photocatalyst activity, and a manufacturing method for the same can be provided.</p>

0009<figref num="1">It is a graph which shows the Cu-K husks XANES spectrum of Example 1 and comparative examples 1-2.</figref><figref num="2">It is an analytical curve which shows the relation between the abundance ratio of Cu(I) in reference samples 1-6, and the no Marize value of a Cu-K husks XANES spectrum.</figref><figref num="3">CO in the sample of Example 3 and comparative examples 1-2₂It is a graph which shows the variation per hour of an yield.</figref><figref num="4">Phage equivalent concentration (LOG (N/N)) in the sample of Example 3 and comparative examples 1-2₀It is a graph which shows the variation per hour which is).</figref><figref num="5">It is a graph which shows change of a Cu-K husks XANES spectrum when light irradiation is carried out under nitrogen and ethanol atmosphere to the rutile type titanium dioxide which supported the 2 value copper compound.</figref><figref num="6">It is a graph which shows change of a Cu-K husks XANES spectrum when light irradiation is carried out under nitrogen and ethanol atmosphere to the Anatase type titanium oxide which supported the 2 value copper compound.</figref><figref num="7">It is a graph which shows change of a Cu-K husks XANES spectrum when light irradiation is carried out under nitrogen and ethanol atmosphere to the brookite type titanium oxide which supported the 2 value copper compound.</figref>

0010[Copper compound support titanium oxide photocatalyst]<br />The copper compound support titanium oxide photocatalyst of the present invention has titanium oxide whose content of a rutile type titanium dioxide is more than 50 mol %, and the 1 value copper compound and 2 value copper compound which were supported by the surface of the above-mentioned titanium oxide.

0011According to the copper compound support titanium oxide catalyst of the present invention, since the 2 value copper compound is supported on the surface of titanium oxide, it excels in the photocatalyst activity by visible light.

0012That is, a titanium oxide simple substance generates an electron and an electron hole by the light excitation by an ultraviolet exposure. This generated electron returns one electron of oxygen which is in the inside of the air which is sticking to the titanium oxide surface, or underwater like the following formula (1).<br />O₂+H⁺+e^--&gt;HO₂(-0.046V vs.SHE, pH=0) (1)<br />In a formula (1), SHE means a standard hydrogen electrode, it means having measured potential on the basis of SHE, and, as for vs.SHE, pH=0 means that all of the amount of Life of hydrogen gas and the amount of Life of a hydrogen ion are 1.<br />When the above-mentioned reaction (1) occurs, the electron hole and electron which were generated by the above-mentioned light excitation can be separated, both re-combination can be prevented, and an oxidized part can understand an organic matter by the strong oxidization power and the high mobility of an electron hole. Thus, in order to return one electron of oxygen of titanium oxide, it is necessary to carry out light excitation of the electron to the high position of -0.046V (pH=0) which is the oxidation-reduction potential.<br />With on the other hand, the copper support titanium oxide which made the copper compound support on the surface of titanium oxide, If light excitation of the electron is carried out by visible light to +0.16V (pH=0) which is an oxidation-reduction potential of a copper ion even if it does not carry out light excitation of the electron in titanium oxide to the above high positions, 2 value copper can be returned. In the back, 1 value copper returns oxygen by following (2) and (3) types, by returning to 2 value copper, 1 value copper itself can separate an electron and an electron hole, and it can prevent both re-combination. Since this electron hole has the strong conventional oxidization power same with titanium oxide and high mobility, an oxidized part can understand an organic matter.<br />O₂+2H⁺+2e^--&gt;H₂O₂(+0.068V vs.SHE, pH=0) (2)<br />O₂+4H⁺+4e^--&gt;2H₂O (+1.23V vs.SHE, pH=0) (3)

0013Since the copper compound support titanium oxide catalyst of the present invention contains both the 1 value copper compound and the 2 value copper compound, it is excellent in virus inactivation nature and photocatalyst activity both. That is, since the copper compound support titanium oxide catalyst of the present invention contains the 1 value copper compound which excels the 2 value copper compound in virus inactivation nature, it is excellent in virus inactivation nature. Since the copper compound support titanium oxide catalyst of the present invention contains a 2 value copper compound required for the photocatalyst activity by the above-mentioned visible light, it is excellent in the photocatalyst activity by visible light. The copper compound support titanium oxide catalyst of the present invention demonstrates the above-mentioned photocatalyst activity also by purple outdoor daylight.

0014Since the main ingredients of titanium oxide are a rutile type titanium dioxide, the copper compound support titanium oxide catalyst of the present invention is excellent in virus inactivation nature and photocatalyst activity compared with the case where Anatase type titanium oxide and brookite type titanium oxide are the main ingredients. Although the reason is not clear, it is surmised that it is because the oxidation-reduction reaction between 1 value copper and 2 value copper which were mentioned above is more efficiently performed under existence of a rutile type titanium dioxide.

0015Here, photocatalyst activity means at least one sort chosen from photoinduced degradation nature and optical induction hydrophilic voltinism. Photoinduced degradation nature is an operation as for which an oxidized part understands the organic matter which is sticking to the surface processed with titanium oxide, and optical induction hydrophilic voltinism is an operation to which the surface processed with titanium oxide becomes water and the hydrophilicity which gets used easily. It is thought that light excitation generates this optical induction hydrophilic voltinism, and it happens with the decrease of the hydroxyl group on the surface of titanium oxide by the diffused electron hole.<br />Although a virus Meaning a DNA virus and a RNA virus, it also includes the bacteriophage (it may be hereafter written as "phage") which is a virus infected with bacteria.<br />Next, each ingredient of a copper compound support titanium oxide photocatalyst is explained.

0016&lt;Titanium oxide&gt;<br />Since titanium oxide in the above-mentioned copper compound support titanium oxide photocatalyst contains many rutile type titanium dioxides, it is excellent in virus inactivation nature (antiviral nature) and photocatalyst activity.

