WO2012063591A1

WO2012063591A1 - Processes for producing porous metal body and porous metal-containing body, and porous metal body and porous metal-containing body

Info

Publication number: WO2012063591A1
Application number: PCT/JP2011/073481
Authority: WO
Inventors: 宇山浩; 辻本敬; 嶋村剛直
Original assignee: 国立大学法人大阪大学
Priority date: 2010-11-09
Filing date: 2011-10-13
Publication date: 2012-05-18
Also published as: JPWO2012063591A1; JP5769153B2

Abstract

A process for producing a porous metal body which includes a step of subjecting a porous metal-ion-containing body to reduction and sintering either simultaneously or successively to obtain a porous metal body, said porous metal-ion-containing body being a body obtained by employing a monolith-shaped starting porous body which comprises a polymer as the main component and which is modified with functional groups having chelating groups, and coordinating metal ions to the chelating groups. A process for producing a porous metal-containing body which includes a step of reducing a porous metal-ion-containing body to obtain a porous metal-containing body, said porous metal-ion-containing body being a body obtained by employing a monolith-shaped starting porous body which comprises a polymer as the main component and which is modified with functional groups having chelating groups, and coordinating metal ions to the chelating groups.

Description

Metal porous body, method for producing metal-containing porous body, metal porous body and metal-containing porous body

The present invention relates to a metal porous body, a method for producing a metal-containing porous body, a metal porous body, and a metal-containing porous body.

Porous materials and porous membranes are often used in various fields as separating agents, adsorbents, and the like. As the inorganic porous material, a great deal of research has been conducted on silica-based porous materials. Among the silica-based porous bodies, a technique for producing porous silica particles is common. This porous silica particle has been put to practical use as an analytical material.

A lump of material having a structure in which a continuous skeleton and voids are intertwined with each other is called a monolith body. The present inventors have already completed a method for producing a thick monolith body by thermally induced phase separation of an acrylic resin or the like (for example, Patent Document 1).

By the way, as a metal porous body, manufacture of the thin film type whose frame | skeleton and pore size are more than a submicron order has already been reported. Specifically, the template method has been reported. The template method is a method in which a metal is attached to the surface of a polymer, colloidal silica, etc., and the polymer is sintered to obtain a porous metal body (for example, Non-Patent Document 1). The thin-film metal porous body obtained by such a method has a pore diameter of about 200 to 600 nm and a medium specific surface area (for example, 10 to 30 m ² / g in the case of Ni). The metal porous body obtained by such a template method can be expected to be applied to optical materials such as metamaterials, but the metal porous body obtained by any method is a thin film type. This is because the submicron pores in the polymer used as a raw material in the template method are narrow, and as a result, it is difficult to infiltrate metals and metal precursors (metal ions, etc.) into the submicron pores. Conceivable.

It is also known that the metal porous body is produced by a sol-gel method, a metal salt sintering method, a dealloying method, or the like. According to the sol-gel method, an organic-inorganic hybrid aerogel can be obtained by a nanomelting process (for example, Non-Patent Document 2). According to this sol-gel method, a porous metal body can be produced in the supercritical phase. A porous metal body obtained by such a sol-gel method has a pore diameter of about 2 to 50 nm, a large specific surface area (95 to 300 m ² / g), a small density (1/170 or less of bulk Fe). Have Such a sol-gel method has the advantage that the porosity can be controlled by annealing. On the other hand, such a sol-gel method has a problem because volume change and cracking of the obtained metal porous body occur.

The metal salt sintering method is a method of obtaining a porous metal body by sintering a paste in which a metal salt and dextrin are mixed (for example, Non-Patent Document 3). The metal porous body obtained by such a metal salt sintering method has a pore diameter of 1 to 15 μm.

The dealloying method uses a difference in reactivity between two or more alloys to elute base metals with electricity or acid (for example, Non-Patent Document 4). The metal porous body obtained by such a dealloying method has a pore diameter of 100 nm or less, a relatively large (70 to 100 m ² / g when using Raney nickel), and a size of several centimeters. Have. However, in such a dealloying method, from the viewpoint of acid resistance, only easy-to-handle metals can be used as raw materials. Specifically, Au—Ag, Au—Cu, Ni—Al (Raney nickel) can be used. Etc. can only be used as raw materials. Furthermore, this dealloying method has a problem in that the metal to be eluted remains in the metal porous body, and the form of the metal porous body obtained is limited to a thin film or a porous body having a small size. There is.

JP 2009-30017 A

Accordingly, the present invention provides a method for producing a thick monolithic metal porous body in a safe and simple manner, and a thick monolithic metal-containing porous body as a raw material for such a metal porous body. The object is to provide a method of manufacturing.

