JP2018023977A - Photocatalyst using reductive organic article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocatalyst available for organic material degradation or high in safety without receiving limitation of using scene or sterilization, and exhibiting activities by absorbing light with wide wavelength including visible light at low cost.SOLUTION: There are provided a photocatalyst consisting of a reaction product manufactured by mixing a reductive organic material having iron reduction performance (ascorbic acid) and an iron feedstock in the presence of water, especially the photocatalyst exhibiting photocatalyst activity when light with wavelength belonging to ultraviolet light, visible light or infrared light, an organic material degradation method including contacting the photocatalyst and a degradation object and exhibiting the light with wavelength belonging to ultraviolet light, visible light or infrared light, and a sterilization method including contacting the photocatalyst and the degradation object and exhibiting the light with wavelength belonging to ultraviolet light, visible light or infrared light.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photocatalyst using a reaction product of a reducing organic substance having iron reducing ability and iron. Moreover, this invention is a technique regarding the organic substance decomposition | disassembly method or the disinfection method using the said photocatalyst.

・ Conventional photocatalytic technology Because photocatalysts can be used for the decomposition and sterilization of organic harmful substances by simply shining light, there is a growing social need as a simple and versatile technology.
In addition to titanium oxide, metal compounds such as tungsten, indium, vanadium, silver, molybdenum, zinc, gallium phosphide, gallium, and arsenic are known as photocatalytic activities, all of which have an ultraviolet wavelength of 400 nm or less. It is a substance that exhibits only photocatalytic activity. Among these, photocatalysts other than titanium oxide have not been put into practical use because they have problems such as being very expensive and highly toxic. At present, only titanium oxide has been put into practical use as a photocatalyst.

When titanium oxide absorbs ultraviolet rays, it generates active oxygen and exhibits photocatalytic activity such as decomposition and sterilization of organic substances. Utilizing this effect, titanium oxide is coated on the outer wall to make it difficult to get dirty.
However, since titanium oxide does not show photocatalytic activity in visible light of 400 nm or more, it cannot be used for sterilization and decomposition in living spaces where only visible light such as fluorescent lamps can be used, and the application scene is limited. There was a problem of being.
In addition, techniques for doping impurities (doping) have been attempted to achieve photocatalytic activity under visible light (see, for example, Patent Documents 1 and 2), but the processing technique is difficult and very expensive. There is. Furthermore, since the activity of the photocatalyst produced by the doping technique is very weak, there is no situation that has been put to practical use.
In addition, in the United States, titanium oxide is a substance that has been certified as a carcinogen, and the safety of titanium oxide itself has been questioned, so the situations where titanium oxide can be used are quite limited. ing.

  From the above situation, it has been expected to develop a photocatalyst that is highly safe and is not limited by the use scene, and that is inexpensive and exhibits activity with visible light.

Japanese Unexamined Patent Publication No. 7-303835 JP 2006-305532 A

  The present invention solves the above problems, is a highly safe photocatalyst that can be used for organic matter decomposition or sterilization, and is not limited by the usage scene, and absorbs light of a wide range of wavelengths including visible light and is active. It aims at providing the photocatalyst shown at low cost.

As a result of extensive research, the inventors of the present invention have found that a reducing organic substance having iron reducing ability, or a reaction product obtained by mixing the reducing organic substance feedstock with an iron feedstock in the presence of water, It has been found that strong photocatalytic activity is imparted. Further, the present inventors have found that the photocatalytic activity is an activity exhibited not only when irradiated with visible light or infrared light but also with ultraviolet light. Furthermore, the present inventors have found that the photocatalyst has stability as a substance and can be used repeatedly. Note that the iron-reducing organic substance and the iron supply material, which are raw materials for the photocatalyst, are inexpensive and familiar substances, and are highly safe materials for the human body and the environment.
Then, the present inventors have found that by using the photocatalyst, it is possible to decompose and sterilize organic matter by irradiating not only ultraviolet rays but also visible light and infrared rays.

The present invention has been made based on these findings.
That is, the present invention according to [Claim 1] is directed to a reducing organic substance having an action of reducing trivalent iron to divalent iron, and an iron feedstock at 40 ° C. to 100 ° C. for 10 seconds to 10 days. A photocatalyst comprising, as an active component, a reaction product containing the Fe ²⁺ complex of the reducing organic compound obtained by mixing in the presence of water,
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The iron feedstock is mixed so that the mixture contains 0.1 to 10 parts by weight in terms of the weight of iron element with respect to a dry weight of 100 parts by weight of the reducible organic substance or the feedstock of the reducible organic substance. It relates to a photocatalyst.
Further, in the present invention according to [Claim 2], the iron feedstock is composed of iron (III) chloride, iron (III) sulfate, iron (III) citrate, iron (III) ammonium citrate, iron EDTA (III ), Iron (III) oxide, iron nitrate (III), iron hydroxide (III), or iron (III) pyrophosphate as a feedstock for one or more trivalent irons. Is.
Further, the present invention according to [Claim 3] is characterized in that the reaction product is obtained by mixing the reducing organic substance, the iron feedstock, and water having a weight twice the total weight thereof. The photocatalyst according to claim 1 or 2.
Further, the present invention according to [Claim 4] is directed to a reducing organic substance having an action of reducing trivalent iron to divalent iron and an iron feedstock at 40 ° C to 100 ° C for 10 seconds to 10 days. Using the reaction product containing the Fe ²⁺ complex of the reducing organic substance obtained by mixing in the presence of water as an active ingredient, and
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The photocatalyst characterized in that the mixing is performed by mixing the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of the dry weight of the reducing organic substance. It is related with the manufacturing method.
Further, the present invention according to [Claim 5] is characterized in that the iron feedstock contains iron (III) chloride, iron (III) sulfate, iron (III) citrate, iron (III) ammonium citrate, iron EDTA (III ), Iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate, and a feedstock of one or more trivalent irons. Is.
Further, the present invention according to [Claim 6] is characterized in that the reaction product is obtained by mixing the reducing organic substance, the iron feedstock, and water having a weight twice the total weight thereof. It is related with the method of Claim 4 or 5.
The present invention according to [Claim 7] is an organic substance decomposing agent comprising the photocatalyst according to any one of claims 1 to 3, wherein hydrogen peroxide is not used. It relates to an organic substance decomposing agent.
Further, the present invention according to [Claim 8] is to obtain a photocatalyst by the method according to any one of claims 4 to 6, and to use the photocatalyst as an active component, and not to use hydrogen peroxide, The present invention relates to a method for producing an organic substance decomposing agent.
Further, the present invention according to [Claim 9] obtains a photocatalyst by the method according to any one of Claims 4 to 6, contacts the photocatalyst with an organic substance to be decomposed, and belongs to ultraviolet light, visible light, or infrared light. The present invention relates to a method for decomposing organic matter characterized by irradiating light of a wavelength and not using hydrogen peroxide.
The present invention according to [Claim 10] relates to the method according to claim 9, wherein the light having a wavelength belonging to visible light or infrared light is irradiated.
Moreover, the present invention according to [Claim 11] is an organic substance comprising the photocatalyst according to any one of Claims 1 to 3, wherein hydrogen peroxide is not used. It relates to a decomposing agent.
Further, the present invention according to [Claim 12] is to obtain a photocatalyst by the method according to any one of claims 4 to 6, and to use the photocatalyst as an active component, and not to use hydrogen peroxide. The present invention relates to a method for producing a bactericide.
Further, the present invention according to [Claim 13] obtains a photocatalyst by the method according to any one of Claims 4 to 6, contacts the photocatalyst with an object to be sterilized, and belongs to ultraviolet light, visible light, or infrared light. The present invention relates to a sterilization method characterized by irradiating light of a wavelength and not using hydrogen peroxide.
Further, the present invention according to [Claim 14] relates to the method according to claim 13, wherein the light having a wavelength belonging to visible light or infrared light is irradiated.

  The photocatalyst of the present invention has a property of exhibiting activity when irradiated with visible light or infrared light as well as ultraviolet light. Accordingly, the present invention is expected to be used in various applications that have been difficult to use with the prior art titanium oxide. For example, it can be used in a normal indoor space.

