JP6592472B2 - Disinfectant manufacturing method and photocatalytic composite material manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a disinfectant composed of a porous carbon material composite, a method for producing a photocatalyst composite material, a method for producing an adsorbent, and a method for producing a purification agent.

For example, functional materials with physical and physicochemical properties such as light absorption properties and adsorption ability for specific substances are added to porous materials, which are both interesting because they have both high specific surface area and physical properties. It is. Here, examples of the porous material include alumina, carbon, and silica. In addition, as a functional material having light absorption characteristics and adsorption ability for a specific substance, metals [Fe, Co, Ni, Au, Ag, Pt, Cu], alloys, oxides [Fe ₂ O ₃ , Fe ₃ O ₄ , Examples include fine particles and thin films such as TiO ₂ , ZnO ₂ ], compounds [CdS, CdSe, ZnS, CaCO ₃ , Ca (CH ₃ COO) ₂ ], or polymer films and monomolecular films containing many amino groups. it can.

  Such a functional material is expected to be applied to, for example, an adsorbent, a catalyst, an electrode of an energy device, and a sensing device (see, for example, JP-A-2006-167694). In addition, most unused parts of plants such as vegetables and cereals are discarded, but effective use of these unused parts is strongly demanded for the preservation and improvement of the global environment. An example of effective use of the unused part is carbonization. An example of using a carbon material produced by carbonizing such a plant-derived material as a dye adsorbent is known from, for example, Dyes and Pigments, Vol 66, 2005, pp 123-128. . Moreover, the manufacturing method of the carbide | carbonized_material which has the deodorizing capability by a plant material, an ion exchange capability, and a catalyst capability is known from Unexamined-Japanese-Patent No. 2000-2111910.

  Furthermore, as a use of such a functional material, a disinfectant can be mentioned, for example. The odor is generated when components such as fatty acid and glycerin contained in sweat are decomposed and altered by bacteria to produce lower fatty acids and the like. To date, silver-containing zeolites are commercially available. In this silver-containing zeolite, the silver ions supported on the zeolite cut off the source of odor by contacting the resident bacteria (Staphylococcus epidermidis, diphtheroid) that act on sweat and inhibiting the action of the bacteria. It is.

JP 2006-167694 A JP2000-2111910A

Dyes and Pigments, Vol 66, 2005, pp 123-128

In order to prevent the foul odor, it is important to deodorize the generated odor and sterilize bacteria that decompose and alter sweat components. However, the silver-containing zeolite described above is effective in deodorizing and sterilizing bacteria. It is difficult to say that it has sufficient performance. In addition, a functional material having a light absorption characteristic in which TiO ₂ is supported on a porous material has a problem that it hardly absorbs light in the visible light region and does not show a high decomposition reaction. Alternatively, the porous carbon material has a problem that it hardly adsorbs metal in some cases.

  Accordingly, an object of the present invention is to provide a disinfectant composed of a porous carbon material and having an excellent deodorizing and disinfecting effect, a photocatalytic composite material that absorbs light in the visible light region and exhibits a decomposition reaction, and adsorbs a metal. It is to provide an adsorbent and a purifying agent.

The fungicide of the present invention for achieving the above object is:
(A) a porous carbon material, and
(B) a silver member (silver material) attached to the porous carbon material;
Consisting of
The value of specific surface area by nitrogen BET method is 10 m ² / gram or more, and the volume of pores by BJH method and MP method is 0.1 cm ³ / gram or more.

The photocatalyst composite material of the present invention for achieving the above object is
(A) a porous carbon material, and
(B) a photocatalytic material attached to the porous carbon material,
Consisting of
The value of specific surface area by nitrogen BET method is 10 m ² / gram or more, and the volume of pores by BJH method and MP method is 0.1 cm ³ / gram or more,
The photocatalytic material is made of titanium oxide doped with a cation or an anion.

In order to achieve the above object, the adsorbent or the purifier of the present invention is:
(A) a porous carbon material, and
(B) an organic material attached to the porous carbon material,
Consisting of
The value of specific surface area by nitrogen BET method is 10 m ² / gram or more, and the volume of pores by BJH method and MP method is 0.1 cm ³ / gram or more,
Organic materials adsorb metals.

  Hereinafter, the bactericidal agent, photocatalyst composite material, adsorbent and purification agent of the present invention may be collectively referred to as “the porous carbon material composite of the present invention”. Further, the silver member, photocatalytic material, and organic material to be attached to the porous carbon material may be collectively referred to as “functional material” hereinafter. Further, the porous carbon material constituting the bactericide, photocatalyst composite material, adsorbent and purification agent of the present invention may be hereinafter referred to as “porous carbon material in the present invention”.

The disinfectant, photocatalyst composite material, adsorbent and purification agent of the present invention have a specific surface area value of 10 m ² / gram or more by the nitrogen BET method and a pore volume of 0.1 cm ³ / gram or more by the BJH method and MP method. And such a requirement can be achieved by a porous carbon material. Then, by attaching a functional material to the porous carbon material, the amount of the functional material attached per unit weight of the porous carbon material can be increased, and the porous carbon material having high characteristics and high functionality. A complex can be obtained.

  And in the disinfectant of the present invention, since the silver member is adhered to the porous carbon material, it is possible to obtain high adsorption characteristics and disinfecting effect, and the deodorant product, deodorant, antibacterial agent, storage It can also be used as an agent. In the photocatalyst composite material of the present invention, since the photocatalyst material is composed of titanium oxide doped with a cation or an anion, it becomes possible to effectively absorb visible light, and the photocatalyst composite material of the present invention Is provided with charge separation, visible light absorption, ultraviolet absorption, and catalytic properties. The photocatalytic effect enables application as a harmful substance decomposing agent and harmful substance removing agent that can be used semipermanently. Furthermore, in the adsorbent and the purifying agent of the present invention, since an organic material is attached (supported, adsorbed, bonded) to the porous carbon material, effective adsorption of metal (metal atom or metal ion) can be achieved. It becomes possible.

  Moreover, the porous carbon material of the present invention has a pore volume defined, and in addition to the micro-region (<2 nm) pores of the conventional activated carbon, the meso region (2 to 50 nm) that cannot be realized with the conventional activated carbon. Have pores. And in the disinfectant of this invention, by such pore size, it shows high adsorption ability with respect to an odor-causing molecule, and in addition to this, macropores (> The growth of the bacteria can also be suppressed by adsorbing and dispersing the bacteria by (50 nm). Moreover, in the photocatalyst composite material of the present invention, the photocatalyst material can be extremely effectively attached to the porous carbon material by such a pore size, and decomposition due to the photocatalytic action can be effectively generated. it can. Furthermore, in the photocatalyst composite material, adsorbent, and purification agent of the present invention as an environmental purification material, it is considered that such a pore size effectively acts on the adsorption of harmful substances. Materials and organic materials can be adhered to the porous carbon material very effectively, and the decomposition and detoxification of harmful substances can be effectively caused. Moreover, diffusion of harmful substances inside the porous carbon material is promoted, decomposition can be caused more effectively, and water purification and air purification can be performed extremely effectively.