0017The content of the rutile type titanium dioxide in the titanium oxide whole quantity is more than 50 mol %. It is inferior to photocatalyst activity and antiviral nature in it being less than [ 50 mol % ]. Content of this viewpoint to a rutile type titanium dioxide is more than 50 mol % preferably. More preferably it is 70-mol %, still more preferably is more than 80 mol %, and, especially preferably is more than 85 mol %.<br />The specific surface areas of titanium oxide are 1-200m preferably.²It is /g. 1m²Since specific surface area is large, it excels in photocatalyst activity that it is more than /g. 200m²It excels in handling nature that it is below /g. The lower limit of the specific surface area of these viewpoints to titanium oxide is 1 m preferably.²It is /g and more preferably is 3 m.²It is /g and, still more preferably is 4 m.²It is /g and, still more preferably is 8 m.²It is /g and upper limit is 200 m preferably.²It is /g and more preferably is 100 m.²It is /g and, still more preferably is 70 m.²It is /g and, still more preferably is 50 m.²It is /g. The specific surface areas of titanium oxide are 3-100m more preferably.²It is /g and, still more preferably they are 4-70m.²It is /g and, especially preferably they are 8-50m.²It is /g. Specific surface area is the value measured by the BET method by nitrogen adsorption here.<br />As for titanium oxide, what was produced by using titanium tetrachloride as materials by the gaseous phase method (how to obtain titanium oxide by the gaseous phase reaction of titanium tetrachloride and oxygen) is preferred. Since it goes via a high temperature process at the time of manufacture while the titanium oxide obtained by the gaseous phase method has a uniform diameter of a particle, its crystallinity is high. When using this feature as a photocatalyst, it is preferred.<br />It is advantageous if the way which uses the titanium oxide marketed as it is considers the processes of catalyst manufacture as for titanium oxide. For example, when using the thing with large specific surface area among titanium oxide of a commercial item which has the low crystallinity of rutile, it must be made the titanium oxide which performs calcination etc. and has the optimal specific surface area and crystallinity. If it passes through such a process to calcinate, the part and excessive time and effort will be taken, and it will become a cause of a cost overrun. The trouble of coloring at the time of calcination may also occur. It is preferred to use the commercial item (Showa titanium incorporated company make rutile type titanium dioxide F-10 grade) of the titanium oxide obtained also from such a viewpoint by the gaseous phase method for having moderate crystallinity and specific surface area as it is.

0018&lt;Copper compound&gt;<br />The copper compound support titanium oxide photocatalyst of the present invention has a 1 value copper compound and a 2 value copper compound on the surface of titanium oxide. Thereby, the copper compound support titanium oxide photocatalyst of the present invention becomes what was excellent in virus inactivation nature (antiviral nature) as above-mentioned, and excellent in the photocatalyst activity by visible light and ultraviolet light.

0019As for the content of a copper compound to titanium oxide, it is preferred that a copper ion (sum total of a 1 value copper ion and a 2 value copper ion) is 0.01-10 mass parts to 100 mass parts of titanium oxide. In the case of 0.01 mass part or more, the antiviral effect and visible light response by copper compound support are satisfactorily revealed. The titanium oxide surface is prevented from it being covered that it is 10 mass parts or less, and the function of a photocatalyst is satisfactorily revealed. A lower limit is preferred to 100 mass parts of titanium oxide, and 0.01 mass part of content [ 0.05 mass part of / 0.07 mass part of ] of these viewpoints to a copper ion is 0.1 mass part still more preferably still more preferably more preferably. 10 mass parts of upper limit [ 7 mass parts of / 5 mass parts of ] are 2 mass parts still more preferably still more preferably more preferably. Content of a copper ion is 0.05-7 mass parts more preferably to 100 mass parts of titanium oxide. Preferably it is 0.07-5 mass parts, and is 0.1-2 mass parts especially preferably.<br />The average particle diameter of the copper compound supported by titanium oxide is 0.5-100 nm preferably. Crystallinity becomes it good that it is 0.5 nm or more, and antiviral nature improves. (i) specific surface area becomes it large that it is 100 nm or less, and it has an effect of etc which is excellent in antiviral nature and which can be satisfactorily supported on the surface of (ii) titanium oxide. Average particle diameter of these viewpoints to a copper compound is 0.5-80 nm more preferably. Preferably it is 1-70 nm, and is 2-50 nm especially preferably. These diameters of a particle can be checked by observing using an electron microscope.

0020The abundance ratio of 1 value copper (Cu(I)) to the sum total of 1 value copper (Cu(I)) and 2 value copper (Cu(II)) is 20-70-mol % preferably. It becomes what was excellent in virus inactivation nature (antiviral nature) in it being more than 20 mol %. The quantity of 2 value copper (Cu(II)) increases relatively that it is less than 70 mol %, and it becomes the thing excellent in photocatalyst activity. A lower limit is preferred and these viewpoints to the above-mentioned abundance ratio is 20-mol %. More preferably it is 25-mol %, and upper limit is 70-mol % preferably, more preferably is 60-mol %, still more preferably is 45-mol %, and, still more preferably is 35-mol %. The abundance ratio concerned is 25-60-mol % more preferably. Preferably it is 25-45-mol %, and is 25-35-mol % especially preferably.

0021&lt;&lt; 1 value copper compound &gt;&gt;<br />As a 1 value copper compound, although there is no restriction in particular, one sort of copper oxide (I), copper sulfide (I), copper iodide (I), copper chloride (I), and copper hydroxide (I) or two sorts or more are mentioned, and especially copper oxide (I) is used suitably.