Moreover, since the photocatalyst of this invention uses polyphenols and ascorbic acid as the iron reducible organic substance which is the raw material, it becomes a high safety | security with respect to a human body and an environment. On the other hand, titanium oxide, which is a conventional technique, is a substance that has been certified as a carcinogen in the United States, and has been impeded by its spread.
In this respect, the photocatalyst of the present invention is expected to be used in various applications that have been difficult to use with titanium oxide.

In addition, according to the present invention, an excellent photocatalyst can be provided by a simple method using only inexpensive raw materials (such as iron compounds and reducing organic substances contained in plants). Photocatalysts are produced at a particularly low cost, especially when plant extract residues (such as coffee cakes and tea husks), plant dry distillation liquids (coal-baked byproducts), and plant juices (such as grape juice) are used as the feedstock for reducing organic substances. It becomes possible. On the other hand, titanium oxide, which is a conventional technology, is an extremely expensive material of tens of thousands of yen per 10 mg.
In this regard, the photocatalyst of the present invention is expected to be a technology that solves the problem of titanium oxide production costs.

The photocatalyst of the present invention is expected to be widely used for sterilization and organic matter decomposition in a wide range of fields such as food, medicine, public health, agriculture, and environmental purification.

In Example 5, it is a photograph image figure which shows the result of having performed visible light irradiation and having performed the bactericidal test of Escherichia coli. The blue colored portion in the photograph (black portion in the black-and-white photograph) indicates a portion where E. coli is present. The colorless part indicates a part where E. coli is not present. In Example 6, it is a photograph image figure which shows the result of having irradiated sunlight and having performed the bactericidal test of colon_bacillus | E._coli. The blue colored portion in the photograph (black portion in the black-and-white photograph) indicates a portion where E. coli is present. The colorless part indicates a part where E. coli is not present. In Example 7, it is a photograph image figure which shows the result of having irradiated sunlight and having performed the bactericidal test of Escherichia coli. The blue colored portion in the photograph (black portion in the black-and-white photograph) indicates a portion where E. coli is present. The colorless part indicates a part where E. coli is not present.

  The present invention relates to a photocatalyst using a reaction product of a reducing organic substance having iron reducing ability and iron. Moreover, this invention is a technique regarding the organic substance decomposition | disassembly method or the disinfection method using the said photocatalyst.

[Reducible organic matter]
In the production of the photocatalyst of the present invention, “reducing organic substance having iron reducing ability” is used as a raw material. When the organic substance is defined, it can be defined as an organic substance having a strong reducing power and an action of reducing trivalent iron to divalent iron.
Specific examples of the organic substance include ascorbic acid and polyphenols. In addition to these compounds, the plant body or processed product thereof may contain a large amount of reducing organic substances having iron reducing ability, and can be suitably used as the raw material of the present invention.

Here, as “ascorbic acid”, not only ascorbic acid free acid but also ascorbic acid compounds (potassium ascorbate, sodium ascorbate, etc.) can be used.
In addition, “polyphenols” refers to phenolic molecules having a plurality of hydroxy groups. It is a compound contained in most plants, and various types such as flavonoids and phenolic acids are known. Specific examples of the compound include catechin (epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, etc.), tannic acid, tannin, chlorogenic acid, caffeic acid, neochlorogenic acid, cyanidin, proanthocyanidin, Thealvidin, rutin, flavonoids (such as quercitrin, anthocyanin, flavanone, flavanol, flavonol, isoflavone), flavones, chalcones (such as naringenin chalcone), xanthophyll, carnosic acid, eriocitrin, nobiletin, tangeretin, magnolol, honokiol, ellagic acid, Lignan, curcumin, coumarin, catechol, procyanidin, theaflavin, rosmarinic acid, xanthone, quercetin, resveratrol, gallic acid, fluorotanni , And the like. In addition, compounds having one or more of these compounds in the molecule (for example, a complex formed by combining these compounds to form a polymer) can also be mentioned.
Moreover, about the polyphenol composition extracted from a certain fruit, it may call as the polyphenol which attached | subjected the name of the fruit. For example, a polyphenol composition extracted from grape fruit is called grape polyphenol.

  In the present invention, when a purified product of the above compound is used as the raw material, the activity of the photocatalyst is increased, which is preferable.

-Feedstock of reducible organic substance In this invention, the plant body containing polyphenols and / or ascorbic acid, or its processed goods can be used as a feedstock of the said reducible organic substance.
Here, examples of the plant include those derived from one or more selected from fruits, seeds, foliage, buds, flowers, roots, and underground stems.

  For example, plant materials rich in 'ascorbic acid' include tomatoes, peppers, chili peppers, winter potatoes, bitter cucumbers, zucchini, cucumbers, peas, pumpkins, eggplants, green peas, broad bean, edamame, okra, acerola, citrus (lemon, lime) , Orange, grapefruit, navel, citron, mandarin orange, pumpkin, summer orange, hassaku, yokan, lime, Wenzhou mandarin orange, shikwasa, mandolin), strawberry, kiwifruit, papaya, blackberry, blueberry, cranberry, raspberry, bilberry, huckleberry, Strawberry, melon, apple, none, western, fig, peach, plum, guava, grape, prune, abalone, durian, pineapple, mango, banana, cherries, pomegranate, watermelon, gummy, loquat, mosquito Shrimp, chestnut, lychee, ginnan, olive, avocado, tea, lettuce, cabbage, kale, mustard, mizuna, komatsuna, radish, turnip, rape blossoms, Chinese cabbage, chingensai, takana, nozawana, morohaya, green onion, samurai, garlic, shrimp , Leek, onion, shallot, shiso, tomato, tsurumura, watercress, asparagus, basil, celery, celery, parsley, spinach, garlic, bamboo shoot, broccoli, cauliflower, sweet potato, potato, yam, lotus root, turnip, radish, Examples include brussels sprouts and seaweed (such as seaweed, wakame, kelp, and seaweed).

  In addition, plant materials rich in 'polyphenols' include grapes, strawberries, blackberries, blueberries, cranberries, raspberries, bilberries, huckleberries, apples, ume, peaches, plums, pears, pears, cherries, citrus fruits (lemons Lime, orange, grapefruit, navel, citron, mandarin orange, pumpkin, summer orange, hassaku, yokan, lime, Wenzhou mandarin orange, shikwasa, mandarin, etc.), loquat, kiwifruit, mango, mangosteen, citrus, prune, persimmon, banana, melon , Dragon fruit, coffee, mulberry, wolfberry, cassis, cashew, viburnum, guava, pomegranate, olive, acai, aronia, eggplant, tomato, grape, cacao, soybean, black soybean, red bean, green beans, peanut, black sesame, buckwheat, Tartary buckwheat, coffee beans, sesame, purple cabbage, tea leaves, urushi, mulde, garlic, broccoli, sugar cane, spinach, komatsuna, honeybee, okra, salmon, onion, morohaya, garlic, garlic, purple onion, asparagus, parsley, eucalyptus, Coffee, Ginkgo, Mint, Udo, Papaya, Perilla, Gymnema Silvesta, Senna, Dandelion, Horsetail, Fern (such as bracken, springfish), Banana, Oyster, Nara, Kunugi, Maple, Sequoia, Metasequoia, Pine, Sugi, Cypress, Acacia, Akamegasiwa, Takanotsume, Achacha, Akebi, Yamakogi, Ryubu, Tamshiba, Kobushi, Sarunasi, Shiromoji, Kuromoji, Kosiabura, Hagi, Hoonoki, Matatabi, Eucalyptus, Guava, Banaba, Rooibos, Ruffa, Kuwa, Kuku , Megurinoki, Urin, Merbao, Aogiri, Suou, Brazil Iku, Meringo, Peach, Sakura, Mokuren, Yerba Mate, Merugi, Ohigi, Yaeyama Hirugi, Hamasakuro, Nippa Palm, Hirugidae, Hirugimodoki, Purple Purple Potato, yam, taro (taro, shrimp, etc.), turmeric, lotus root, konjac, seaweed (seaweed, wakame, kelp, Aosa, arame, sagarame, etc.).