1 is an electron microscopic image of the fungicides of Example 1-A and Example 1-B and the sample of Comparative Example 1. FIG. (A), (B), and (C) of FIG. 2 show the fungicides of Example 1-A and Example 1-B and the X obtained by the powder X-ray diffraction method of the sample of Comparative Example 1. It is a chart of a line diffraction result, (D) of Drawing 2 is standard data of Ag in X-ray diffraction analysis. (A) and (B) of FIG. 3 are the microbicidal distribution and micropore fine distribution of the fungicides of Example 1-A and Example 1-B and the sample of Comparative Example 1, respectively. It is a graph showing pore distribution. FIG. 4 is a graph showing the measurement results of the pore size distribution obtained by the delocalized density functional method in Example 1-A, Example 1-B, and Comparative Example 1. FIG. 5 is a diagram conceptually illustrating a state in which the photocatalytic material absorbs light energy in the photocatalytic composite material of Example 2. FIG. 6 is a graph showing the light absorption characteristics of TiO ₂ . FIG. 7 is a graph showing the measurement results of pore (mesopore) distribution in the samples of Example 2-A and Example 2-B. FIG. 8 is a graph showing the measurement results of the pore size distribution obtained by the delocalized density functional method in Example 2-A and Example 2-B. FIG. 9 is a graph showing a state in which the photocatalytic composite material of Example 2-A and the sample of Comparative Example 2 decompose the aqueous tannic acid solution over time. FIG. 10 is a graph showing a state in which the photocatalyst composite material of Example 2-B and the sample of Comparative Example 2 decompose the aqueous methyl orange solution over time. FIG. 11A is a graph showing the results of a microcystin decomposition test based on the sample of Example 2-B and commercially available porous carbon, and FIG. 11B is the graph of Example 2-B. It is a conceptual diagram explaining decomposition | disassembly of the microcystin in a sample. FIG. 12 is a diagram schematically illustrating a state in which polyethyleneimine is attached to the porous carbon material as an organic material in the adsorbent and the purifying agent of Example 3. FIG. 13 is a diagram schematically showing a state where the ion exchange capacity can be increased by performing the treatment with FeCl ₃ .6H ₂ O in the adsorbent and the purifying agent of Example 3. FIG. 14 is a graph showing a state where the adsorbent and the purifying agent of Example 3 and the activated carbon of Comparative Example 3 adsorb potassium chromate. FIG. 15 is a diagram schematically showing a state where the adsorbent and the purifying agent of Example 3 adsorb chromate ions. FIG. 16 is a graph showing the measurement results of the pore diameter distribution obtained by the delocalized density functional method in Example 3 and Comparative Example 3.

Hereinafter, the present invention will be described based on examples with reference to the drawings. However, the present invention is not limited to the examples, and various numerical values and materials in the examples are examples. The description will be given in the following order.
1. 1. General description of the bactericide, photocatalyst composite material, adsorbent and purification agent of the present invention Example 1 (Fungicide of the present invention)
3. Example 2 (photocatalyst composite material of the present invention)
4). Example 3 (adsorbent and cleaning agent of the present invention), others

[Explanation about the bactericide, photocatalyst composite material, adsorbent and purification agent of the present invention in general]
In the disinfectant of the present invention, the silver member (silver material) is composed of ions containing silver ions; particles containing silver, silver alloy or silver ions; or a thin film containing silver, silver alloy or silver ions. Can do. Here, as silver alloy, silver and ruthenium alloy, silver and rhodium alloy, silver and palladium alloy, silver and gold alloy, silver and platinum alloy, silver and cobalt alloy, silver and nickel alloy, silver An alloy of copper and copper can be exemplified, and examples of silver ions include a form of silver nitrate, a form of silver chloride, and a form of silver sulfate. Examples of the method for attaching the silver member to the porous carbon material include impregnation in an aqueous silver salt solution, and further, a method of reducing precipitation of silver with a reducing agent.

  In the photocatalyst composite material of the present invention, the photocatalyst material can be configured to absorb energy of light having a wavelength of 200 nm to 600 nm. The photocatalyst material is composed of titanium oxide doped with a cation (cation) or anion (anion). Here, specific examples of the cation include chromium ion, iron ion, silver ion, platinum ion, copper ion, tungsten. Ions, cobalt ions, and nickel ions can be exemplified, and specific examples of anions include nitrogen ions, carbon ions, and sulfur ions. As a method of doping cations or anions into titanium oxide, a method of crystal growth in a state where a material containing cations or anions and a raw material of titanium oxide are mixed, a gaseous material containing cations or anions and a gaseous raw material of titanium oxide Examples include a method of growing a crystal by using, and a method of supporting a cation or an anion on the surface after titanium oxide synthesis. Examples of the form of adhesion of titanium oxide to the porous carbon material include adhesion in the form of fine particles and adhesion in the state of a thin film. Note that zinc oxide (ZnO) can be used instead of titanium oxide.

  A purification agent can be obtained from the photocatalyst composite material of the present invention. In decomposing and removing harmful substances, the photocatalyst composite material of the present invention may be irradiated with visible light. Examples of harmful substances include harmful substances present in water or air. Specific examples include microcystins, various viruses, and allergen-causing substances. This purifier functions as a water purifier or an air purifier, and can be applied, for example, as a filter of an air purifier. As a usage form of the photocatalyst composite material (or purifier) of the present invention, it is used in a sheet form, in a state where it is packed in a column or a cartridge, or shaped into a desired shape using a binder (binder) The use in the state and the use in a powder form can be illustrated. Moreover, when using as a purification | cleaning agent or adsorbent disperse | distributed in the solution, the surface can be used after hydrophilic treatment or hydrophobic treatment.

In the adsorbent or the purifying agent of the present invention, the organic material is at least one selected from the group consisting of phenol group, carboxyl group, amino group, thiol group, ketone group, phosphate group, alkyl group, ether group and thionyl group. An organic material having various types of groups, specifically, for example, polyethyleneimine can be mentioned. Also, as metals (including metal atoms and metal ions), chromium, mercury, arsenic, lead, cadmium, tin, copper, zinc, lithium, beryllium, boron, titanium, vanadium, manganese, cobalt, nickel, gallium, germanium, Selenium, rubidium, strontium, zirconium, niobium, molybdenum, palladium, indium, antimony, tellurium, cesium, barium, hafnium, tantalum, tungsten, rhenium, platinum, thallium, bismuth, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, Mention may be made of promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. Examples of methods for attaching an organic material to a porous carbon material (including concepts such as support, adsorption, bonding, and surface modification) include, for example, a C—C bond and a C—N bond between a porous carbon material and an organic molecule. Examples thereof include a method of forming a CO bond, a method of coating SiO ₂ and bonding by silane coupling, and a method of mixing and stirring. Examples of the form of adhesion of the organic material to the porous carbon material include layered adhesion and island-shaped adhesion. In addition, the adsorbent and the purifying agent of the present invention can have various forms of metals (metal atoms, metal ions) by, for example, enhancing anion exchange capacity and cation exchange capacity, or replacing metal coordination. Can be adsorbed. Further, it is possible to improve the dispersibility in a solvent or a solvent.

  Here, the adsorbent or the purification agent of the present invention functions as, for example, a water purification agent, and can be applied as, for example, a filter. And as its usage form, it is used in the form of a sheet, in a state where it is packed in a column or cartridge, in a state of being shaped into a desired shape using a binder (binder), etc. The use of can be illustrated. It is also possible to absorb metals contained in gases such as smoke.

  When the raw material of the porous carbon material in the present invention is a plant-derived material containing silicon (Si), the material is not specifically limited, but the porous carbon material contains silicon (Si). A plant-derived material having a rate of 5% by weight or more is used as a raw material, and the content of silicon (Si) is 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less.

  The porous carbon material composite of the present invention is obtained by, for example, carbonizing a plant-derived material at 400 ° C. to 1400 ° C. and then treating it with an acid or alkali to obtain a porous carbon material. It can be produced by attaching a functional material to the porous carbon material. In such a method for producing a porous carbon material in the present invention (hereinafter sometimes simply referred to as “a method for producing a porous carbon material”), the plant-derived material is carbonized at 400 ° C. to 1400 ° C. A material obtained by converting into a material before being treated with an acid or alkali is called a “porous carbon material precursor” or a “carbonaceous material”.