0022&lt;&lt; 2 value copper compound &gt;&gt;<br />As a 2 value copper compound, although there is no restriction in particular, they are copper hydroxide (II) and copper oxide (II), One sort of copper chloride (II), copper acetate (II), copper sulfate (II), cupric nitrate (II), copper fluoride (II), copper iodide (II), and copper bromide (II) or two sorts or more are mentioned, and it is especially copper hydroxide (II) (Cu (OH)).₂It is used suitably.<br />It is preferred that acid value copper (I) and copper hydroxide (II) are included, and even if the 1 value copper compound and 2 value copper compound which were supported by titanium oxide consist of acid value copper (I) and copper hydroxide (II), they are preferred. A rate of acid value copper (I) in a total amount of a 1 value copper compound in which a 1 value copper compound and a 2 value copper compound which were supported by titanium oxide were supported by titanium oxide including acid value copper (I) and copper hydroxide (II), and a 2 value copper compound, and copper hydroxide (II) is more than 80 mass % preferably. More preferably it is more than 90 mass %, still more preferably is more than 95 mass %, and, still more preferably is 100 mass %.<br />&lt;&lt; copper compound support titanium oxide photocatalyst &gt;&gt;<br />Content of a rutile type titanium dioxide of a copper compound support titanium oxide photocatalyst of the present invention is more than 80 mol %. And it is preferred that an abundance ratio of 1 value copper (Cu(I)) to the sum total of 1 value copper (Cu(I)) and 2 value copper (Cu(II)) is 20-70-mol %.

0023[A manufacturing method of a copper compound support titanium oxide photocatalyst]<br />The manufacturing method of the copper compound support titanium oxide photocatalyst of the present invention supports a 1 value copper compound and a 2 value copper compound on the surface of titanium oxide whose content of a rutile type titanium dioxide is more than 50 mol %.<br />Next, the example of the manufacturing method of the copper compound support titanium oxide photocatalyst of the present invention is explained.<br />&lt;The example of manufacture which is the 1&gt;<br />This example of manufacture adds the reducing agent for returning 2 value copper (Cu(II)) to 1 value copper (Cu(I)) to the suspension in which the content of the rutile type titanium dioxide blended titanium oxide which is more than 50 mol %, and a 2 value copper compound.

0024Manufacture process &gt;&gt; of &lt;&lt; suspension<br />In this process, the content of a rutile type titanium dioxide blends titanium oxide and the 2 value copper compound which are more than 50 mol %, and prepares suspension. It is 60 or more, preferably 70-100 , more preferably 80-95 after the above-mentioned combination, and it is preferred several hours, preferably to agitate for about 1 hour and to prepare suspension.

0025(Titanium oxide)<br />The characteristics (content and specific surface area of a rutile type titanium dioxide in the titanium oxide whole quantity) of the titanium oxide used in this example of manufacture are as explanation of the above-mentioned copper compound support titanium oxide photocatalyst having indicated.

0026(2 value copper compound)<br />It is preferred that it is one sort chosen from copper chloride (II), copper sulfate (II), cupric nitrate (II), and copper acetate (II) or two sorts or more as a 2 value copper compound to add, it is more preferred that copper chloride (II) is included, and consisting of copper chloride (II) is still more preferred.

0027Addition process &gt;&gt; of &lt;&lt; reducing agent<br />Subsequently, the reducing agent for returning 2 value copper (Cu(II)) to 1 value copper (Cu(I)) is added to the above-mentioned suspension.<br />As a reducing agent, they are an alkaline metal, alkaline-earth metals, and aluminum, for example, The amalgam of zinc, and an alkaline metal and zinc, the hydrogenation thing of boron or aluminum, At least one sort of substances chosen from the group which consists of metal salt of a low oxidation state, hydrogen sulfide, a sulfide, thiosulfate salt, oxalic acid, formic acid, ascorbic acid, a substance that has aldehyde binding, an alcoholic compound containing phenol, etc. can be used. Preferably, the substance which has aldehyde binding can be used as a reducing agent. As a substance which has aldehyde binding, although sugars, more preferably glucose can be used, it is not limited to these, for example. Sugars are desirable reducing agents from it being cheap, and there being no toxicity and being able to remove easily by general-purpose operation of washing etc. after a reduction reaction.

0028In the case of reduction processing, it reacts by adjusting to base the suspension containing a 2 value copper compound and titanium oxide. Although the regulation agent of pH does not have limitation in particular in that case, it is sodium hydroxide, for example, A potassium hydrate, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, Triethyl amine, trimethylamine, ammonia, and a basic surface-active agent One sort chosen from (Big Chemie Japan BYK-9077 [ for example, ]) etc. or two sorts or more can be used, one sort chosen from sodium hydroxide and a potassium hydrate or two sorts can use it conveniently, and sodium hydroxide can use it more conveniently.<br />As a concrete example of the addition process of a reducing agent, it is sodium hydroxide (NaOH/Cu) to the above-mentioned suspension, for example.²⁺= 0-8 (molar ratio), and sugars (for example, glucose etc.: sugars/Cu)²⁺= Add 2-5 (molar ratio). And it is pH nine or more conditions, and several hours, preferably the solid produced by agitating for about 1 hour are Filter(ed), for example at 60 or more, preferably about 65-95 , and it dries after a flush. Thus, a 1 value copper compound and a 2 value copper compound can prepare the copper compound support titanium oxide photocatalyst supported on the surface of titanium oxide.<br />Copper compound support titanium oxide photocatalysts obtained by this reaction are the complex particles with which - value copper compound and a 2 value copper compound were supported by the surface of titanium oxide particles. It has virus inactivation nature and photocatalyst activity.<br />As for this suspension, it is preferred that 2 value copper (II) contains a copper chloride, a reducing agent contains sugar, and a pH adjuster contains sodium hydroxide, and it is preferred that 2 value copper (II) consists of copper chlorides, a reducing agent consists of glucose, and a pH adjuster consists of sodium hydroxide.

0029&lt;The example of manufacture which is the 2&gt;<br />Titanium oxide whose content of a rutile type titanium dioxide of this example of manufacture is more than 50 mol %, The process of carrying out light irradiation in the atmosphere which contains nitrogen and alcohol preferably to the catalyst precursor containing the 2 value copper compound supported by the surface of the above-mentioned titanium oxide, and returning some above-mentioned 2 value copper compounds to a 1 value copper compound is included.