The present invention is a method for producing a porous metal body,
The manufacturing method includes:
Reduction treatment and sintering to a metal ion-containing porous body in which a chelate group and a metal ion of a raw material porous body modified with a functional group having a chelate group are monolithic and containing a polymer as a main component. Including performing a process simultaneously or sequentially to obtain a porous metal body,
The metal ion-containing porous body is modified with a functional group having a chelate group, the monolithic raw material porous body containing a polymer as a main component is brought into contact with metal ions, and the chelate group of the raw material porous body Obtained by coordination bond with the metal ion,
The monolithic porous material containing a polymer as a main component, modified with a functional group having a chelate group, is converted into a monolithic porous material containing a polymer as a main component, and a functional group having a chelate group. Obtained by modifying with a compound containing,
The monolithic porous body containing a polymer as a main component is:
A polymer solution is prepared by dissolving the polymer in a liquid containing water and a poor solvent for the polymer, which is miscible with water and excluding water, and water.
Separating the polymer precipitate deposited from the polymer solution;
Obtained by drying the polymer precipitate,
The polymer is
A homopolymer of esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
A copolymer containing esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
Homopolymers of methacrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of hydroxy, carboxyl, oxiranyl and halogen atoms, and methacrylic acid and hydroxy 1 or more selected from the group consisting of copolymers containing esters with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, a carboxyl group, an oxiranyl group and a halogen atom It is.

Further, the present invention is a method for producing a metal-containing porous body,
The manufacturing method includes:
The metal ion-containing porous body in which the chelate group and metal ion of the raw material porous body modified with a functional group having a chelate group, which is monolithic, and containing a polymer as a main component is coordinated, is subjected to a reduction treatment, Including a step of obtaining a metal-containing porous body,
The metal ion-containing porous body is modified with a functional group having a chelate group, the monolithic raw material porous body containing a polymer as a main component is brought into contact with metal ions, and the chelate group of the raw material porous body Obtained by coordination bond with the metal ion,
The monolithic porous material containing a polymer as a main component, modified with a functional group having a chelate group, is converted into a monolithic porous material containing a polymer as a main component, and a functional group having a chelate group. Obtained by modifying with a compound containing,
The monolithic porous body containing a polymer as a main component,
A polymer solution is prepared by dissolving the polymer in a liquid containing water and a poor solvent for the polymer, which is miscible with water and excluding water, and water.
Separating the polymer precipitate deposited from the polymer solution;
Obtained by drying the polymer precipitate,
The polymer is
A homopolymer of esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
A copolymer containing esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
Homopolymers of methacrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of hydroxy, carboxyl, oxiranyl and halogen atoms, and methacrylic acid and hydroxy 1 or more selected from the group consisting of copolymers containing esters with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, a carboxyl group, an oxiranyl group and a halogen atom It is.

According to the present invention, it is possible to provide a method for producing a thick monolithic metal porous body and a metal-containing porous body in a safe and simple manner.

FIG. 1 shows an SEM image of the raw material porous material of p (GM) obtained in Example 1 (2). FIG. 2 shows an SEM image of the PEI-formed raw material porous body obtained in Example 1 (3). FIG. 3 shows an SEM image of the Ni metal-containing porous material obtained in Example 1 (5). FIG. 4 shows an SEM image of the Ni metal porous body obtained in Example 1 (6). FIG. 5 shows an SEM image of the Au metal-containing porous material obtained in Example 2 (2). FIG. 6 shows an SEM image of the Au metal porous body obtained in Example 2 (3). FIG. 7 shows an SEM image of the Cu metal-containing porous material obtained in Example 3 (2). FIG. 8 shows an SEM image of the Cu metal porous body obtained in Example 3 (3). FIG. 9 shows an SEM image of the Ni metal-containing porous material obtained in Example 4 (2). FIG. 10 shows an SEM image of the Ni metal porous body obtained in Example 4 (3). FIG. 11 shows an SEM image of the Ni metal porous body obtained in Example 5 (1).

In the present invention, the “metal-containing porous body” is a material containing a metal, preferably a material other than a metal having a plurality of holes, in an object made of a material other than a metal having a plurality of holes. It means a material containing metal on the surface of an object (including the surface in a hole). The “metal porous body” means a metal material having a plurality of pores. This porous metal means that it is substantially made of metal. For example, this metal material means that 90% by weight or more of metal is contained. Further, the “metal ion-containing porous body” is made of a material containing a metal ion in an object made of a material other than a metal having a plurality of pores, preferably a material other than a metal having a plurality of pores. It means a material containing metal ions on the surface of an object (including the surface in a hole).

As described above, the present invention is a method for producing a metal porous body, which is a monolithic raw material porous body modified with a functional group having a chelate group and containing a polymer as a main component. The metal ion-containing porous body in which the chelate group and the metal ion are coordinated and bonded, and a reduction process and a sintering process are performed simultaneously or sequentially to obtain a metal porous body.

The metal ion-containing porous body is subjected to reduction treatment and sintering treatment simultaneously or sequentially to obtain a metal porous body. For example, the reduction treatment and the sintering treatment are performed simultaneously, or the reduction treatment is followed by sintering. This is done by performing processing. The said reduction process will not be limited if it is a process which reduces the metal ion contained in the said metal ion containing porous body. Moreover, the said sintering process will not be limited if it is a process which sinters the polymer contained in the said metal ion containing porous body.

The metal ion-containing porous body is subjected to reduction treatment and sintering treatment simultaneously or sequentially to obtain a metal porous body,
Sintering the metal ion-containing porous body in a hydrogen atmosphere, or
Reducing the metal ion-containing porous body with a reducing agent to convert the metal ions to metal and then sintering in an air atmosphere,
It is preferable to be carried out either way.