  In the method for producing a porous carbon material, after the treatment with acid or alkali, a step of applying an activation treatment can be included before the functional material is attached to the porous carbon material, and after the activation treatment is carried out. Treatment with acid or alkali may be performed. Further, in the method for producing a porous carbon material including such a preferred form, depending on the plant-derived material to be used, before the carbonization of the plant-derived material, the temperature for carbonization is determined. Alternatively, the plant-derived material may be subjected to a heat treatment (preliminary carbonization treatment) at a low temperature (for example, 400 ° C. to 700 ° C.) in a state where oxygen is blocked. As a result, the tar component that will be generated in the carbonization process can be extracted. As a result, the tar component that will be generated in the carbonization process can be reduced or eliminated. The state in which oxygen is shut off is, for example, an inert gas atmosphere such as nitrogen gas or argon gas, or a vacuum atmosphere, or a plant-derived material is in a kind of steamed state. Can be achieved. Moreover, in the method for producing a porous carbon material, depending on the plant-derived material to be used, in order to reduce mineral components and moisture contained in the plant-derived material, and in the process of carbonization. In order to prevent the generation of the off-flavor, the plant-derived material may be immersed in alcohol (for example, methyl alcohol, ethyl alcohol, isopropyl alcohol). In addition, in the manufacturing method of a porous carbon material, you may perform a preliminary carbonization process after that. As a material that is preferably heat-treated in an inert gas, for example, a plant that generates a large amount of wood vinegar liquid (tar or light oil) can be mentioned. In addition, examples of materials that are preferably pretreated with alcohol include seaweeds that contain a large amount of iodine and various minerals.

  In the method for producing a porous carbon material, a plant-derived material is carbonized at 400 ° C. to 1400 ° C. Here, carbonization is generally an organic substance (porous carbon in the present invention). In the case of materials, it means that a plant-derived material) is heat-treated and converted into a carbonaceous substance (for example, see JIS M0104-1984). The atmosphere for carbonization can include an atmosphere in which oxygen is shut off. Specifically, a vacuum atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas, and a plant-derived material as a kind of steamed state. The atmosphere to do can be mentioned. The rate of temperature rise until reaching the carbonization temperature is not limited, but in such an atmosphere, 1 ° C / min or more, preferably 3 ° C / min or more, more preferably 5 ° C / min or more. be able to. The upper limit of the carbonization time can be 10 hours, preferably 7 hours, more preferably 5 hours, but is not limited thereto. The lower limit of the carbonization time may be a time during which the plant-derived material is reliably carbonized. Moreover, the plant-derived material may be pulverized as desired to obtain a desired particle size, or may be classified. Plant-derived materials may be washed in advance. Alternatively, the obtained porous carbon material precursor or porous carbon material may be pulverized as desired to obtain a desired particle size or classified. Alternatively, the porous carbon material after the activation treatment may be pulverized as desired to obtain a desired particle size or may be classified. Further, the porous carbon material finally obtained may be sterilized. There is no restriction | limiting in the form, structure, and structure of the furnace used for carbonization, It can also be set as a continuous furnace and can also be set as a batch furnace (batch furnace).

  In the method for producing a porous carbon material, as described above, when the activation treatment is performed, micropores (described later) having a pore diameter smaller than 2 nm can be increased. Examples of the activation treatment method include a gas activation method and a chemical activation method. Here, the gas activation method uses oxygen, water vapor, carbon dioxide gas, air or the like as an activator, and in such a gas atmosphere, at 700 ° C. to 1400 ° C., preferably at 700 ° C. to 1000 ° C. More preferably, by heating the porous carbon material at 800 ° C. to 1000 ° C. for several tens of minutes to several hours, the microstructure is developed by the volatile components and carbon molecules in the porous carbon material. is there. More specifically, the heating temperature may be appropriately selected based on the type of plant-derived material, the type and concentration of gas, and the like. The chemical activation method is activated with zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, sulfuric acid, etc. instead of oxygen and water vapor used in the gas activation method, washed with hydrochloric acid, alkaline In this method, the pH is adjusted with an aqueous solution and dried.

In the method for producing a porous carbon material, the silicon component in the plant-derived material after carbonization is removed by treatment with acid or alkali. Here, examples of the silicon component include silicon oxides such as silicon dioxide, silicon oxide, and silicon oxide salts. Thus, by removing the silicon component in the plant-derived material after carbonization, a porous carbon material having a high specific surface area can be obtained, and the functional material adhesion amount per unit weight of the porous carbon material Can be increased. In some cases, the silicon component in the plant-derived material after carbonization may be removed based on a dry etching method. That is, in a preferred form of the porous carbon material in the present invention, a plant-derived material containing silicon (Si) is used as a raw material, but when converted into a porous carbon material precursor or a carbonaceous material, By carbonizing a plant-derived material at a high temperature (for example, 400 ° C. to 1400 ° C.), silicon contained in the plant-derived material does not become silicon carbide (SiC), but silicon dioxide (SiC). It exists as a silicon component (silicon oxide) such as SiO _x ), silicon oxide, or silicon oxide salt. Therefore, by treating with an acid or alkali (base) in the next step, silicon components (silicon oxide) such as silicon dioxide, silicon oxide, and silicon oxide salt are removed, resulting in a large specific surface area by nitrogen BET method. A value can be obtained. Moreover, in a preferred form of the porous carbon material in the present invention, it is an environmentally compatible material derived from a natural product, and its microstructure is a silicon component (silicon oxide) previously contained in a raw material that is a plant-derived material. ) Is removed by treatment with acid or alkali. Therefore, the pore arrangement maintains the bioregularity of the plant.

  As described above, the porous carbon material can be made from a plant-derived material. Here, as plant-derived materials, rice husks and straws such as rice (rice), barley, wheat, rye, straw, millet, coconut beans, tea leaves (for example, leaves such as green tea and tea), Sugar cane (more specifically, sugar cane squeezed straw), corn (more specifically, corn core), fruit peel (eg, citrus or banana peel), or Examples include, but are not limited to, stem wakame, and other examples include vascular plants, fern plants, moss plants, algae, and seaweeds that are vegetated on land. In addition, these materials may be used independently as a raw material, and multiple types may be mixed and used. Further, the shape and form of the plant-derived material are not particularly limited, and may be, for example, rice husk or straw itself, or may be a dried product. Furthermore, what processed various processes, such as a fermentation process, a roasting process, an extraction process, can also be used in food-drinks processing, such as beer and western liquor. In particular, it is preferable to use straws and rice husks after processing such as threshing from the viewpoint of recycling industrial waste. These processed straws and rice husks can be easily obtained in large quantities from, for example, agricultural cooperatives, liquor manufacturers, food companies, and food processing companies.

  In the porous carbon material composite according to the present invention, although depending on the type, configuration, structure, and form of the functional material, as described above, as the form of adhesion of the functional material to the porous carbon material, porous carbon The surface of the material (including inside the pores) is attached as ions, attached as fine particles, attached in a thin film state, sea / island (the surface of the porous carbon material When it is regarded as “the sea”, it can be mentioned that the functional material is attached to the “island”. Adhesion refers to an adhesion phenomenon between different kinds of materials. As a general method for attaching the functional material to the porous carbon material, depending on the functional material, the surface of the porous carbon material is immersed by immersing the porous carbon material in a solution containing the functional material or its precursor. A method of depositing a functional material on a surface, a method of depositing a functional material on the surface of a porous carbon material by an electroless plating method (chemical plating method) or a chemical reduction reaction, a porous material in a solution containing a functional material precursor A method of precipitating a functional material on the surface of the porous carbon material by immersing the carbonaceous material and performing a heat treatment, immersing the porous carbon material in a solution containing a precursor of the functional material, and irradiating with ultrasonic waves A method of depositing a functional material on the surface of a porous carbon material by performing a treatment, and a porous carbon material by immersing the porous carbon material in a solution containing a precursor of the functional material and performing a sol-gel reaction Material surface The method of precipitating the functional material can be mentioned.