0030&lt;&lt; catalyst precursor &gt;&gt;<br />If the content of the rutile type titanium dioxide contains titanium oxide which is more than 50 mol %, and the 2 value copper compound supported by the surface of the above-mentioned titanium oxide as this catalyst precursor, there will be no restriction in particular. For example, only a 2 value copper compound may be supported on the surface of titanium oxide, and a 1 value copper compound may be supported with a 2 value copper compound. In the copper compound support titanium oxide catalyst which starts the present invention as this catalyst precursor, Abundance ratio Cu(I)[ of the above-mentioned 1 value copper ]/{Cu(I)+Cu(II)} may fall for a certain reason, and it can use this example of manufacture in this case as a regeneration method of the copper compound support titanium oxide catalyst concerning the present invention.<br />As an example of the manufacturing method of this catalyst precursor, suspension is first manufactured according to the manufacture processes of the above-mentioned suspension, and the same process. Subsequently, without adding the above reducing agents, for example on pH nine or more conditions, several hours, preferably the solid produced by agitating for about 1 hour are Filter(ed) at 60 or more, preferably 70-100 , more preferably about 80 to 95 , and it dries after a flush. Thus, a catalyst precursor can be prepared.<br />titanium oxide -- a rutile type titanium dioxide -- more than 50 mol % -- it is necessary to contain In the reduction process mentioned below as it is less than [ 50 mol % ], some 2 value copper compounds cannot be satisfactorily returned to a 1 value copper compound.

0031&lt;&lt; reduction process &gt;&gt;<br />In this process, to the above-mentioned catalyst precursor, preferably light irradiation is carried out in nitrogen and an alcoholic content atmosphere, and some 2 value copper compounds in a catalyst precursor are returned to a 1 value copper compound.<br />That is, if light excitation of the electron in titanium oxide is carried out by light irradiation, the electron which carried out light excitation will return 2 value copper (Cu(II)) to 1 value copper (Cu(I)). Since the electron hole which produced by light excitation is consumed by decomposition of alcohol, re-combining with the electron which carried out light excitation is controlled. Thus, it is thought that some 2 value copper compounds can be satisfactorily returned to a 1 value copper compound.

0032As the above-mentioned alcohol, ethanol, methanol, 2-propanol, denatured alcohol, etc. are mentioned preferably.<br />Content of alcohol in atmosphere is one to 30 volume % preferably. More preferably it is two to 20 volume %, and, still more preferably is three to 15 volume %. Some 2 value copper compounds can be satisfactorily returned to a 1 value copper compound as it is more than 1 volume %.<br />As a light at the time of light irradiation, it may be visible light and may be purple outdoor daylight. At visible light irradiation, the light which penetrated the L-42 light filter (made by AGC techno glass incorporated company) can be used with the light emitted from light sources, such as sunlight, a mercury lamp, a xenon lamp, a white fluorescent light, and LED. In purple outdoor daylight irradiation, sunlight, a mercury lamp, a xenon lamp, a black light, or a white fluorescent light can be used.

0033Copper compound support titanium oxide photocatalysts obtained by a described method are the complex particles with which - value copper compound and a 2 value copper compound were supported by the surface of titanium oxide particles. It has virus inactivation nature and photocatalyst activity.

0034[The type of usage of a copper compound support titanium oxide photocatalyst]<br />Although the type of usage in particular of the copper compound support titanium oxide photocatalyst of the present invention is not limited, For example, a proper container can be filled up with solid-like forms, such as fine powder and granulation, and it can be used as it is, or can be used for one side or the both sides of the surface of arbitrary substrates, and an inside according to the form containing a copper compound support titanium oxide photocatalyst, and, generally the latter mode is preferred.

0035Although the compound substrate consisting of the substrate and two or more sorts of members which consist of general single members, such as metal, ceramics, and glass, as a substrate, for example can be mentioned, it is not limited to these. A copper compound support titanium oxide photocatalyst may be included in the coating agent which can exfoliate by a proper means like a floor polish. A copper compound support titanium oxide photocatalyst can be fixed on a film, and a copper compound support titanium oxide photocatalyst can also be exposed on the surface of a continuation film. Or the copper compound support titanium oxide photocatalyst etc. of the shape of a film which carried out sputtering of the thin film of a copper compound support titanium oxide photocatalyst can also be used for the surface of the filmy titanium oxide which carried out sputtering to glass.

0036The material which generally fixed the copper compound support titanium oxide photocatalyst on the substrate surface using fixed means, such as a binder, as a material which fixed the copper compound support titanium oxide photocatalyst on the substrate surface can be mentioned. Although any of an organic system binder or an inorganic system binder may be used as a binder, in order to avoid disassembly of the binder by a photocatalyst substance, it is preferred to use an inorganic system binder. Since it is not limited, for example, a photocatalyst substance is fixed on the substrate surface, especially the kind of binder can use arbitrary binders, such as a polymers binder which can form a thin film, by a polymerization or solvent volatilization besides inorganic system binders usually used, such as a silica system.

0037The material which can be obtained by stiffening the distributed thing which distributed the above-mentioned copper compound support titanium oxide photocatalyst in resin as a material which contains a copper compound support titanium oxide photocatalyst inside a substrate can be mentioned. As resin, any of a natural resin or a synthetic resin may be used. Although the metaphor can mention an acrylic resin, phenol resin, polyurethane resin, acrylonitrile / styrene copolymerization resin, acrylonitrile / butadiene / styrene copolymerization (ABS) resin, polyester resin, an epoxy resin, etc., it is not Eye determination(ed) by these specific resin.