As said feedstock, what processed the plant body into states, such as a dried material, a juice, and an extract (especially water or a hot-water extract, an alcohol extract, a hydrous alcohol extract), can be used. Further, the juice or the extract can be used in the state of a dried product.
When making a dry product, it is desirable to perform processing such as crushing, crushing, and powdering. In view of the reaction efficiency with iron, a powder having a small particle size is preferable.
As a solvent used for extraction here, it is preferable to use water in the case of ascorbic acid. For polyphenols, it is preferable to use water, hot water, ethanol, or hydrous ethanol.

Moreover, as the said feedstock, a plant body or its processed product is extracted with water or hot water, and the residue which remained after that can also be used suitably.
Moreover, it can use suitably also about the dry distillation liquid (plant dry distillation liquid) obtained by thermally decomposing a plant body or its processed goods in a reduced state.

-Plant-derived raw materials with advantageous raw material costs In the present invention, the use of fruit juice, stem and leaf juice, plant distillate, roasted coffee beans, and tea leaves as raw materials as the feedstock for the reducing organic matter further reduces the raw material cost. A photocatalyst can be produced at low cost, and an economically advantageous effect can be expected.

(a) Fruit juice liquid It is preferable to use “fruit juice liquid” as a feedstock for the reducing organic matter. As a kind of fruit used for fruit squeezing, the fruit described in the said paragraph can be used suitably. In particular, those having a large total amount of polyphenols are suitable in terms of titer. From the viewpoint of raw material costs, it is preferable to use juices such as grapes, bananas, apples, oysters, tomatoes and citrus fruits.

(b) Stalk-and-leaves juice As a feedstock for the reducing organic matter, “stem-and-leaf juice” is preferably used. As the kind of plant used for the foliage juice, the plant foliage described in the above paragraph can be suitably used. In particular, those having a large total amount of polyphenols are suitable in terms of titer. From the viewpoint of raw material costs, it is preferable to use a juice of cedar, cypress, pine, cedar and the like.

(c) Plant dry distillation liquid As a feedstock for the reducing organic matter, it is preferable to use a “plant dry distillation liquid”. In addition to being rich in polyphenols, the raw materials contain many reducible organic molecules such as phenols, organic acids, carbonyls, alcohols, amines, basic components, and other neutral components. It is estimated that
Here, the plant dry distillation liquid refers to a dry distillation liquid (liquid having a dark brown color) obtained by pyrolyzing a reduced plant body. Appearance is reddish brown to dark brown. Although it can be used as the stock solution, it can also be used as a concentrated solution, a diluted solution, or a dried product thereof.
Specific examples of the plant dry distillation liquid include wood vinegar, bamboo vinegar, and persimmon vinegar. These can also be suitably used from the viewpoint of raw material costs.

(d) Roasted coffee beans It is preferable to use a raw material derived from 'roasted coffee beans' as the feedstock for the reducing organic matter. The raw material contains a large amount of polyphenols.
In the present invention, the roasted coffee beans can be used as they are or in a pulverized state. In addition, a component obtained by extracting the pulverized product with water or hot water (a so-called brewed coffee component) can be used. Moreover, the residue (what is called coffee lees) after extracting with water or hot water can be used.
In particular, from the viewpoint of raw material cost, it is most preferable to use 'coffee koji' that is discarded in large quantities after coffee component extraction.

Here, the roasted coffee beans include any coffee beans roasted according to a normal method. This includes the state of so-called ground (ground) coffee beans. Moreover, what crushed coffee beans and roasted them may be used.
Here, any coffee beans can be used as long as they are seeds of Coffea arabica, C. canephora (Robusta) and C. liberica (Coffea arabica), which are coffee trees. In addition, although raw coffee beans may be used, those that have been dried and stored as are commonly used are suitable. From the viewpoint of raw material costs, it is preferable industrially to use non-standard coffee beans.
Here, as the roasting, any method that is usually performed can be exemplified, for example, direct-fire roasting, hot-air roasting, far-infrared roasting, microwave roasting, heated steam roasting, low-temperature roasting, etc. be able to.
The pulverization may be performed by using a coffee mill, a grinder, a stone mortar or the like to grind ordinary coffee beans, and includes a wide range from coarsely ground to powdered. Considering the viewpoint of the reaction efficiency with iron, it is preferable to have a large surface area. Therefore, crushing, pulverization, pulverization and the like are preferable.

(d) Tea leaves It is preferable to use raw materials derived from 'tea leaves' as the feedstock for the reducing organic matter. The raw material contains a large amount of polyphenols.
In the present invention, the tea leaves can be used as they are or in a pulverized state. In addition, a component obtained by extracting the pulverized product with water or hot water (a so-called brewed tea component) can be used. Further, a residue (so-called tea husk) after extraction with water or hot water can be used. In particular, from the viewpoint of raw material costs, it is most preferable to use “tea husk” that is discarded in large quantities after extraction of tea components.

Here, any tea leaves can be used as long as the leaves of the camellia Camellia sinensis are picked. The picking method may be any method, but from the viewpoint of cost, mechanical picking is particularly preferable.
The picked tea leaves are mixed with the contents of the cells to cause oxidative fermentation. In the present invention, any tea leaves at any fermentation stage can be used. For example, green tea (such as sencha, bancha, stem tea, and roasted tea) that has been heated to suppress oxidative fermentation; blue tea (such as oolong tea) that has been fermented to some extent; black tea that has been fully fermented; Black tea (such as puer tea), and the like can be used. Preferable examples include green tea, black tea, and oolong tea. From the viewpoint of raw material costs, it is preferable industrially to use nonstandard tea leaves.
In view of the reaction efficiency with iron, it is preferable to have a large surface area, so that it is preferable to use after crushing, pulverizing, pulverizing and the like.

[Iron feedstock]
In the present invention, as a raw material for supplying the iron element, any of a bivalent iron feedstock, a trivalent iron feedstock, or a metallic iron feedstock can be used. Moreover, a plurality of things can be mixed and used.

Here, as the feedstock for divalent iron, iron chloride (II), iron nitrate (II), iron sulfate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), lactic acid Water-soluble iron compounds such as iron (II), sodium iron (II) citrate, iron (II) gluconate; and insoluble iron compounds such as iron (II) carbonate and iron (II) fumarate .
In addition, even if it is a compound insoluble in water among the said bivalent iron compounds, since it water-solubilizes by the chelating ability of the said reducing organic substance, it can be directly used as the iron feedstock of this invention.

In addition, as a feedstock for trivalent iron, water-soluble iron compounds such as iron (III) chloride, iron (III) sulfate, iron (III) citrate, iron (III) ammonium citrate, iron EDTA (III), etc. And insoluble iron compounds such as iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, and iron (III) pyrophosphate.
In addition, natural raw materials that contain a large amount of trivalent iron compounds include red jade soil, Kanuma soil, loam (soils rich in allophane iron), laterite (soils rich in iron (III) oxide), goethite (non-crystalline). Soil containing high quality minerals); natural iron ore such as pyrite, pyrite, siderite, magnetite, goethite; sand iron in which the iron ore has become dust; heme iron, shells, etc. Substances; Many trivalent iron compounds contained in soil and iron ore usually show insolubility in water.

  Moreover, iron materials, such as wrought iron and an alloy, can be mentioned as a feedstock of metallic iron. In addition, rust can also be used as a raw material. These metallic irons are usually insoluble in water.

Moreover, the aqueous solution containing the bivalent iron ion and / or trivalent iron ion which the said iron compound melt | dissolved in water can also be used.
In addition, even if it is insoluble in water among the said iron supply materials, since iron is water-solubilized by the chelating ability of the said reducing organic substance, it can be directly used as the iron supply material of the present invention.