  The porous carbon material in the present invention includes magnesium (Mg), potassium (K), calcium (Ca), nonmetallic elements such as phosphorus (P) and sulfur (S), and metal elements such as transition elements. It may be. Magnesium (Mg) content of 0.01 wt% to 3 wt%, potassium (K) content of 0.01 wt% to 3 wt%, calcium (Ca) content of 0.05 wt% % To 3% by weight, phosphorus (P) content of 0.01% to 3% by weight, and sulfur (S) content of 0.01% to 3% by weight. In addition, although the content rate of these elements changes with uses of the porous carbon material composite_body | complex of this invention, the one where it is smaller is preferable from a viewpoint of the increase in the value of a specific surface area. It can be said that the porous carbon material may contain an element other than the above-described elements, and the range of the content of each of the above-described elements can be changed depending on the intended use of the porous carbon material composite of the present invention. Not too long.

  In the present invention, analysis of various elements can be performed by an energy dispersion method (EDS) using, for example, an energy dispersive X-ray analyzer (for example, JED-2200F manufactured by JEOL Ltd.). Here, the measurement conditions may be, for example, a scanning voltage of 15 kV and an irradiation current of 10 μA.

The porous carbon material composite of the present invention has many pores. The pores include “mesopores” having a pore diameter of 2 nm to 50 nm and “micropores” having a pore diameter smaller than 2 nm. Specifically, the mesopores include, for example, many pores having a pore diameter of 20 nm or less, and particularly many pores having a pore diameter of 10 nm or less. The micropores include, for example, many pores having a pore diameter of about 1.9 nm, pores of about 1.5 nm, and pores of about 0.8 nm to 1 nm. In the porous carbon material composite of the present invention is the pore volume by the BJH method and the MP method is 0.1 cm ³ / g or more, and more preferably 0.3 cm ³ / g or more. Alternatively, the pore volume by the BJH method is preferably 0.1 cm ³ / gram or more, more preferably 0.3 cm ³ / gram or more, and still more preferably 0.5 cm ³ / gram or more.

In the porous carbon material composite of the present invention, the specific surface area value by the nitrogen BET method (hereinafter sometimes simply referred to as “specific surface area value”) is preferable in order to obtain even more excellent functionality. Is 50 m ² / gram or more, more preferably 100 m ² / gram or more, and still more preferably 400 m ² / gram or more.

The nitrogen BET method is an adsorption isotherm measured by adsorbing and desorbing nitrogen as an adsorbed molecule on an adsorbent (here, a porous carbon material composite), and the measured data is represented by the formula (1). This is a method of analysis based on the equation, and based on this method, the specific surface area, pore volume, etc. can be calculated. Specifically, when calculating the value of the specific surface area by the nitrogen BET method, first, an adsorption isotherm is obtained by adsorbing and desorbing nitrogen as an adsorbed molecule on the adsorbent (porous carbon material composite). Then, [p / {V _a (p ₀ −p)}] is calculated from the obtained adsorption isotherm based on the formula (1) or the formula (1 ′) obtained by modifying the formula (1), and the equilibrium relative pressure is calculated. Plot against (p / p ₀ ). Then, this plot is regarded as a straight line, and based on the least square method, the slope s (= [(C-1) / (C · V _m )]) and the intercept i (= [1 / (C · V _m )]) Is calculated. Then, V _m and C are calculated from the obtained slope s and intercept i based on the equations (2-1) and (2-2). Furthermore, the specific surface area a _sBET is calculated from V _m based on the formula (3) (see BELSORP-mini and BELSORP analysis software manual, pages 62 to 66, manufactured by Bell Japan Co., Ltd.). The nitrogen BET method is a measurement method according to JIS R 1626-1996 “Measurement method of specific surface area of fine ceramic powder by gas adsorption BET method”.

_{V a = (V m · C} · p) / [(p 0 -p) {1+ (C-1) (p / p 0)}] (1)
[P / {V _a (p ₀ −p)}]
= [(C-1) / (C · V _m )] (p / p ₀ ) + [1 / (C · V _m )] (1 ′)
V _m = 1 / (s + i) (2-1)
C = (s / i) +1 (2-2)
_{a sBET = (V m · L} · σ) / 22414 (3)

However,
V _a : Adsorption amount V _m : Adsorption amount of monolayer p: Nitrogen equilibrium pressure p ₀ : Nitrogen saturated vapor pressure L: Avogadro number σ: Nitrogen adsorption cross section.

When the pore volume V _p is calculated by the nitrogen BET method, for example, the adsorption data of the obtained adsorption isotherm is linearly interpolated to obtain the adsorption amount V at the relative pressure set by the pore volume calculation relative pressure. The pore volume V _p can be calculated from this adsorption amount V based on the formula (4) (see BELSORP-mini and BELSORP analysis software manual, page 62 to page 65, manufactured by Bell Japan Co., Ltd.). Hereinafter, the pore volume based on the nitrogen BET method may be simply referred to as “pore volume”.

V _p = (V / 22414) × (M _g / ρ _g ) (4)

However,
V: Adsorption amount at relative pressure M _g : Nitrogen molecular weight ρ _g : Nitrogen density.

The pore diameter of the mesopores can be calculated as a pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the BJH method. The BJH method is widely used as a pore distribution analysis method. When performing pore distribution analysis based on the BJH method, first, a desorption isotherm is obtained by adsorbing and desorbing nitrogen as an adsorbed molecule on an adsorbent (porous carbon material composite). Then, based on the obtained desorption isotherm, the thickness of the adsorption layer when the adsorption molecules are attached and detached in stages from the state where the pores are filled with adsorption molecules (for example, nitrogen), and the pores generated at that time obtains an inner diameter (twice the core radius) of calculating the pore radius r _p based on equation (5) to calculate the pore volume based on the equation (6). Then, the pore radius and the pore volume variation rate relative to the pore diameter (2r _p) from the pore volume (dV _p / dr _p) pore distribution curve is obtained by plotting the (Nippon Bel Co. Ltd. BELSORP-mini And BELSORP analysis software manual, pages 85-88).

r _p = t + r _k (5)
V _pn = R _n · dV _n -R _n · dt _n · c · ΣA _pj (6)
However,
R _n = r _pn ² / (r _kn −1 + dt _n ) ² (7)

here,
r _p : pore radius r _k : core radius (inner diameter / 2) when the adsorption layer having a thickness t is adsorbed on the inner wall of the pore having the pore radius r _p at that pressure
V _pn : pore volume dV _n when the nth attachment / detachment of nitrogen occurs: change amount dt _{n at} that time: change in the thickness t _n of the adsorption layer when the nth attachment / detachment of nitrogen occurs Amount r _kn : Core radius c at that time c: Fixed value r _pn : Pore radius when the nth attachment / detachment of nitrogen occurs. ΣA _pj represents the integrated value of the area of the wall surfaces of the pores from j = 1 to j = n−1.

  The pore diameter of the micropores can be calculated as a pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the MP method. When performing pore distribution analysis by the MP method, first, an adsorption isotherm is obtained by adsorbing nitrogen to an adsorbent (porous carbon material composite). Then, this adsorption isotherm is converted into a pore volume with respect to the thickness t of the adsorption layer (t plotted). A pore distribution curve can be obtained based on the curvature of this plot (the amount of change in pore volume with respect to the amount of change in the thickness t of the adsorption layer) (BELSORP-mini and BELSORP analysis software manuals manufactured by Bell Japan Co., Ltd.). 72 to 73 and 82).