0038The forms of application in particular of the copper compound support titanium oxide photocatalyst of the present invention are not limited, but can be used also in a dark place besides under existence of arbitrary light. The copper compound support titanium oxide photocatalyst of the present invention, Under dry states (for example, state of the low humidity in winter etc., etc.), the state of high humidity, or coexistence of an organic matter, it has high virus inactivation ability under existence (for example, underwater, inside of sea water, etc.) of water, and can carry out inactivation of the virus continuously. A metaphor is applicable to arbitrary subjects, such as inner Buro of buildings, such as the others and the hospital which are a wall, a floor, a ceiling, etc., and a factory, a machine tool, or measuring devices and electric appliances, and parts (insides, such as inside of a refrigerator and a washing machine, and a dish washer, the filter of an air wash machine, etc.). Although application to the hospital plants (a waiting room, an operating room, etc.) which serve as a dark place at the time of the inside of machinery, the storage room of a refrigerator, night, or non-use is mentioned as a suitable example as an example of a dark place, it is not limited to these. - of for example, the measure against influenza -- although the product incorporating the light source for carrying out suddenly, and coating and carrying out the ultraviolet exposure of the titanium oxide to the ceramics filter and nonwoven fabric filter of an air wash machine is proposed By applying the copper compound support titanium oxide photocatalyst of the present invention to a filter, it becomes less indispensable, and the source of ultraviolet light can reduce cost and can improve safety.