Among these, in order to efficiently produce the photocatalyst of the present invention, it is preferable to use a water-soluble iron compound. In particular, inexpensive iron chloride, iron sulfate, or the like is preferably used. The iron valence of the compound can be either divalent, trivalent or any other.
Moreover, in order to manufacture in view of raw material costs and stable supply, it is preferable to use natural soil (especially red jade soil, Kanuma soil, loam, etc.) and metallic iron as iron supply materials.

[Mixing process]
In the present invention, the reducing organic substance (or the reducing organic substance feedstock) and the iron feedstock (or iron ions) are mixed in the presence of water to convert iron into divalent iron ions, A reaction product which is an active ingredient having photocatalytic ability in a coordinated form can be obtained.

-Mixing ratio of raw materials The mixing ratio of the raw materials is 0.1 parts by weight of the iron feedstock in terms of the weight of the iron element with respect to 100 parts by weight of the dry weight of the reducing organic substance or the reducing organic feedstock. The mixing may be performed so as to contain 0.5 part by weight or more, more preferably 1 part by weight or more, further preferably 2 parts by weight or more, particularly preferably 3 parts by weight or more, and still more preferably 4 parts by weight or more. When the ratio of iron element is too small (when the mixing ratio of the reducing organic substance is too large with respect to iron element), the excess reducing organic substance functions as a radical scavenging substance (scavenger), so photocatalytic activity May be disturbed.
Further, the upper limit of the amount of iron element is 10 parts by weight or less, preferably 8 parts by weight or less, more preferably 6 parts by weight or less in terms of the weight of iron element. When the ratio of the iron element is too large (when the mixing ratio of the reducing organic substance is too small with respect to the iron element), the iron ions cannot be maintained in a divalent state and the photocatalytic activity is lowered, which is not preferable.

Mixing operation The mixing operation of the present invention is performed in the presence of water. Here, the presence of water may be any condition as long as the reducing organic substance and iron can react with water as a medium. More specifically, the reaction is presumed to be a reaction in which the reducing organic substance turns iron ions into a reduced state (a state of Fe ²⁺ that is a divalent iron ion) to form a complex.

The amount of water may be at least a liquid amount capable of mixing and stirring the raw materials, and may be an amount sufficient to wet the mixture of the raw materials (reducing organic substance and iron).
Note that any water can be used as long as the conditions under which the reaction occurs. For example, tap water, well water, ground water, river water, deionized water, distilled water and the like can be mentioned.
In addition, when using a plant body juice, a plant dry distillation liquid, etc. as a liquid as a feedstock of reducible organic substance, it can be made to mix and react directly with an iron feedstock, without newly adding a medium. .

The mixing operation may be simple stirring and mixing, but can also be performed using a mixer, a large stirring tank, a vortex, a shaker, or the like.
Here, the temperature of the water may be a temperature at which the water is in a liquid state (for example, 1 to 100 ° C. if it is 1 atm).
It is possible to employ a room temperature that does not require heating (for example, 10 to 35 ° C.), but when heating, the reaction product is formed by heating at 40 ° C. or higher, preferably 50 ° C. or higher. Is promoted and suitable. The upper limit of the temperature can be 200 ° C. (in the case of pressure heating), but from the viewpoint of production cost, it is 100 ° C. or lower, preferably 90 ° C. or lower, which is the boiling point in normal heating under normal pressure conditions, It is desirable to carry out at 70 ° C. or lower. Note that, under reaction conditions of 100 ° C. or higher, it is preferable to perform the reaction in a sealed container in order to suppress thermal decomposition of the reducing organic substance.

The mixing time may be approximately 10 seconds or more until the reducing organic substance and iron sufficiently come into contact with each other. However, in order to improve uniformity, it is preferably 1 minute or more, more preferably 3 minutes or more, and even more preferably. It is desirable to perform a mixing process for 5 minutes or more.
In addition, the upper limit is 10 days, preferably 7 days, more preferably 5 days, more preferably 3 days, and particularly preferably 1 day in order to prevent the decay of organic matter due to the growth of microorganisms. It is desirable. However, there is no upper limit especially when sterilization is involved.
When an insoluble iron compound is used as the iron feedstock, the amount of the reaction product can be increased by increasing the reaction time after mixing.

[photocatalyst]
The reaction product (reaction product of reducing organic substance and iron) obtained through the above steps has excellent photocatalytic activity. In the reaction product, it is presumed that the reducing organic substance forms a complex by ^changing the iron ion to a divalent state (Fe ²⁺ state).

  The said reaction product obtained at the said process can be used as a photocatalyst with the supernatant obtained after reaction, or a hydrous precipitate. In addition, the supernatant and the precipitate can be separated and recovered and used as a photocatalyst. In addition, a dried product of the supernatant and / or precipitate (eg, natural drying, roasting, etc.), and a supernatant or suspension obtained by further dissolving the dried product in water can also be used as a photocatalyst. .

・ Characteristics of the photocatalyst of the present invention The reaction product emits these lights even when irradiated with light in a wide wavelength range of 200 to 1400 nm, that is, when irradiated with visible light or infrared light as well as ultraviolet light. Absorbs and exhibits excellent photocatalytic activity.
Here, 'ultraviolet rays' refers to light having a wavelength range of 380 nm or less. “Visible light” refers to light having a wavelength range of 380 to 750 nm, which is a wavelength range visible to the human eye. Specifically, 380-450 nm (purple light), 450-495 nm (blue light), 495-570 nm (green light), 570-590 nm (yellow light), 590-620 nm (orange light), 620-750 nm (red) Light). Infrared rays refer to light having a wavelength range of 750 nm or more.

The photocatalytic activity of the reaction product exhibits extremely strong photocatalytic activity when irradiated with ultraviolet rays. In particular, the intensity of the activity in the near ultraviolet light having a wavelength of 200 to 380 nm shows a much higher titer than that of titanium oxide.
In addition, the reaction product exhibits strong photocatalytic activity even when irradiated with visible light and infrared light in a wavelength region that does not exhibit activity with titanium oxide. Visible light exhibits strong activity especially in the wavelength range of violet light to blue light (380 to 495 nm) having a short wavelength. Infrared rays exhibit strong activity in the near infrared range of 750 to 1400 nm (especially around 900 to 1300 nm, more particularly around 1100 to 1300 nm). Such photocatalytic activity with visible light or infrared light is not found in the prior art.

  The reaction product absorbs irradiated light energy and exhibits an activity of decomposing nearby organic substances. The activity is presumed to be a phenomenon exhibited by radicals generated by a photocatalyst excited by light energy.

When the reaction product is continuously irradiated with light, it has a property of continuously exhibiting photocatalytic activity during irradiation. Moreover, even when light irradiation is interrupted once, photocatalytic activity is exhibited by re-irradiation. That is, the reaction product is a material that can be used repeatedly as a photocatalyst.
This is because the resonance structure in the molecule of the reaction product (the Fe ²⁺ complex of the reducing organic substance) efficiently transmits radicals by transmitting light energy to Fe ²⁺ , and its own molecule is attacked by radicals. However, it is presumed that this is a stable structure that scavenges due to the resonance structure.

[Specific use of photocatalyst]
The photocatalyst (reaction product of reducing organic substance and iron) of the present invention is a substance that is highly safe for the human body and the environment, so it is used for various uses such as medicine, food, public health, agriculture, industry, etc. be able to.
For example, when ascorbic acid and polyphenols are used as the reducing organic substance, since these are substances derived from food-derived feedstocks, they are expected to be used particularly in the food field. Ascorbic acid is particularly suitable because it is colorless and transparent.
Moreover, when a plant dry distillation liquid is used as a reducing organic substance feedstock, the component contains a substance having a slight odor. However, since the raw material is very inexpensive, it is expected to be used in fields such as agriculture, medicine, and public health.

-Organic substance decomposition In this invention, although the organic substance decomposition | disassembly activity which the said photocatalyst has can be utilized, decomposition | disassembly of organic substance whole is possible, but it can use suitably especially for decomposition | disassembly of an organic type pollutant and a harmful substance. That is, it can be usefully used in one process of environmental purification.