  JIS Z8831-2: 2010 “Pore diameter distribution and pore characteristics of powder (solid) —Part 2: Method for measuring mesopores and macropores by gas adsorption” and JIS Z8831-3: 2010 “Powder” Pore size distribution and pore properties of solid bodies (solid)-Part 3: Nonlocalized density functional theory method (NLDFT method, Non Localized Density Functional Theory method) In that case, software attached to an automatic specific surface area / pore distribution measuring device “BELSORP-MAX” manufactured by Bell Japan Co., Ltd. is used as analysis software. As a precondition, the model is assumed to be a cylinder shape and carbon black (CB) is assumed, the distribution function of the pore distribution parameter is “no-assumtion”, and the obtained distribution data is smoothed 10 times.

Here, when the fungicide of the present invention is defined based on the delocalized density functional theory, the fungicide of the present invention for achieving the above-described object is:
(A) a porous carbon material, and
(B) a silver member (silver material) attached to the porous carbon material;
Consists of.

Further, when the photocatalyst composite material of the present invention is defined based on the delocalized density functional method, the photocatalyst composite material of the present invention for achieving the above-described object is
(A) a porous carbon material, and
(B) a photocatalytic material attached to the porous carbon material,
Consisting of
The photocatalytic material is made of titanium oxide doped with a cation or an anion.

Furthermore, when the adsorbent or the purifying agent of the present invention is defined based on the delocalized density functional theory, the adsorbent or the purifying agent of the present invention for achieving the above object is
(A) a porous carbon material, and
(B) an organic material attached to the porous carbon material,
Consisting of
Organic materials adsorb metals.

And in the disinfectant of the present invention, the photocatalyst composite material of the present invention, the adsorbent or the purifier of the present invention, the value of the specific surface area by nitrogen BET method is 10 m ² / gram or more, the delocalized density functional The total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the method is 0.1 cm ³ / gram or more. Alternatively, the specific surface area value by nitrogen BET method is 10 m ² / gram or more, and the pore size distribution determined by the delocalized density functional method has at least one peak in the range of 3 nm to 20 nm, The ratio of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm is 0.2 or more of the total volume of all pores.

The porous carbon material precursor is treated with an acid or alkali. Specific treatment methods include, for example, a method of immersing the porous carbon material precursor in an acid or alkali aqueous solution, or a porous carbon material precursor and an acid. Or the method of making it react with an alkali by a gaseous phase can be mentioned. More specifically, when treating with an acid, examples of the acid include fluorine compounds exhibiting acidity such as hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, and sodium fluoride. When a fluorine compound is used, the amount of fluorine element may be four times the amount of silicon element in the silicon component contained in the porous carbon material precursor, and the concentration of the fluorine compound aqueous solution is preferably 10% by weight or more. When the silicon component (for example, silicon dioxide) contained in the porous carbon material precursor is removed by hydrofluoric acid, the silicon dioxide is mixed with hydrofluoric acid as shown in chemical formula (A) or chemical formula (B). It reacts and is removed as hexafluorosilicic acid (H ₂ SiF ₆ ) or silicon tetrafluoride (SiF ₄ ) to obtain a porous carbon material. Thereafter, washing and drying may be performed.

SiO ₂ + 6HF → H ₂ SiF ₆ + 2H ₂ O (A)
SiO ₂ + 4HF → SiF ₄ + 2H ₂ O (B)

Moreover, when processing with an alkali (base), sodium hydroxide can be mentioned as an alkali, for example. When an alkaline aqueous solution is used, the pH of the aqueous solution may be 11 or more. When the silicon component (for example, silicon dioxide) contained in the porous carbon material precursor is removed with the aqueous sodium hydroxide solution, the silicon dioxide is heated as shown in the chemical formula (C) by heating the aqueous sodium hydroxide solution. It reacts and is removed as sodium silicate (Na ₂ SiO ₃ ) to obtain a porous carbon material. In addition, when processing by reacting sodium hydroxide in the gas phase, the sodium hydroxide solid is heated to react as shown in the chemical formula (C) and is removed as sodium silicate (Na ₂ SiO ₃ ). A porous carbon material can be obtained. Thereafter, washing and drying may be performed.

SiO ₂ + 2NaOH → Na ₂ SiO ₃ + H ₂ O (C)

Alternatively, as the porous carbon material in the present invention, for example, a porous carbon material in which pores disclosed in JP 2010-106007 have a three-dimensional regularity (so-called porous carbon material having an inverse opal structure). More specifically, it has three-dimensionally arranged spherical holes having an average diameter of 1 × 10 ⁻⁹ m to 1 × 10 ⁻⁵ m, and has a surface area of 3 × 10 ² m ² / gram or more. Porous carbon material, preferably macroscopically arranged with pores in an arrangement corresponding to a crystal structure, or macroscopically arranged corresponding to (111) plane orientation in a face-centered cubic structure In the state, a porous carbon material having pores arranged on the surface thereof can also be used.

Example 1 relates to the fungicide of the present invention. The fungicide of Example 1 is
(A) Porous carbon material, specifically, a porous carbon material made from a plant-derived material containing silicon, more specifically, a plant-derived material having a silicon content of 5% by weight or more. A porous carbon material having a silicon content of 1% by weight or less, and
(B) a silver member (silver material) attached to the porous carbon material;
Consisting of
The value of specific surface area by nitrogen BET method is 10 m ² / gram or more, and the volume of pores by BJH method and MP method is 0.1 cm ³ / gram or more.

Alternatively, the fungicide of Example 1 is
(A) a porous carbon material, and
(B) a silver member (silver material) attached to the porous carbon material;
Consisting of
The value of specific surface area by nitrogen BET method is 10 m ² / g or more, and the total volume of pores with diameters of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by delocalized density functional method is 0 .1 cm ³ / gram or more. Alternatively, the specific surface area value by nitrogen BET method is 10 m ² / gram or more, and the pore size distribution determined by the delocalized density functional method has at least one peak in the range of 3 nm to 20 nm, The ratio of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm is 0.2 or more of the total volume of all pores.

  In Example 1, rice (rice) rice husk was used as the plant-derived material that is the raw material of the porous carbon material. And the porous carbon material in Example 1 is obtained by carbonizing the chaff as a raw material, converting it into a carbonaceous substance (porous carbon material precursor), and then performing an acid treatment. And after obtaining a porous carbon material, a porous carbon material complex (bactericidal agent) can be obtained by attaching (supporting, adsorbing, bonding) a functional material (silver member) to the porous carbon material. . Specifically, in Example 1, the silver member is made of silver (metallic silver) and adheres to the surface (including the inside of the pores) of the porous carbon material in the form and shape of fine particles. . Hereinafter, the manufacturing method of the disinfectant of Example 1 will be described.

[Step-100A]
In the production of the fungicide of Example 1, first, a plant-derived material was carbonized at 400 ° C. to 1400 ° C. and then treated with an acid or an alkali to obtain a porous carbon material. That is, first, heat treatment (preliminary carbonization treatment) is performed on the rice husk in an inert gas. Specifically, the rice husk was carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain a carbide. In addition, by performing such a process, the tar component which will be produced | generated at the time of the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was placed in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./minute in a nitrogen stream (5 liters / minute). And it carbonized at 800 degreeC for 1 hour, after converting into a carbonaceous substance (porous carbon material precursor), it cooled to room temperature. In addition, nitrogen gas was continued to flow during carbonization and cooling. Next, this porous carbon material precursor was subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed with water and ethyl alcohol until pH 7 was reached. In addition, the porous carbon material obtained in this way is called "porous carbon material-A" for convenience. Next, after drying at 120 ° C., the porous carbon material could be obtained by performing activation treatment by heating in a steam stream at 900 ° C. for 3 hours. In addition, the porous carbon material obtained in this way is called "porous carbon material-B" for convenience.