<p num="0039">Hereinafter, although an example explains the present invention more concretely, the present invention is not limited to the following example.<br />&lt;Example 1&gt;<br />It is a 50-g rutile type titanium dioxide (F-10, Showa titanium incorporated company make, BET specific surface area: 12 m) to distilled water 1000mL.²It is 0.293gCuCl so that /g may be made suspended and a copper ion may be 0.22 mass part to 100 mass parts of titanium oxide.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . CuCl₂2H₂O:C₆H₁₂O₆: 1 mol/L, 13.75 ml of sodium hydroxide (made by Kanto Kagaku, Inc.) solution and 1 mol/L, and 6.88 ml of glucose (made by Kanto Kagaku, Inc.) solution were added, and it heat-treated at 1 h and 70 so that the molar ratio of NaOH might be set to 1:4:8. The granular material produced by filtering slurry was washed with pure water, and it dried at 80 , cracked by the mixer, and obtained the sample.<br />Under [ it heats the obtained sample in fluoric acid solution, it all dissolves and there is a fixed quantity / ICP / liquid / extraction ]. As a result, the copper ion was 0.22 mass part to 100 mass parts of titanium oxide. Namely, the copper ion of preparation (CuCl)₂2H₂The whole quantity of O origin was supported by the titanium oxide surface.<br />In the example and the comparative example, BET specific surface area was measured using the full automatic BET surface area measuring instrument made from a Maun, Inc. tech "Macsorb, HM model-1208."</p><p num="0040">&lt;Example 2&gt;<br />It is a 50-g rutile type titanium dioxide (F-10, Showa titanium incorporated company make, BET specific surface area: 12 m) to distilled water 1000mL.²/g is made suspended and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . CuCl₂2H₂O:C₆H₁₂O₆: The molar ratio of NaOH added 1 mol/L, 6.88-ml sodium hydroxide (made by Kanto Kagaku, Inc.) solution and 1 mol/L, and 6.88-ml glucose (made by Kanto Kagaku, Inc.) solution, and heat-treated at 1 h and 70 so that it might be set to 1:4:4. The granular material produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by the mixer, and obtained the sample.</p><p num="0041">&lt;Example 3&gt;<br />It is a 50-g rutile type titanium dioxide (F-10, Showa titanium incorporated company make, BET specific surface area: 12 m) to distilled water 1000mL.²/g is made suspended and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . CuCl₂2H₂O:C₆H₁₂O₆: The molar ratio of NaOH added 1 mol/L, 3.44 ml of sodium hydroxide (made by Kanto Kagaku, Inc.) solution and 1 mol/L, and 6.88 ml of glucose (made by Kanto Kagaku, Inc.) solution, and heat-treated at 1 h and 70 so that it might be set to 1:4:2. The granular material produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by the mixer, and obtained the sample.</p><p num="0042">&lt;Example 4&gt;<br />It is a 50-g rutile type titanium dioxide (F-10, Showa titanium incorporated company make, BET specific surface area: 12 m) to distilled water 1000mL.²/g is made suspended and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . CuCl₂2H₂O:C₆H₁₂O₆: The molar ratio of NaOH added 1 mol/L and 6.88 ml of glucose (made by Kanto Kagaku, Inc.) solution, and heat-treated at 1 h and 70 so that it might be set to 1:4:0. The granular material produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by Mixer, and obtained the sample.</p><p num="0043">&lt;Example 5&gt;<br />Rutile type titanium dioxide (MT-150A, the TAYCA CORP. make, BET specific surface area of 100 m)²With the electric furnace, /g was calcinated at 950 for 3 hours. And it cracked and obtained the crack thing (a "MT-150A calcination article" is called hereafter). It is 5.3 m when the BET specific surface area of this MT-150A calcination article was measured.²It was /g.<br />The 50-g above-mentioned MT-150A calcination article is made suspended to distilled water 1000mL, and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . CuCl₂2H₂O:C₆H₁₂O₆: 1 mol/L, 13.75 ml of sodium hydroxide (made by Kanto Kagaku, Inc.) solution and 1 mol/L, and 6.88 ml of glucose (made by Kanto Kagaku, Inc.) solution were added, and it heat-treated at 1 h and 70 so that the molar ratio of NaOH might be set to 1:4:8. The granular material produced by filtering slurry was washed with pure water, and it dried at 80 , cracked by the mixer, and obtained the sample.</p><p num="0044">&lt;Comparative example 1&gt;<br />It is 50 g of Anatase type titanium oxide (FP-6, Showa titanium incorporated company make, BET specific surface area: 99 m) to distilled water 1000mL.²/g is made suspended and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . CuCl₂2H₂O:C₆H₁₂O₆: The molar ratio of NaOH added 1 mol/L, 13.75 ml of sodium hydroxide (made by Kanto Kagaku, Inc.) solution and 1 mol/L, and 6.88 ml of glucose (made by Kanto Kagaku, Inc.) solution, and heat-treated at 1 h and 70 so that it might be set to 1:4:8. The granular material produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by the mixer, and obtained the sample.</p><p num="0045">&lt;Comparative example 2&gt;<br />It is 50 g of brookite type titanium oxide (NTB-01, Showa titanium incorporated company make, BET specific surface area: 160 m) to distilled water 1000mL.²/g is made suspended and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . CuCl₂2H₂O:C₆H₁₂O₆: The molar ratio of NaOH added 1 mol/L, 13.75 ml of sodium hydroxide (made by Kanto Kagaku, Inc.) solution and 1 mol/L, and 6.88 ml of glucose (made by Kanto Kagaku, Inc.) solution, and heat-treated at 1 h and 70 so that it might be set to 1:4:8. The powder produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by the mixer, and obtained the sample.</p><p num="0046">&lt;Comparative example 3&gt;<br />It is a 50-g rutile type titanium dioxide (F-10, Showa titanium incorporated company make, BET specific surface area: 12 m) to distilled water 1000mL.²/g is made suspended and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . The granular material produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by the mixer, and obtained the sample.</p><p num="0047">&lt;Comparative example 4&gt;<br />It is a 50-g rutile type titanium dioxide (F-10, Showa titanium incorporated company make, BET specific surface area: 12 m) to distilled water 1000mL.²/g is made suspended and it is CuCl.₂2H₂O:C₆H₁₂O₆: It is 0.293gCuCl so that the molar ratio of NaOH may be set to 1:4:8.₂2H₂Adding and agitating O (made by Kanto Kagaku, Inc.), 1 mol/L, 13.75 ml of sodium hydroxide (made by Kanto Kagaku, Inc.) solution and 1 mol/L, and 6.88 ml of glucose (made by Kanto Kagaku, Inc.) solution, it heated at 70 and performed 1h heat treatment. The granular material produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by the mixer, and obtained the sample.</p><p num="0048">&lt;Measurement&gt;<br />Measurement &gt;&gt; of the rutile content in &lt;&lt; materials titanium oxide<br />The content of the rutile type titanium dioxide in the above-mentioned materials titanium oxide (F-10, MT-150A, FP-6, and NTB-01) was measured with the powder X-ray diffraction method.<br />That is, the product "X'pertPRO" made by PANalytical is used as a measuring device about the dried materials titanium oxide, X diffraction measurement was performed on condition of the tube voltage of 45 kV, 40 mA of tube current, time base range 2theta=20 - 80deg, sampling width 0.0167deg, and scan speed 1.1 deg/min using Cu-Kalpha1 line using the copper target.<br />The peak height (Hr) corresponding to a rutile type crystal, the peak height (Hb) corresponding to a brookite type crystal, and the peak height (Ha) corresponding to a Anatase type crystal were found, and the content (rutile content) of the rutile type titanium dioxide in titanium oxide was calculated by the following formulas.