Here, the pollutants and harmful substances are substances that cause water pollution, soil pollution, and air pollution. Examples include organic substances that are harmful to humans and the environment, such as domestic wastewater, human waste water, factory wastewater, polluted river and lake water, soil in garbage disposal sites, industrial waste, farmland, and factory sites. it can.
Specific organic substances to be decomposed include, for example, detergents, food and drink residues, human waste, feces, agricultural chemicals, malodorous substances, waste oil, dioxins, PCBs, DNA, RNA, and organic waste such as proteins. it can.

When the photocatalyst of the present invention is used as an active ingredient of an organic substance decomposing agent, examples of its form include solid forms such as powder, granule, sheet form, board form, cube form and sponge form. Moreover, liquid forms, such as a concentrate and a liquid ampule, can be mentioned. In addition, powdered forms, forms solidified by mixing with excipients, forms filled in capsules, gel-like forms, and the like can also be exemplified.
In the present invention, after the photocatalyst is sprayed, dispersed, added, mixed, applied, kneaded, etc. to the decomposition target, the organic matter can be decomposed by irradiating with light.

The amount of the photocatalyst used may be a solution concentration that exhibits an organic substance decomposing action. For example, the iron equivalent concentration is 0.001 ppm or more, preferably 0.01 ppm or more, more preferably 0.05 ppm or more, further preferably 0.1 ppm or more, particularly preferably 0.5 ppm or more, more preferably 1 ppm or more, and even more preferably 2.5 ppm or more. Further, it is desirable to prepare and use it so that it becomes 5 ppm or more, particularly preferably 5.5 ppm or more, even more preferably 10 ppm or more, and even more preferably 20 ppm or more.
Further, although there is no particular upper limit, for example, an iron equivalent concentration of 40,000 ppm or less, preferably 10,000 ppm or less, more preferably 5000 ppm or less, still more preferably 1000 ppm or less, particularly preferably 750 ppm, more preferably 500 ppm or less. .

Since the decomposition effect of the photocatalyst is extremely strong, it is possible to efficiently decompose a hardly decomposable organic substance (for example, basic fuchsin). For example, in the case of irradiation with light of 100 W / m ² , it is possible to decompose organic substances at least 2.5 mg / L or more per day, and 35 mg / L or more when there are many.

-Sterilization Utilizing the powerful organic substance decomposition action of the photocatalyst of the present invention, it can be used for sterilization in various fields. Specific examples of the sterilization target include medical equipment, hospital room walls, affected areas of patients, clothes, bedding, food production equipment lines, foodstuffs, cutting boards, kitchen knives, kitchen utensils, tableware, toilet seats, handrails, farm equipment Examples include hydroponic equipment and nutrient solutions. Since the photocatalyst of the present invention can be used for irradiation with visible light or infrared light, unlike the conventional sterilization method using titanium oxide, the usage and usage scene are greatly improved.
In addition, as a target that can be sterilized, not only bacteria but also eukaryotic microorganisms, algae, archaea, viruses, viroids, and the like can be sterilized.

When the photocatalyst of the present invention is used as an active ingredient of a bactericide, examples of its form include solid forms such as powder, granule, sheet form, board form, cube form and sponge form. Moreover, liquid forms, such as a dilution liquid, a concentrated liquid, and a liquid ampule, can be mentioned. In addition, powdered forms, forms solidified by mixing with excipients, forms filled in capsules, gel-like forms, and the like can also be exemplified.
In the present invention, the photocatalyst can be sterilized by irradiating it with light after spraying, spreading, adding, mixing, applying, kneading and the like to the decomposition target.

The amount of the photocatalyst used may be a solution concentration that exhibits a bactericidal action. For example, the iron equivalent concentration is 0.001 ppm or more, preferably 0.01 ppm or more, more preferably 0.05 ppm or more, further preferably 0.1 ppm or more, particularly preferably 0.5 ppm or more, more preferably 1 ppm or more, and even more preferably 2.5 ppm or more. Further, it is desirable to prepare and use it so that it becomes 5 ppm or more, particularly preferably 5.5 ppm or more, even more preferably 10 ppm or more, and even more preferably 20 ppm or more.
Further, although there is no particular upper limit, for example, an iron equivalent concentration of 40,000 ppm or less, preferably 10,000 ppm or less, more preferably 5000 ppm or less, still more preferably 1000 ppm or less, particularly preferably 750 ppm, more preferably 500 ppm or less. .

Since the sterilization effect of the photocatalyst is extremely strong, for example, in the case of surface sterilization, a sufficient sterilization effect is exhibited by treatment with sunlight irradiation for about several minutes, preferably 10 minutes or more, more preferably 20 minutes or more. .
Even when a relatively weak light such as an LED or a fluorescent lamp is irradiated, a sufficient bactericidal effect is exhibited by treatment for 1 hour or longer, preferably 6 hours or longer, more preferably 12 hours or longer.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited to an Example.

[Example 1] “Raw material containing reducing organic substances”
By examining whether it has an activity to reduce trivalent iron to divalent iron, it was determined whether various raw materials were reducing organic substances.

(1) "Verification of iron reduction ability"
Each aqueous solution containing 100 parts by weight (in terms of dry weight) of each raw material shown in Table 1 containing the same weight of iron (III) chloride in terms of iron element (0.1 wt% each raw material, 0.1 wt% iron chloride solution) Was prepared and allowed to stand at room temperature for several minutes. Thereafter, each aqueous solution was mixed with dipyridyl 2 g / L and acetic acid 100 g / L, and the presence or absence of a color reaction was examined. Here, dipyridyl is a substance that does not react with trivalent iron and remains colorless, but turns red when reacted with divalent iron. Used for detection of divalent iron. Further, as a control, a 0.1 wt% iron (III) chloride aqueous solution was prepared, and the same operation was performed. The results are shown in Table 1.

As a result, in the solution containing various raw materials derived from plants (samples 1-1 to 1-8), polyphenols (samples 1-9 to 1-13), and ascorbic acid (sample 1-14), Presented. That is, these raw materials were shown to be raw materials containing a reducing organic substance having an action of reducing trivalent iron to divalent iron. Moreover, it was shown that the divalent iron reduced here is stably maintained in the state of divalent iron.
On the other hand, in the solution to which citric acid (sample 1-15) was added, the solution remained colorless. That is, these raw materials were shown to be raw materials that have no action of reducing trivalent iron to divalent iron.

(2) Discussion From this result, it was shown that polyphenols and ascorbic acid are reducing organic substances having iron reducing ability. Moreover, it was shown that the various raw materials derived from a plant body (especially the raw material which contains many polyphenols) become a supply raw material of the reducing organic substance which has iron reduction ability. In addition, since divalent iron ions were stably maintained, it was assumed that the reducing organic substance formed a complex structure of divalent iron ions.
On the other hand, citric acid is a substance known as a chelating agent exhibiting reducibility, but it has been shown that it has no reducing ability for iron.

[Example 2] “Wavelength for exciting photocatalytic activity”
'Reaction product of reducing organic substance and iron' was prepared from tea husk or coffee cake as raw material, and the photocatalytic activity of the substance was examined.

(1) "Measurement of photocatalytic activity"
4 parts by weight of iron (III) chloride in terms of iron element (100 parts by weight in terms of dry weight) per 100 parts by weight (dry weight equivalent) of tea husk (tea leaf hot water extraction residue) or coffee cake (roasted coffee beans ground residue) FeCl ₃ ) was mixed, water twice the total amount of both was added, and heat treatment was performed at 98 ° C. for 1 hour to obtain a reaction product. The filtrate obtained by filtration was designated as “tea leaf component / iron” (sample 2-1) or “coffee bean roast product / iron” (sample 2-2). In addition, titanium oxide (TiO ₂ : titanium oxide (IV) anatase type, particle size 100 to 300 nm, manufactured by WAKO) (Comparative 2-1) was prepared as a comparative sample.