[Step-110A]
Next, a silver member was adhered (supported, adsorbed, bonded) to the obtained porous carbon material-B. Hereinafter, the process of attaching the functional material to the porous carbon material may be referred to as “compositing process”. Specifically, 0.43 grams of porous carbon material-B was added to 182 milliliters of distilled water and stirred for 30 minutes. Then, 8 ml of a 5 mmol / liter silver nitrate aqueous solution was added thereto, and further stirred for 1 hour, and then 10 ml of 40 mmol / liter sodium borohydride was added and stirred overnight. The obtained powder was filtered through a filter, washed with distilled water, and dried at 120 ° C. to obtain a bactericide of Example 1-A.

[Step-110B]
Alternatively, a silver member was adhered (supported, adsorbed, bonded) to the obtained porous carbon material-B by a method different from that described above. Specifically, 0.215 grams of porous carbon material-B was added to 15 milliliters of a 1.33 millimol / liter aqueous silver nitrate solution and stirred for 30 minutes. Then, after heating to 100 ° C. and confirming boiling, 5 ml of 20 mmol / liter trisodium citrate aqueous solution was dropped and refluxed for 15 minutes. Then, the obtained powder was filtered through a filter, washed with distilled water, and dried at 120 ° C. to obtain a bactericide of Example 1-B.

  Further, the porous carbon material-B was subjected to various tests as Comparative Example 1.

  Table 1 below shows the results of elemental analysis of Example 1-A, Example 1-B and Comparative Example 1 using an energy dispersive X-ray analyzer based on the energy dispersal method.

[Table 1]

  From Table 1, in the fungicides of Example 1-A and Example 1-B, the silver deposition ratio of [Step-110A] or [Step-110B] is increased because the composition ratio of silver is increased. Thus, it is assumed that the silver member was attached (supported, adsorbed, bonded) to the porous carbon material.

  FIG. 1 shows electron microscope images of the fungicide of Example 1-A, the fungicide of Example 1-B, and the sample of Comparative Example 1. From these electron microscope images, Example 1-A and Example 1 In the bactericidal agent of Example 1-B, it was confirmed that fine particles having a particle diameter of about several tens of nm were precipitated.

  Furthermore, the product was identified and the particle size was estimated by X-ray diffraction analysis (see (A), (B), (C) and (D) of FIG. 2). Here, an X-ray diffractometer (RINT-TTRII) manufactured by Rigaku Corporation was used, and the X-ray source was Cu-Kα ray. The wavelength is 0.15405 nm. The applied voltage was 50 kilovolts and the scanning step was 0.04 °. From the fungicides of Example 1-A and Example 1-B, diffraction lines found in standard data of Ag could be confirmed, suggesting that a complex of carbon and Ag was formed. From the Scherrer equation, it was found that the grain size of the precipitated silver was about 40 nm in both Example 1-A and Example 1-B.

A nitrogen adsorption / desorption test was performed using BELSORP-mini (manufactured by Nippon Bell Co., Ltd.) as a measuring instrument for determining the value of the specific surface area and the pore volume. As measurement conditions, the measurement equilibrium relative pressure (p / p ₀ ) was set to 0.01 to 0.99. And based on BELSORP analysis software, the value of the specific surface area and the pore volume were calculated. In addition, the pore size distribution of mesopores and micropores was calculated based on the BJH method and the MP method using BELSORP analysis software after performing a nitrogen adsorption / desorption test using the above-described measuring instrument. In the examples and comparative examples described later, the specific surface area value, pore volume, mesopore size, and pore size distribution of micropores were measured in the same manner. Further, in the analysis based on the delocalized density functional method (NLDFT method), analysis software attached to an automatic specific surface area / pore distribution measuring apparatus “BELSORP-MAX” manufactured by Bell Japan Ltd. was used. In the measurement, the sample was dried at 200 ° C. for 3 hours as a pretreatment.

About the sample of Example 1-A and Example 1-B, and the sample of the comparative example 1 (porous carbon material-B), when the value of specific surface area and pore volume were measured, the result shown in Table 2 was obtained. It was. Further, when the distribution of the pore diameters of the mesopores and the micropores was measured, the results shown in FIGS. 3A and 3B were obtained. In Table 1, “specific surface area” and “total pore volume” indicate specific surface area (unit: m ² / gram) and total pore volume by nitrogen BET method, and “BJH (T)” and “MP “(T)” refers to the value of cumulative pore volume (unit: m ² / gram) by the BJH method and the MP method. Furthermore, FIG. 4 shows the measurement results of the pore diameter distribution obtained by the delocalized density functional method of Example 1-A, Example 1-B, and Comparative Example 1. The ratio of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm with respect to the total volume was as follows. Since Comparative Example 1 is a porous carbon material-B, there is no significant difference in the proportion of the total volume of pores in Example 1-A and Example 1-B. .
Example 1-A: 0.435 (total volume of all pores: 1.381 cm ³ / gram)
Example 1-B: 0.538 (total volume of all pores: 1.293 cm ³ / gram)
Comparative Example 1: 0.435 (total pore volume: 1.533 cm ³ / gram)

[Table 2]
Specific surface area Total pore volume BJH (T) MP (T)
Example 1-A 1169 1.04 0.64 0.50
Example 1-B 1217 1.08 0.66 0.52
Comparative Example 1 (porous carbon material-B) 1300 1.16 0.76 0.48
Porous carbon material-A 566 0.60 0.47 0.17

  In the fungicides of Example 1-A and Example 1-B that were subjected to the composite treatment, the value of the specific surface area and the total pore volume were higher than those of the sample of Comparative Example 1 that was not subjected to the composite treatment. small. This result is due to the fact that the pores of the porous carbon material are blocked by the adhesion (precipitation) of silver particles or the weight is increased by the adhesion (precipitation) of silver particles by performing the composite treatment. It is thought to do.

  From the pore distribution curve of FIG. 3, a decrease in the pore volume is recognized as a whole. In particular, in the mesopore region shown in FIG. In A and Example 1-B, a decrease in pore volume was remarkably confirmed. This is considered due to the precipitation of the functional material.

  Further, in the porous carbon material composites of Example 1-A and Example 1-B, the silicon (Si) content was remarkably reduced, so that the porous carbon material precursor was treated with an acid. Thus, it was suggested that silicon components such as silicon dioxide contained were removed and contributed to an increase in the specific surface area. Furthermore, it was confirmed that the mesopores and micropores increased by the treatment with acid. The same applies to the embodiments described later. Similar results were obtained with a porous carbon material obtained by treatment with an alkali (base) such as an aqueous sodium hydroxide solution instead of an aqueous hydrofluoric acid solution.

In the disinfectant of Example 1, the value of the specific surface area by nitrogen BET method is 10 m ² / gram or more, the content of porous carbon material, specifically silicon is 1% by weight or less, BJH method And a porous carbon material having a pore volume of 0.1 cm ³ / gram or more by the MP method, and by attaching the silver material to the porous carbon material, adhesion of the silver material per unit weight of the porous carbon material The amount could be increased and high deodorizing ability and bactericidal effect could be obtained. Here, the disinfectant of Example 1 can be used as a deodorant product, a deodorant, an antibacterial agent, and a preservative.

Example 2 relates to the photocatalyst composite material of the present invention. The photocatalyst composite material of Example 2 (or a purification agent based on this photocatalyst composite material)
(A) Porous carbon material, specifically, a porous carbon material made from a plant-derived material containing silicon, more specifically, a plant-derived material having a silicon content of 5% by weight or more. A porous carbon material having a silicon content of 1% by weight or less, and
(B) a photocatalytic material attached to the porous carbon material,
Consisting of
The value of specific surface area by nitrogen BET method is 10 m ² / gram or more, and the volume of pores by BJH method and MP method is 0.1 cm ³ / gram or more,
The photocatalytic material is made of titanium oxide doped with a cation or an anion.