<br />Rutile content (Mol %) = {Hr/(Ha+Hb+Hr)} x100</p><p num="0049">Fixed quantity &gt;&gt; of the abundance ratio (Mol %) of &lt;&lt; 1 value copper (Cu(I)) and 2 value copper (Cu(II))<br />(1) A measuring device and a measuring method<br />As a measuring device, beamline BL14 B-2 of the large-sized synchrotron orbital radiation facilities (SPring-8) of Japan Synchrotron Radiation Research Institute is used, and it is the detailed-near X ray absorption end structure (X-ray absorption near-edge fine structure.) of a Cu-K husks absorption end. It outlines the following "XANES". The spectrum was measured.<br />As a measuring method, the penetration method was used for other samples using the fluorescence method at the time of measurement of the sample obtained by the example and the comparative example. Specifically, a built-in fluorescence method measurement unit or penetration method measurement unit was used for beamline BL14 B-2 of SPring-8.</p><p num="0050">(2) XANES measurement of the sample obtained by the example and the comparative example<br />About each sample obtained by the example and the comparative example, it mixed so that a sample and BN (boron nitride, Kanto Kagaku, Inc. make) might be set to 1:1 both in quality and in quantity, and it was made the pellet with the disk molding machine.<br />XANES measurement was performed about these pellets. The measurement result of Example 1, comparative example 1, and comparative example 2 is shown in Drawing 1. In Drawing 1, the peak revealed near 8975-8980 eV originates in Cu(I), and the peak which exists near 8990-8995 eV originates in both Cu(I) and Cu(II).<br />(3) Specification of the copper compound in a sample<br />CuO, Cu₂O, Cu (OH)₂And about each of metal Cu, what was mixed with BN of the specified quantity was made into the pellet with the disk molding machine, and the XANES spectrum was measured so that absorption-index mut might be set to 1, when a 0.5-mm-thick pellet was used. Subsequently, these spectra were compared with the XANES spectrum (especially near [ above-mentioned ] 8975-8980 eV and near 8990-8995 eV) of the sample of an example and a comparative example obtained above (1).<br />As a result, the copper compound in these samples is Cu.₂O and Cu (OH)₂It turned out that it exists by carrying out.</p><p num="0051">(4) Creation of an analytical curve<br />Then, Cu₂O and Cu (OH)₂Mixtures 1-6 which mixed When by the different mixture ratio were prepared. That is, it is Cu so that the abundance ratio {Cu(I)/(Cu(I)+Cu(II))} (Mol %) of 1 value copper Cu(I) and 1 value copper Cu(I) in the total amount of 2 value copper Cu(II) may become as follows.₂O and Cu (OH)₂Mixtures 1-6 which mixed When were prepared.<br />1:0 mol of mixture %<br />2:25.4 mol of mixture %<br />3:47.6 mol of mixture %<br />4:67.2 mol of mixture %<br />5:84.5 mol of mixture %<br />6:100 mol of mixture %<br />About these mixtures 1-6, reference samples 1-6 which made the pellet what was mixed with BN of the specified quantity with the disk molding machine were created, and the XANES spectrum was measured so that absorption-index mut might be set to 1, when a 0.5-mm-thick pellet was used. Here, it can ask for absorption-index mut with a following formula.<br />mut=In (I)₀/I)<br />mu: Linear absorption coefficient<br />t: Thickness of a reference sample<br />I₀: X line strength before entering into a reference sample<br />I: X line strength after a reference sample penetration<br />About each reference sample 1-6, the value which broke the intensity of the pre edge peak originating in Cu(I) revealed near 8977 eV by the highest intensity in the spectrum which exists near 8990-8995 eV was calculated as a no Marize value as shown in the following formula.<br />No Marize value = the intensity / the highest intensity of a pre edge peak<br />Therefore, it means that the abundance ratio {Cu(I)/(Cu(I)+Cu(II))} (Mol %) of Cu(I) is so large that this no Marize value is large.<br />The horizontal axis was made into the abundance ratio (Mol %) of the above-mentioned Cu(I), the data of (the molar ratio and no Marize value) of reference samples 1-6 was plotted in the graph which makes a vertical axis the above-mentioned no-Marize value, and the analytical curve was prepared in quest of the linear equation with the least square method as shown in Drawing 2.</p><p num="0052">(5) A fixed quantity of the abundance ratio (%) of Cu(I) of each sample, and Cu(II)<br />About the sample obtained by the example and the comparative example, from the XANES spectrum measured above (2), the above-mentioned no-Marize value was calculated and it asked for the abundance ratio (Mol %) of the above-mentioned Cu(I) and Cu(II) using the analytical curve produced above (4). The result is shown in Table 1.</p><p num="0053">&lt;&lt; volatile organic compound (VOC) decomposition -- active evaluation:CO₂Measurement &gt;&gt; of Generation amount<br />In the glass reaction vessels (capacity 0.5L) of a direct vent type, glass petri dishes 1.5 cm in diameter have been arranged, and 0.3 g of samples obtained by the example and the comparative example were placed on the petri dish. The volume ratio of oxygen and nitrogen replaces the inside of a reaction vessel with the mixed gas which is 1:4, Water (about (25 ) 50% of relative humidity) of 5.2microL, 5.1 volume % acetaldehyde standard reference gas (mixed gas with nitrogen) 5.0mL enclosure of the normal condition (25 , 1 atmosphere) was carried out (acetaldehyde concentration in glass reaction vessels is set to 500 volume ppm), and it irradiated with visible light from from outside the reaction vessel.<br />It installed in the position where the illumination in a reaction vessel will be 100000 luxs, using as a light source what equipped with the filter (brand name: L-42, AGC techno glass incorporated company make) which cuts ultraviolet rays with a wavelength of 400 nm or less into a xenon lamp at irradiation of visible light. The reduction speed of acetaldehyde and the generating speed of the carbon dioxide which is oxidative decomposition output were temporally measured with gas chromatography. CO at irradiation of visible light to the time of 1-hour progress₂Generation amount (mass ppm) is shown in Table 1. The measurement result of the sample of Example 3, comparative example 1, and comparative example 2 is shown in Drawing 3.</p><p num="0054">Evaluation of &lt;&lt; virus-inactivation ability: LOG (N/N)₀Measurement &gt;&gt;<br />Virus inactivation ability was checked by the following methods by the model experiment which used the bacteriophage. A method of using inactivation ability to a bacteriophage as a model of virus inactivation ability is indicated, for example to Appl.**Microbiol Biotechnol., 79, **pp.127-133, and 2008. It is known that a reliable result will be obtained.<br />It covered with filter paper in the Deep type petri dish, and added a little sterile water. Glass stands about 5 mm thick were placed on filter paper, and the glass board (50mmx50mmx1mm) which applied 1.5 mg of samples of the example and the comparative example on it was placed. Besides it acclimates beforehand and 100micro of QB phage (NBRC20012) suspension whose concentration is also clear was dropped L times, and the OHP film was put in order to contact the sample surface and phage. What covered this Depth type petri dish with the glass board was considered as the set for measurement. Multiple same sets for measurement were prepared.<br />It is a 15W white fluorescent light (Panasonic incorporated company, full white fluorescent light) as a light source. Using what attached the ultraviolet-rays cut filter (an incorporated company king factory, KU-1000100) to FL15N, two or more sets for measurement were settled on the position where illumination will be 800 luxs (illuminometer: measure in TOPCON IM-5). Phage density measurement of the sample on a glass board was performed after progress for a predetermined period.