Next, a plurality of 3.5 ppm basic fuchsin aqueous solutions in which each sample or comparative sample was added to 35 ppm in terms of iron element (in terms of titanium element in terms of titanium oxide) were prepared for each sample. Each aqueous solution was irradiated with LEDs with different wavelengths for 24 hours and allowed to stand, and basic fuchsin was quantified over time. Here, the irradiation intensity of the LED was 1 mW / cm ² for ultraviolet rays (375 nm). For the irradiation intensity of visible light (blue light (470nm), green light (525nm), yellow light (570nm), red light (660nm)) and infrared light (940nm, 1200nm), the photon density is 100μmol / m ² / sec. I went there. Basic fuchsin was quantified by measuring absorbance at 540 nm. As a control, the sample was allowed to stand in dark conditions for 24 hours, and basic fuchsin was quantified over time.
The absorbance at 540 nm (basic fuchsin quantification result) was measured, and the decomposition rate was calculated and shown in Tables 2-A to 2-D.

As a result, not only ultraviolet light (375 nm) but also visible light (470 nm) is added to the solution containing “tea leaf / iron” (sample 2-1) or “roasted coffee beans / iron” (sample 2-2). , 525 nm, 570 nm, 660 nm) and infrared rays (940 nm, 1200 nm), the basic fuchsin (refractory organic matter) was decomposed.
Specifically, when “tea leaf component / iron” (sample 2-1) was added, strong decomposition activity was observed by irradiation with visible light and infrared light (particularly, 1200 nm which is infrared having a long wavelength). In particular, when ultraviolet rays were irradiated, rapid decomposition was confirmed within a short period of 6 hours from the start of irradiation.
In addition, even when “coffee beans roasted ingredient / iron” (Sample 2-2) was added, degradation activity by visible light irradiation was observed. In particular, strong activity was observed when irradiated with infrared rays (particularly with a long wavelength of 1200 nm). In particular, when ultraviolet rays were irradiated, extremely rapid decomposition was observed within a short period of 6 hours from the start of irradiation.
On the other hand, when titanium oxide (Comparative 2-1), which is a comparative sample, was added, decomposition of basic fuchsin was observed only when irradiated with 375 nm, which is an ultraviolet wavelength. In addition, decomposition of basic fuchsin was not recognized at all at wavelengths longer than visible light (> 470 nm). That is, the photocatalytic activity of titanium oxide was confirmed only when irradiated with ultraviolet rays.

(2) `` Discussion ''
From the above results, it has been clarified that the reaction product of reducible organic substance and iron prepared from tea husk or coffee cake has a strong photocatalytic ability. In particular, it has been shown that the reaction product exhibits strong photocatalytic activity even when irradiated with visible light and infrared light having wavelengths that do not react with titanium oxide (conventional photocatalyst).
The photocatalytic activity of these reaction products showed a particularly strong value when irradiated with ultraviolet rays and infrared rays (especially infrared rays having a long wavelength). In particular, when irradiated with ultraviolet rays, it was shown that photocatalytic activity that is more rapid and stronger than titanium oxide is exhibited in a short time.

[Example 3] "Examination with various reducing organic substances"
It was investigated whether photocatalytic activity was observed even when reaction products of various reducing organic substances and iron were prepared.

(1) "Measurement of photocatalytic activity"
For 100 parts by weight (as dry weight) of ascorbic acid, grape polyphenol, catechin, chlorogenic acid, caffeic acid, tannic acid, or persimmon vinegar, 4 parts by weight of iron (III) chloride in terms of iron element ( FeCl ₃ ) was mixed, water having a weight twice the total amount of both was added, and heat treatment was performed at 98 ° C. for 1 hour to obtain reaction products shown in Table 3 (Samples 3-1 to 3-7). In addition, titanium oxide (TiO ₂ : titanium oxide (IV) anatase type, particle size 100 to 300 nm, manufactured by WAKO) was prepared as a comparative sample (Comparative 3-1).

Next, a plurality of 3.5 ppm basic fuchsin aqueous solutions in which each sample or comparative sample was added to 5.5 ppm in terms of iron element (in terms of titanium element in terms of titanium oxide) were prepared. The aqueous solution was irradiated with LEDs with different wavelengths for 24 hours and allowed to stand, and basic fuchsin was quantified over time. Basic fuchsin quantification and LED irradiation were carried out in the same manner as in Example 2. Further, as a control, the sample was allowed to stand in dark conditions for 24 hours, and basic fuchsin was quantified over time.
Absorbance at 540 nm (basic fuchsin quantification result) was measured, and the decomposition rate was calculated and shown in Tables 3-A to 3-D.

As a result, the solution containing the reaction product of various reducing organic substances and iron can emit light with any wavelength of ultraviolet (375 nm), visible light (470 nm, 525 nm, 570 nm, 660 nm) or infrared (940 nm, 1200 nm). Even when irradiated, degradation of basic fuchsin was observed. That is, strong decomposition activity was recognized by irradiation with visible light and infrared rays (particularly, 1200 nm which is an infrared ray having a long wavelength). Moreover, rapid decomposition activity was confirmed in a short time when irradiated with ultraviolet rays.
In particular, when irradiated with visible light and infrared light, strong photocatalytic activity was observed in the reaction products of polyphenols such as catechin, chlorogenic acid, caffeic acid, and tannic acid with iron (Samples 3-3 to 3-6) ). In addition, when UV light was irradiated, particularly strong photocatalytic activity was observed in all reaction product samples (Samples 3-1 to 3-7).
On the other hand, when titanium oxide as a comparative sample was added, the decomposition activity was not observed when irradiated with visible light and infrared light, and the decomposition activity was confirmed only when irradiated with ultraviolet light (Comparative 3-1). The decomposition rate was linear and slow.

(2) `` Discussion ''
From the above results, it was speculated that the photocatalytic activity is a property commonly found in the reaction product of a reducing organic substance having iron reducing ability and iron. In particular, it has been shown that photocatalytic activity is exhibited when irradiated with visible light and infrared light, which are wavelengths that do not react with titanium oxide (conventional photocatalyst).
Moreover, it was shown that the photocatalytic activity when irradiated with visible light and infrared rays is a property that is strongly retained by the reaction product of the present invention.

[Example 4] “Comparison with an organic substance having no iron reducing ability”
It was investigated whether photocatalytic activity was observed when reaction products of various organic substances not having iron reducing ability and iron were prepared.

(1) "Measurement of photocatalytic activity"
4 parts by weight of iron (III) chloride (FeCl ₃ ) in terms of iron element for each 100 parts by weight (as dry weight) of ascorbic acid, grape polyphenol, catechin, chlorogenic acid, caffeic acid, or persimmon vinegar Were added, water having a weight twice the total amount of the two was added, and heat treatment was performed at 98 ° C. for 1 hour to obtain reaction products shown in Table 4 (Samples 4-1 to 4-6). Moreover, as a comparative sample, iron (II) chloride, iron (III) chloride, iron (III) EDTA, iron (III) citrate, titanium oxide (TiO ₂ : titanium oxide (IV) anatase type, particle size 100 to 300 nm, WAKO) was prepared (Comparative 4-1 to 4-5).

Next, a plurality of 3.5 ppm basic fuchsin aqueous solutions in which each sample or comparative sample was added to 5.5 ppm in terms of iron element (in terms of titanium element in terms of titanium oxide) were prepared. The aqueous solution was irradiated with visible light (red light: 660 nm, photon density 100 μmol / m ² / sec) LED for 24 hours and allowed to stand, and basic fuchsin was quantified over time. Basic fuchsin quantification and LED irradiation were carried out in the same manner as in Example 2. Further, as a control, the sample was allowed to stand in dark conditions for 24 hours, and basic fuchsin was quantified over time.
The absorbance at 540 nm (basic fuchsin quantification result) was measured, and the decomposition rate was calculated and shown in Table 4.

As a result, when 660 nm, which is a visible light wavelength, was irradiated, decomposition of basic fuchsin was observed in the solution to which reaction products (samples 4-1 to 4-6) of various reducing organic substances and iron were added. .
On the other hand, when various iron compounds or titanium oxides as comparative samples were added, the decomposition of basic fuchsin was not confirmed (Comparison 4-1 to 4-5). In particular, even when EDTA iron (III) (comparative 4-3) or iron (III) citrate (comparative 4-4), which is a complex of iron and an organic substance that does not have iron reducing ability, is added. Decomposition of was not confirmed.