Alternatively, the photocatalyst composite material of Example 2 (or a purifier based on this photocatalyst composite material)
(A) a porous carbon material, and
(B) a photocatalytic material attached to the porous carbon material,
Consisting of
The photocatalytic material is made of titanium oxide doped with a cation or an anion. The total volume of pores having a specific surface area of 10 m ² / gram or more determined by the nitrogen BET method and a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the delocalized density functional method. Is 0.1 cm ³ / gram or more. Alternatively, the photocatalyst composite material of Example 2 (or a purifier based on this photocatalyst composite material) has a specific surface area value of 10 m ² / gram or more determined by the nitrogen BET method, and is determined by a delocalized density functional method. In the pore size distribution, the ratio of the total volume of pores having at least one peak in the range of 3 nm to 20 nm and having a pore size in the range of 3 nm to 20 nm is the total volume of all pores. 0.2 or more.

Here, in Example 2, the photocatalytic material (functional material) is composed of titanium oxide (TiO ₂ ) that functions as a photocatalyst, as described above. Titanium oxide is attached (supported, adsorbed, bonded) to the porous carbon material in the form of fine particles. Thereby, charge separation, ultraviolet absorption, and catalytic properties are imparted to the porous carbon material composite, and it can be used as a harmful substance decomposing agent and a harmful substance removing agent that can be used semipermanently due to the photocatalytic effect. Moreover, since titanium oxide is doped with a cation or an anion, for example, it is possible to absorb light energy having a wavelength of 200 nm to 600 nm or visible light energy. A conceptual diagram of this energy absorption is shown in FIG. Further, the light absorption characteristics of TiO ₂ are shown in FIG.

  In Example 2, a functional material made of titanium oxide doped with a cation or an anion was attached (supported, adsorbed, bonded) to the porous carbon material-B described above. Specifically, The composite treatment was performed as shown below.

  That is, 0.5 g of porous carbon material-B, 4.57 ml of acetic acid and an appropriate amount of tetraisopropyl orthotitanate (TIPO) were added to 100 ml of ethanol, and the mixture was stirred for 1 hour. Thereafter, the mixture was centrifuged, the supernatant was discarded, a small amount of ethanol was added to the solid phase, and added in small portions while adding ultrasonic waves to 100 ml of pure water. Thereafter, centrifugation was performed again, and the obtained solid phase was dried at 100 ° C. The sample obtained at this stage was used as the sample of “Comparative Example 2”. Next, crystal growth was performed at 400 ° C. in an ammonia gas atmosphere, whereby titanium oxide was doped with an anion composed of nitrogen, and the photocatalytic composite material (purifier) of Example 2-A could be obtained.

Alternatively, 0.24 grams of FeCl ₃ .6H ₂ O is dissolved in 150 ml of pure water and the resulting photocatalyst composite material of Example 2-A is dispersed in an aqueous solution adjusted to pH 2 with hydrochloric acid, and stirred for 1 hour. Then, it was filtered through a filter, washed with distilled water, and dried at 150 ° C., whereby the photocatalyst composite material (cleaning agent) of Example 2-B could be obtained. Such treatment is performed for the purpose of doping titanium oxide with iron ions as cations.

X-ray diffraction analysis (XRD) was performed, and it was confirmed that TiO ₂ was contained in the samples of Example 2-A and Example 2-B. Table 3 below shows the results of measuring the specific surface area and the total pore volume based on the nitrogen BET method, the BJH method, and the MP method. FIG. 7 shows the measurement results of the pore (mesopore) distribution. Further, FIG. 8 shows the measurement results of the pore diameter distribution obtained by the delocalized density functional method of Example 2-A and Example 2-B, and shows 3 nm with respect to the total volume of all pores. The ratio of the total volume of pores having a pore diameter in the range of 20 nm to 20 nm was as follows.
Example 2-A: 0.561
Example 2-B: 0.367

[Table 3]
Example 2-A Example 2-B
TiO ₂ content (% by weight) 23.1 29.1
Specific surface area (m ² / g) 1235 934
Total pore volume (cm ³ / g) 0.9404 0.7088
BJH (T) (cm ³ / g) 0.5468 0.4254
MP (T) (cm ³ / g) 0.4993 0.4439
NFDLT (cm ³ / g) 1.1354 0.9796

  For evaluation, 13 milligrams of each of Example 2-A and Comparative Example 2 were added to 50 milliliters of a 0.08 millimol / liter tannic acid aqueous solution and irradiated with simulated sunlight after 24 hours. The results are shown in FIG. 9, and in Example 2-A, the tannic acid aqueous solution could be reliably decomposed.

  For evaluation, 15 milligrams of each of Example 2-B and Comparative Example 2 were added to 50 milliliters of a 0.15 mmol / liter methyl orange aqueous solution and irradiated with simulated sunlight. The result is shown in FIG. 10, and in Example 2-B, it was confirmed that most of methyl orange was decomposed 8 hours after the start of irradiation.

  Furthermore, 1.5 milligrams of the sample of Example 2-B and porous carbon material-B (Comparative Example 2 ′) were added to 5 milliliters of water, and 100 micrograms of microcystin was added every 24 hours for 12 hours. Every other experiment was repeated with simulated sunlight irradiation and shading. The result is shown in FIG. Porous carbon material-B (Comparative Example 2 ') almost did not absorb the third time, whereas the sample of Example 2-B showed sharp adsorption many times. From this result, it was confirmed that in the sample of Example 2-B, microcystin was taken into the mesopores and then decomposed by light (see the conceptual diagram of FIG. 11B). In FIG. 11B, the sawtooth waveform indicated by the solid line indicates the test result of the sample of Example 2-B, and the waveform indicated by the dotted line indicates the test result of the sample of Comparative Example 2 '.

More specifically, the porous carbon material in Example 2 is an environmentally compatible material derived from a natural product, and its microstructure is a silicon component (silicon oxide) previously contained in a raw material that is a plant-derived material. Can be obtained by treatment with acid or alkali and removal. Accordingly, the pores have a size and meso region (2 to 50 nm) that cannot be realized by conventional activated carbon, and the pore arrangement maintains the bioregularity of plants. In the photocatalyst composite material of Example 2, the photocatalyst material can be attached to the porous carbon material very effectively by such pore size and arrangement, and the decomposition by the photocatalytic action is effectively generated. be able to. Further, even in cleaning agents based on the photocatalytic composite material of Example 2 is for environment purification material, such a pore size and array, when considered effectively act on the adsorption of harmful substances at the same time The photocatalytic material can be extremely effectively adhered to the porous carbon material, and the decomposition and detoxification of harmful substances due to the photocatalytic action can be effectively caused. Further, the diffusion of harmful substances inside the purifying agent is promoted, the decomposition by the photocatalytic action can be caused more effectively, and the water purification and the air purification can be performed extremely effectively. And since the photocatalyst composite material of Example 2 can absorb the energy of visible light, the photocatalyst composite material which shows the outstanding decomposition reaction can be provided.

Example 3 relates to the adsorbent and the purifier of the present invention. The adsorbent or purifier of Example 3 is
(A) A photocatalytic composite material, specifically, a porous carbon material made from a plant-derived material containing silicon, more specifically, a plant-derived material having a silicon content of 5% by weight or more. A porous carbon material having a silicon content of 1% by weight or less, and
(B) an organic material attached to the porous carbon material,
Consisting of
The value of specific surface area by nitrogen BET method is 10 m ² / gram or more, and the volume of pores by BJH method and MP method is 0.1 cm ³ / gram or more,
Organic materials adsorb metals.