</p><p num="0055">Measurement of phage concentration was performed by the following methods. The recovering liquid (SM Buffer) of 10mL was permeated, and the sample on a glass board was made to shake for 10 minutes with a shaker. Culture solution (OD) of the coliform bacillus (NBRC13965) which carried out Righteousness dilution and cultivated this phage recovering liquid independently₆₀₀＞１．０、１×１０⁸It mixes with CFU/mL, and after agitating, it settled for 10 minutes into a 37 homoiothermal warehouse, and infected phage with coliform bacillus. This liquid was sprinkled in the agar medium, and after cultivating at 37 for 15 hours, the number of plaques of phage was measured visually. It asked for phage concentration N by multiplying the obtained number of plaques by the dilution magnification of phage recovering liquid.<br />Initial phage concentration N₀From phage concentration N after predetermined time to phage equivalent concentration (LOG (N/N))₀) -- it asked. The result is shown in Table 1 and Drawing 4.</p><p num="0056">[Supplement 14.08.2012 based on rule 26]<br /><tables num="1"><img file="WO2013002151A1_D0001.tif" /></tables></p><p num="0057">&lt;Result&gt;<br />The abundance ratio of copper (I) in the titanium oxide photocatalyst powder in which Example 3 (main ingredients: rutile type titanium dioxide), comparative example 1 (main ingredients: Anatase type titanium oxide), and comparative example 2 (main ingredients: brookite type titanium oxide) were acquired is the same (13 to 14%) in abbreviation. And CO₂When an yield is measured, Example 3 (main ingredients: rutile type titanium dioxide) has the highest yield. This shows that the photocatalyst activity (photoinduced degradation nature) by visible light improves by using what makes a rutile type titanium dioxide the main ingredients as titanium oxide.</p><p num="0058">Since both Cu(I) and Cu(II) are included, Examples 1-5 are antiviral nature (LOG (N/N)).₀It is photocatalyst activity (CO) as).₂It excels in both yields. Photocatalyst activity (CO) according [ Examples 1-4 ] to visible light to this order in this order, since the abundance ratio of Cu(II) is high₂It excels in the yield. On the contrary, since the abundance ratio of Cu(I) is high, Examples 4, 3, 2, and 1 are excellent in this order to virus inactivation nature at this order. Since Example 5 has the abundance ratio of Cu(I) higher than Examples 1-4, it excels Examples 1-4 in virus inactivation nature. Although Example 5 has an abundance ratio of Cu(II) lower than Examples 1-4, it excels Examples 1-4 in photocatalyst activity. As one of reasons, Example 5 can consider that the rutile type titanium dioxide content (100-mol %) in titanium oxide is higher than Examples 1-4 (85-mol %).</p><p num="0059">Example 1 (main ingredients: rutile type titanium dioxide), comparative example 1 (main ingredients: Anatase type titanium oxide), and comparative example 2 (main ingredients: brookite type titanium oxide) carry out the same procedure except titanium oxide materials differing. And when the abundance ratio of Cu(I) in the obtained sample is compared, Example 1 (main ingredients: rutile type titanium dioxide) is the highest. This shows that the method of manufacturing a titanium oxide photocatalyst using what makes a rutile type titanium dioxide the main ingredients as titanium oxide is preferred, in order to make the abundance ratio of Cu(I) high for the purpose of antivirus improvement etc.</p><p num="0060">&lt;Example 6&gt;<br />It is a 50-g rutile type titanium dioxide (F-10, Showa titanium incorporated company make, BET specific surface area: 12 m) to distilled water 1000mL.²/g is made suspended and it is 0.293gCuCl.₂2H₂O (made by Kanto Kagaku, Inc.) was added, and 1h heat treatment was performed, heating and agitating at 90 . The granular material produced by filtering slurry was washed with pure water, and was dried 80 , and it cracked by the mixer, and obtained sample A.<br />The 0.5-mm-thick pellet was produced for what mixed the above-mentioned samples A and BN by 1:1 both in quality and in quantity with the disk molding machine. In the tedlar bag, the produced pellet and the filter paper into which 1 g of ethanol was infiltrated were put in, and replacement by nitrogen gas of the atmosphere in a tedlar bag was performed.<br />Subsequently, it irradiated with visible light from from outside the reaction vessel with the following procedure, and performed XANES spectral measurement by the fluorescence method. That is, it is while irradiating with visible light (100000 luxs) for 30 minutes, After carrying out XANES measurement of nitrogen and the copper compound support titanium oxide under an alcoholic content atmosphere, light was intercepted and XANES measurement (for 30 minutes) of the sample which opened copper compound support titanium oxide wide in the atmosphere from the tedlar bag was carried out. The result is shown in Drawing 5 and Table 2.<br />The filter paper in which the above-mentioned sample A(with no mixture with BN) 0.3g and ethanol were included was put into the 500mL glass container, and it irradiated with visible light (100000 luxs) overnight. The titanium oxide surface was made to generate Cu(I) by this. Then, the volume ratio of oxygen and nitrogen replaces the inside of a reaction vessel with the mixed gas which is 1:4, Water (about (25 ) 50% of relative humidity) of 5.2microL, 5.1 volume % acetaldehyde standard reference gas (mixed gas with nitrogen) 5.0mL enclosure of the normal condition (25 , 1 atmosphere) was carried out (acetaldehyde concentration in glass reaction vessels is set to 500 volume ppm), and it irradiated with visible light (100000 luxs) from from outside the reaction vessel. CO by the irradiation for 1 hour₂The amount of Generation is shown in Table 2.</p><p num="0061">&lt;Comparative example 5&gt;<br />It replaces with a rutile type titanium dioxide, and is Anatase type titanium oxide (FP-6, Showa titanium incorporated company make, BET specific surface area: 99 m).²The same operation as Example 6 was performed except having used /g. The result is shown in Drawing 6 and Table 2.</p><p num="0062">&lt;Comparative example 6&gt;<br />It replaces with a rutile type titanium dioxide, and is brookite type titanium oxide (NTB-01, Showa titanium incorporated company make, BET specific surface area: 160 m).²The same operation as Example 6 was performed except having used /g. The result is shown in Drawing 7 and Table 2.</p><p num="0063"><tables num="2"><img file="WO2013002151A1_D0002.tif" /></tables></p><p num="0064">&lt;Result&gt;<br />The pellet which makes the main ingredients the rutile type titanium dioxide of Example 6 had the amount of generation of Cu(I) by visible light irradiation as high as 67-mol %, and its reduction speed from Cu(II) to Cu(I) was quick. Sample A which makes the main ingredients the rutile type titanium dioxide of Example 6 is CO.₂The amount of Generation was as high as 163 mass ppm. Thus, CO₂It is thought that the reason to which the amount of Generation became high is because the electron hole which produced by reduction to Cu(I) from Cu(II) decomposed acetaldehyde efficiently.<br />On the other hand, compared with the pellet of Example 6, and sample A, the reduction speed from Cu(II) to Cu(I) is slow, and the pellet and sample A which do not make the main ingredients the rutile type titanium dioxide of comparative examples 5 and 6 are COs.₂The amount of Generation was also little.<br />These results show that the rutile type titanium dioxide is excellent in the reproduction ability and photoinduced degradation ability from Cu(II) to Cu(I) compared with Anatase type titanium oxide and brookite type titanium oxide.</p>