(2) `` Discussion ''
From the above results, it was suggested that the photocatalytic activity was not exhibited at all in the “complex having no iron reducing ability” iron complex (reaction product). This suggests that the photocatalytic activity of the reaction product of the reducing organic substance and iron is a property specific to the reaction product of “reducing organic substance having iron reducing ability” and iron.

[Example 5] “Bactericidal effect by visible light irradiation”
Using the reaction product of the reducing organic substance and iron, it was verified whether sterilization of E. coli irradiated with visible light was possible.

(1) "Sterilization test"
4 parts by weight of iron (III) chloride (FeCl ₃ ) in terms of iron element is mixed with 100 parts by weight (converted to dry weight) of tea husk (tea leaf hot water extraction residue), twice the total weight of both Was added, and heat treatment was performed at 98 ° C. for 1 hour to obtain a reaction product. The solid content obtained by filtration was designated as “tea leaf component / iron” (Sample 5-1). Moreover, titanium oxide (TiO ₂ : titanium oxide (IV) anatase type, particle size 100 to 300 nm, manufactured by WAKO) (Comparative 5-1) was prepared as a comparative sample.

A sample of the concentration shown in Table 5 is added to and mixed with 10 ⁶ cfu / mL suspension of E. coli (ATCC1124) in terms of iron element (in the case of titanium oxide), and visible light (blue light: 470 nm, photon) (Density 50 μmol / m ² / sec) was irradiated for 24 hours. Then, it was applied to an Escherichia coli assay plate and the number of surviving E. coli was examined. As a control, only E. coli was applied in the same manner and the same experiment was performed. The results are shown in FIG. The presence or absence of bactericidal power was evaluated in two stages (“+”: with bactericidal power, “−”: without bactericidal power), and are shown in Table 5.

As a result, it was shown that Escherichia coli can be killed by adding 20 ppm or more of the tea leaf component / iron (solid content after filtration) and irradiating it with visible light (Sample 5-1) .
On the other hand, when titanium oxide as a comparative sample was added, no decrease in E. coli due to visible light irradiation could be confirmed even when added at a high concentration (Comparative 5-1).

(2) `` Discussion ''
From the above results, it was shown that the bactericidal action by the photocatalytic activity is sufficiently exerted by irradiating only visible light using a reaction product of a reducing organic substance having iron reducing ability and iron. It was also confirmed that the bactericidal effect was sufficiently exhibited even when added at a concentration of 20 ppm. Further, it was shown that the photocatalytic activity also has a strong activity in the solid part of the reaction solution. (Example 2 shows that the filtrate of the reaction solution has a stronger activity.)
On the other hand, when titanium oxide was used, it was shown that photocatalytic activity was not exhibited only by irradiation with visible light, and no bactericidal action was achieved.

[Example 6] "Bactericidal effect due to sunlight"
Using the reaction product of the reducing organic substance and iron, it was verified whether sterilization of E. coli irradiated with sunlight was possible.

(1) "Sterilization test"
4 parts by weight of iron (III) chloride in terms of iron element (100 parts by weight in terms of dry weight) per 100 parts by weight (dry weight equivalent) of tea husk (tea leaf hot water extraction residue) or coffee cake (roasted coffee beans ground residue) FeCl ₃ ) was mixed, water twice the total amount of both was added, and heat treatment was performed at 98 ° C. for 1 hour to obtain a reaction product. The solid content obtained by filtration was designated as “tea leaf component / iron” (sample 6-1) or “coffee beans roasted product component / iron” (sample 6-2). In addition, titanium oxide (TiO ₂ : titanium oxide (IV) anatase type, particle size 100 to 300 nm, manufactured by WAKO) (Comparative 6-1) was prepared as a comparative sample.

The sample shown in Table 6 was added to and mixed with a suspension of E. coli (ATCC1124) (10 ⁶ cfu / mL) at a concentration of 5.5 ppm in terms of iron element (in terms of titanium element in the case of titanium oxide). Irradiance 763 W / m ² , UV (A + B) 3.28 mW / cm ² , photon density 1514 μmol / m ² / sec) was irradiated for 10 minutes. Then, it was applied to an Escherichia coli assay plate and the number of surviving E. coli was examined. As a control, only E. coli was applied in the same manner and the same experiment was performed. The results are shown in FIG. The presence or absence of bactericidal power was evaluated in two stages (“+”: bactericidal power, “−”: no bactericidal power), and are shown in Table 6.

As a result, Escherichia coli was killed by irradiating sunlight with the addition of tea leaf components and iron (solid content after filtration) or roasted coffee bean components and iron (solid content after filtration) as reaction products. (Samples 6-1 and 6-2). The bactericidal action was shown to be sufficiently effective even with the addition of an extremely low concentration of 5.5 ppm in terms of iron element. Moreover, it was shown that a sufficient effect can be obtained even when the irradiation time of sunlight is as short as 10 minutes.
On the other hand, when titanium oxide, which is a comparative sample, was added, E. coli survived in large quantities only by irradiating sunlight under the same conditions as Samples 2-1 and 2-2 (Comparative 6-1).

(2) `` Discussion ''
From this result, it was shown that the bactericidal action by extremely strong photocatalytic activity is exhibited by irradiating sunlight using the reaction product of the reducing organic substance and iron. Further, it was confirmed that a sufficient bactericidal effect was exhibited even when added at an extremely low concentration of 5.5 ppm and irradiated for 10 minutes.
On the other hand, when titanium oxide was used, photocatalytic activity was not sufficiently exhibited only by irradiating sunlight for a short time, indicating that the bactericidal action was insufficient.

[Example 7] “Bactericidal effect when irradiated with sunlight multiple times continuously”
Using the reaction product of the reducing organic substance and iron, it was verified whether Escherichia coli could be sterilized even when sunlight was continuously irradiated several times.

(1) `` Continuous sterilization test ''
30 mg of roasted coffee bean component prepared in Example 6 and iron (sample 6-1: solid content after filtration) was added to 300 mL of sterilized water, mixed, and sealed in a sealable PET bottle. 90 μL of a suspension of Escherichia coli (ATCC1124) (3.5 × 10 ⁸ cfu / mL) was added to the PET bottle and irradiated with sunlight for 10 minutes. 1 mL of bacterial solution after irradiation was collected.
After 1 hour, the same amount of the E. coli suspension was added to the PET bottle again, and a second solar irradiation was performed for 10 minutes, and 1 mL of the bacterial solution after irradiation was collected. Further, 1 hour later, the same amount of the E. coli suspension was added to the PET bottle again, and a third solar irradiation was performed for 10 minutes, and 1 mL of the bacterial solution after irradiation was collected.
Each collected bacterial solution was applied to an Escherichia coli assay plate, and the number of surviving E. coli was examined. As a control, only E. coli was applied in the same manner and the same experiment was performed. The results are shown in FIG. In addition, the presence or absence of bactericidal power was evaluated in two stages (“+”: with bactericidal power, “−”: without bactericidal power).

  As a result, the solution containing the roasted coffee beans component and iron, which is the reaction product, can be sterilized three times in succession by irradiating light again after sterilizing once with photocatalytic activity. It was shown. Moreover, since E. coli was completely killed in any of the samples after the first to third sterilizations, no decrease in the titer of photocatalytic activity due to continuous use was observed.

(2) `` Discussion ''
From this result, it was shown that the photocatalytic activity of the reaction product of the reducing organic substance and iron was not the activity lost by one photocatalytic reaction. That is, the reaction product was shown to be a substance that can be used stably and repeatedly for a long time as photocatalytic activity.
In addition, it was estimated that the said property is a property resulting from the said reaction product (The Fe2 ⁺ complex of the said reducing organic substance) being a stable structure.

  The photocatalyst of the present invention is expected to be widely used for sterilization and organic matter decomposition in a wide range of fields such as food, medicine, public health, agriculture, and environmental purification.