Alternatively, the adsorbent or purification agent of Example 3 is
(A) a porous carbon material, and
(B) a photocatalytic material attached to the porous carbon material,
Consisting of
Organic materials adsorb metals. The total volume of pores having a specific surface area of 10 m ² / gram or more determined by the nitrogen BET method and a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the delocalized density functional method. Is 0.1 cm ³ / gram or more. Alternatively, the adsorbent or the purifying agent of Example 3 has a specific surface area value of 10 m ² / gram or more according to the nitrogen BET method, and a pore size distribution determined by the delocalized density functional method is 3 nm to 20 nm. The ratio of the total volume of pores having at least one peak in the range and having a pore diameter in the range of 3 nm to 20 nm is 0.2 or more of the total volume of all pores.

In Example 3, polyethyleneimine was used as the organic material. FIG. 12 schematically shows a state in which polyethyleneimine is attached (supported, adsorbed, bonded) to the porous carbon material. Further, chromium (Cr) ions were adsorbed as a metal. In the adsorbent and the purifier of Example 3, 0.3 gram of the above-described porous carbon material-B and 1.5 gram of polyethyleneimine were dispersed in 100 ml of pure water, and 1 hour. By stirring, polyethyleneimine was adhered (supported, adsorbed, bonded) to the pores of the meso region of the porous carbon material-B. Thereafter, the solid phase obtained by filtration was put into an aqueous solution in which 0.5 gram of FeCl ₃ .6H ₂ O was dissolved in 100 ml of pure water, and stirred for 1 hour. The obtained powder was filtered through a filter, washed with distilled water, and dried at 120 ° C. to obtain the adsorbent and the purifying agent of Example 3. In addition, by performing the treatment with FeCl ₃ .6H ₂ O in this way, the ion exchange capacity can be enhanced. This state is schematically shown in FIG.

Using Example 3 and commercially available activated carbon (Comparative Example 3), 10 milligrams of each was dispersed in 5 milliliters of potassium chromate having various concentrations, stirred for 1 hour, and then the absorbance was measured. The results are shown in FIG. 14. Compared with commercially available activated carbon (indicated by “B” in FIG. 13), the adsorbent and the purifying agent of Example 3 (indicated by “A” in FIG. 13). Was confirmed to have 20 times the adsorption performance. That is, in the adsorbent and the purifying agent of Example 3, since the organic material is attached (supported, adsorbed, bonded) to the porous carbon material, the metal (metal atom or metal ion) is effectively adsorbed. It becomes possible. In addition, the state in which the adsorbent and the purifying agent of Example 3 adsorb chromate ions is schematically shown in FIG. In addition, Table 4 below shows the results of measuring the specific surface area and the total pore volume based on the nitrogen BET method, the BJH method, and the MP method. Further, FIG. 16 shows the measurement results of the pore size distribution obtained by the delocalized density functional method of Example 3 and Comparative Example 3, and the range of 3 to 20 nm with respect to the total volume of all pores. The ratio of the total volume of pores having a pore diameter therein was as follows.
Example 3: 0.415
Comparative Example 3: 0.134

[Table 4]
Example 3 Comparative Example 3
Specific surface area (m ² / g) 957 1184
Total pore volume (cm ³ / g) 0.7817 0.0573
BJH (T) (cm ³ / g) 0.4948 0.0816
MP (T) (cm ³ / g) 0.3743 0.5702
NFDLT (cm ³ / g) 1.0511 0.7557

  As mentioned above, although this invention was demonstrated based on the preferable Example, this invention is not limited to these Examples, A various deformation | transformation is possible. In the examples, the case where rice husk is used as the raw material of the porous carbon material has been described, but other plants may be used as the raw material. Here, examples of other plants include pods, cocoons or stem wakame, vascular plants vegetated on land, fern plants, moss plants, algae and seaweeds, and these may be used alone. Further, a plurality of types may be mixed and used.

  Specifically, for example, plant-derived materials that are raw materials for porous carbon materials are rice straw (eg, from Kagoshima; Isehikari), and porous carbon materials are carbonized from raw straw as a carbonaceous material. It can be obtained by converting to (porous carbon material precursor) and then performing acid treatment. Alternatively, a plant-derived material, which is a raw material of the porous carbon material, is used as a rice bran, and a carbonaceous material (porous carbon material precursor) is obtained by carbonizing the porous carbon material as a raw material. And then acid treatment. Similar results were obtained with a porous carbon material obtained by treatment with an alkali (base) such as an aqueous sodium hydroxide solution instead of an aqueous hydrofluoric acid solution. In addition, the manufacturing method of a porous carbon material composite_body | complex can be made to be the same as that of Example 1-3.

  Alternatively, the plant-derived material, which is the raw material of the porous carbon material, is used as stem wakame (from Sanriku, Iwate Prefecture), and the porous carbon material is carbonized from the stem wakame as raw material to produce a carbonaceous material (porous carbon material precursor Body) and then subjected to acid treatment. Specifically, first, for example, the stem wakame is heated at a temperature of about 500 ° C. and carbonized. In addition, you may process the stem wakame used as a raw material with alcohol before a heating, for example. As a specific treatment method, there is a method of immersing in ethyl alcohol or the like, thereby reducing moisture contained in the raw material, and other elements other than carbon contained in the porous carbon material finally obtained or , Mineral components can be eluted. Moreover, generation | occurrence | production of the gas at the time of carbonization can be suppressed by the process with this alcohol. More specifically, the stem wakame is soaked in ethyl alcohol for 48 hours. In addition, it is preferable to perform ultrasonic treatment in ethyl alcohol. Subsequently, this stem wakame is carbonized by heating in a nitrogen stream at 500 ° C. for 5 hours to obtain a carbide. In addition, by performing such a process (preliminary carbonization process), a tar component that will be generated in the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide is put in an alumina crucible and heated to 1000 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonizes at 1000 degreeC for 5 hours, and after converting into a carbonaceous substance (porous carbon material precursor), it cools to room temperature. In addition, nitrogen gas is kept flowing during carbonization and cooling. Next, the porous carbon material precursor is subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed until it becomes pH 7 using water and ethyl alcohol. And the porous carbon material can be obtained by making it dry at the end. Then, what is necessary is just to give the compounding process and activation process which were demonstrated in Example 1-3.

Claims (3)

(A) a porous carbon material, and
(B) a silver member attached to the porous carbon material,
Consisting of
The value of specific surface area by nitrogen BET method was 10 m ² / gram or more, the volume of pores by BJH method and MP method was 0.1 cm ³ / gram or more, and was determined by delocalized density functional method. In the pore size distribution, the proportion of the total volume of pores having at least one peak in the range of 4 nm to 20 nm and having a pore size in the range of 3 nm to 20 nm is 0% of the total volume of all pores. A method for producing a disinfectant that is 2 or more,
A method for producing a bactericidal agent in which a fine silver member is adhered to the surface of a porous carbon material including the inside of pores based on impregnation in a silver salt aqueous solution containing silver ions and further reduction and precipitation of silver by a reducing agent. (A) a porous carbon material, and
(B) a photocatalytic material attached to the porous carbon material,
Consisting of
The value of specific surface area by nitrogen BET method was 10 m ² / gram or more, the volume of pores by BJH method and MP method was 0.1 cm ³ / gram or more, and was determined by delocalized density functional method. In the pore size distribution, the proportion of the total volume of pores having at least one peak in the range of 3 nm to 20 nm and having a pore size in the range of 3 nm to 20 nm is 0% of the total volume of all pores. .2 or more,
The photocatalytic material is a method for producing a photocatalytic composite material comprising titanium oxide doped with a cation or an anion,
Based on a method of crystal growth using a gaseous substance containing a cation or an anion and titanium oxide , or
Based on the method of supporting cations or anions on the surface of titanium oxide after the synthesis based on the wet method,
A method for producing a photocatalytic composite material, wherein titanium oxide is doped with a cation or an anion.   The method for producing a photocatalyst composite material according to claim 2, wherein the photocatalyst material absorbs energy of light having a wavelength of 200 nm to 600 nm.