The present invention has been made based on these findings.
That is, the present invention according to [Claim 1 ] is an organic substance decomposing agent containing a photocatalyst ,
The photocatalyst is mixed with a reducing organic substance having an action of reducing trivalent iron to divalent iron and an iron feedstock at 40 ° C. to 100 ° C. for 10 seconds to 10 days in the presence of water. A photocatalyst comprising, as an active component, a reaction product containing the Fe ²⁺ complex of the obtained reducing organic substance ,
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The mixing is to mix the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of dry weight of the reducing organic substance, and
The present invention relates to an organic substance decomposing agent characterized by not using hydrogen peroxide.
Further, the present invention according to [Claim 2 ] is directed to a reducing organic substance having an action of reducing trivalent iron to divalent iron and an iron feedstock at 40 ° C to 100 ° C for 10 seconds to 10 days. in, mixed with water presence to obtain a photocatalyst by using a reaction product containing Fe ²⁺ complex of the reducing organic substance obtained as an active ingredient, which comprises using the photocatalyst as active ingredient A method for producing an organic substance decomposing agent comprising:
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The mixing is to mix the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of dry weight of the reducing organic substance, and
The present invention relates to a method for producing an organic substance decomposing agent characterized by not using hydrogen peroxide.
Further, the present invention according to [Claim 3 ] is directed to a reducing organic substance having an action of reducing trivalent iron to divalent iron, and an iron feedstock at 40 ° C to 100 ° C for 10 seconds to 10 days. In the presence of water, a photocatalyst is obtained by using the obtained reaction product containing the Fe ²⁺ complex of the reducing organic substance as an active component, the photocatalyst and the organic substance to be decomposed are brought into contact with each other, ultraviolet rays, An organic material decomposition method characterized by irradiating light having a wavelength belonging to visible light or infrared light ,
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The mixing is to mix the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of dry weight of the reducing organic substance, and
The present invention relates to a method for decomposing organic substances characterized by not using hydrogen peroxide.
Further, the present invention according to [Claim 4 ] relates to a method according to claim 3 , wherein light having a wavelength belonging to visible light or infrared light is irradiated.
The present invention according to [Claim 5 ] is a bactericidal agent containing a photocatalyst ,
The photocatalyst is mixed with a reducing organic substance having an action of reducing trivalent iron to divalent iron and an iron feedstock at 40 ° C. to 100 ° C. for 10 seconds to 10 days in the presence of water. A photocatalyst comprising, as an active component, a reaction product containing the Fe ²⁺ complex of the obtained reducing organic substance ,
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The mixing is to mix the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of dry weight of the reducing organic substance, and
The present invention relates to a disinfectant characterized by not using hydrogen peroxide.
Further, the present invention according to [Claim 6 ] is directed to a reducing organic substance having an action of reducing trivalent iron to divalent iron, and an iron feedstock at 40 ° C to 100 ° C for 10 seconds to 10 days. in, mixed with water presence to obtain a photocatalyst by using a reaction product containing Fe ²⁺ complex of the reducing organic substance obtained as an active ingredient, which comprises using the photocatalyst as active ingredient A method for producing a bactericide,
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The mixing is to mix the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of dry weight of the reducing organic substance, and
The present invention relates to a method for producing a disinfectant characterized by not using hydrogen peroxide.
Further, the present invention according to [Claim 7 ] is directed to a reducing organic substance having an action of reducing trivalent iron to divalent iron and an iron feedstock at 40 ° C to 100 ° C for 10 seconds to 10 days. In the presence of water, a photocatalyst is obtained by using the obtained reaction product containing the Fe ²⁺ complex of the reducing organic substance as an active component, the photocatalyst and the sterilization object are brought into contact with each other, ultraviolet rays, A sterilization method characterized by irradiating light having a wavelength belonging to visible light or infrared light ,
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The mixing is to mix the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of dry weight of the reducing organic substance, and
The present invention relates to a sterilization method characterized by not using hydrogen peroxide.
The present invention according to [Claim 8 ] relates to a method according to claim 7 , wherein the light having a wavelength belonging to visible light or infrared light is irradiated.

Claims (14)

A reducing organic substance having an action of reducing trivalent iron to divalent iron and an iron feedstock were mixed at 40 ° C. to 100 ° C. for 10 seconds to 10 days in the presence of water, and obtained. A photocatalyst comprising, as an active ingredient, a reaction product containing the Fe ²⁺ complex of the reducing organic substance,
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The iron feedstock is mixed so that the mixture contains 0.1 to 10 parts by weight in terms of the weight of iron element with respect to a dry weight of 100 parts by weight of the reducible organic substance or the feedstock of the reducible organic substance. Photocatalyst that is to be.   Said iron feedstock is iron (III) chloride, iron (III) sulfate, iron (III) citrate, iron (III) citrate ammonium, EDTA iron (III), iron (III) oxide, iron (III) nitrate The photocatalyst according to claim 1, wherein the photocatalyst is a feedstock of one or more trivalent irons selected from iron (III) hydroxide and iron (III) pyrophosphate.   The photocatalyst according to claim 1 or 2, wherein the reaction product is obtained by mixing the reducing organic material, the iron feedstock, and water having a weight twice the total weight thereof. A reducing organic substance having an action of reducing trivalent iron to divalent iron and an iron feedstock were mixed at 40 ° C. to 100 ° C. for 10 seconds to 10 days in the presence of water, and obtained. Using a reaction product containing the Fe ²⁺ complex of the reducing organic substance as an active ingredient, and
The reducing organic substance is ascorbic acid,
The iron feedstock is iron (II) chloride, iron nitrate (II), iron hydroxide (II), iron oxide (II), iron acetate (II), iron lactate (II), iron citrate (II) sodium , Iron (II) gluconate, iron carbonate (II), divalent iron feedstock selected from iron (II) fumarate; iron (III) chloride, iron (III) sulfate, iron (III) citrate, citric acid A feedstock of trivalent iron selected from iron (III) ammonium oxide, iron (III) EDTA, iron (III) oxide, iron (III) nitrate, iron (III) hydroxide, iron (III) pyrophosphate One or more
The photocatalyst characterized in that the mixing is performed by mixing the iron feedstock so as to contain 0.1 to 10 parts by weight in terms of the weight of iron element with respect to 100 parts by weight of the dry weight of the reducing organic substance. Manufacturing method.   Said iron feedstock is iron (III) chloride, iron (III) sulfate, iron (III) citrate, iron (III) citrate ammonium, EDTA iron (III), iron (III) oxide, iron (III) nitrate The method according to claim 4, wherein the feedstock is one or more trivalent irons selected from iron (III) hydroxide and iron (III) pyrophosphate.   The method according to claim 4 or 5, wherein the reaction product is obtained by mixing the reducing organic material, the iron feedstock, and water having a weight twice the total weight thereof.   An organic substance decomposing agent comprising the photocatalyst according to any one of claims 1 to 3, wherein hydrogen peroxide is not used.   A method for producing an organic substance decomposing agent, comprising: obtaining a photocatalyst by the method according to any one of claims 4 to 6, using the photocatalyst as an active ingredient, and not using hydrogen peroxide.   A photocatalyst is obtained by the method according to any one of claims 4 to 6, the photocatalyst is brought into contact with an organic substance to be decomposed, irradiated with light having a wavelength belonging to ultraviolet light, visible light, or infrared light, and hydrogen peroxide. Organic substance decomposition method characterized by not using.   The method of Claim 9 which irradiates the light of the wavelength which belongs to visible light or infrared rays.   A disinfectant comprising the photocatalyst according to any one of claims 1 to 3, wherein hydrogen peroxide is not used.   A photocatalyst is obtained by the method according to any one of claims 4 to 6, the photocatalyst is used as an active ingredient, and hydrogen peroxide is not used.   A photocatalyst is obtained by the method according to any one of claims 4 to 6, the photocatalyst and an object to be sterilized are brought into contact with each other, irradiated with light having a wavelength belonging to ultraviolet light, visible light, or infrared light, and hydrogen peroxide. A sterilization method, characterized by not using.   The method of Claim 13 which irradiates the light of the wavelength which belongs to visible light or infrared rays.