The step of obtaining the metal porous body by sintering the metal ion-containing porous body in a hydrogen atmosphere includes, for example, 1 to 20 in a mixed atmosphere of an inert gas and hydrogen gas. It can be carried out by heating at a rate of ° C / min, preferably 1 to 12 ° C / min. Examples of the mixed atmosphere of the inert gas and hydrogen gas include an atmosphere of inert gas: hydrogen gas (volume ratio) = 3 to 1: 1. Examples of the inert gas include argon gas and nitrogen gas.

Of the steps of reducing the metal ion-containing porous body with a reducing agent, converting the metal ions to metal, and then sintering in an air atmosphere, reducing the metal ion-containing porous body, The step of converting ions into metal can be performed, for example, as follows.

For example, the metal ion-containing porous material is added to the reducing agent solution and shaken at room temperature (eg, 0 to 50 ° C., preferably 20 to 30 ° C.) for 1 to 72 hours. Examples of the reducing agent include hydrogen, sodium borohydride, ammonium borohydride, aldehyde, hydrazine, dimethylaminoborane, reducing sugar, alcohol and the like. Examples of the solvent for the pre-reducing agent solution include water, methanol, ethanol, 1-propanol, 2-propanol, butanol, dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, acetone, pyrrolidone and the like. Examples of the concentration of the reducing agent solution include 0.05 to 2M. Thereafter, the porous body is washed with a solvent such as water, and the obtained porous body is dried at room temperature under reduced pressure. In this way, the metal ion-containing porous body can be reduced to convert the metal ions into metal.

Of the steps of reducing the metal ion-containing porous body with a reducing agent, converting the metal ions to metal, and then sintering in an air atmosphere, the step of sintering in an air atmosphere is, for example, Can be done in this way. For example, the metal ion-containing porous body can be reduced and heated at a rate of 1 to 20 ° C./min, preferably 1 to 2 ° C./min while blowing air. Thereafter, a step of further sintering in a hydrogen atmosphere may be optionally performed. The step of sintering in an arbitrary hydrogen atmosphere is performed by reducing the metal ion-containing porous body and sintering it in an air atmosphere, and then, for example, 1 to 20 ° C./min, preferably 1 in a hydrogen atmosphere. Heating can be performed at a rate of ˜10 ° C./min.

According to the production method of the present invention, a porous metal body that is monolithic and thicker than the membrane can be obtained. Although the shape of the metal porous body is not limited, the shortest of the three directions of the height and width of the metal porous body is referred to as thickness for convenience. The thickness of the metal porous body is, for example, 0.05 mm or more, preferably 0.1 mm or more, more preferably 0.2 mm or more. The porous metal body has, for example, a pore diameter of, for example, 0.001 μm to 5 μm, preferably 0.002 μm to 3 μm, and a skeleton diameter of the pores of, for example, 0.001 μm to 5 μm, preferably 0.002 μm to 2 μm. is there. Such a metal porous body is useful as a catalyst, a battery material, a sensor material, and a deodorizing material.

As described above, the metal ion-containing porous body is obtained by bringing a raw material porous body modified with a functional group having a chelate group into contact with a metal ion and a raw material porous body containing a polymer as a main component. It can be obtained by coordinating the metal chelate group and the metal ion. The raw material porous body containing a polymer as a main component, which is modified with a functional group having a chelate group, is contacted with a metal ion, and the chelate group of the raw material porous body is coordinated with the metal ion. The step of obtaining the bonded metal ion-containing porous body can be performed, for example, as follows.

First, for example, a solution containing a compound containing a metal ion is added to a raw material porous body that is modified with a functional group having a chelate group and includes a polymer as a main component, and is added at room temperature (for example, 0 to 50 And shake for 1 to 72 hours. The compound containing a metal ion is not limited as long as it contains a metal that can be dissolved in water. For example, the metal halide salt, the metal sulfate, the sulfite, the hydroxide salt, Nitrate, nitrite, phosphate, organic acid salt (acetate, naphthenate, 2-ethylhexane salt) and the like. Examples of the metal include gold, silver, platinum, palladium, nickel, copper, manganese, rhodium, cobalt, ruthenium, rhenium, molybdenum, tin, zinc, iron, titanium, vanadium, chromium, osmium, iridium, bismuth, cadmium and gallium. Is mentioned. Examples of the solvent for the solution of the compound include water. Examples of the concentration of the solution containing the compound containing metal ions include 0.01 to 2M. Thereafter, the porous body is washed with a solvent such as water, and the obtained porous body is dried at room temperature under reduced pressure. In this way, the step of obtaining a metal ion-containing porous body in which the raw material porous body and metal ions are brought into contact and the chelate group of the raw material porous body and the metal ions are coordinated is performed. it can.

In the production method of the present invention, the metal ions are gold, silver, platinum, palladium, nickel, copper, manganese, rhodium, cobalt, ruthenium, rhenium, molybdenum, tin, zinc, iron, titanium, vanadium, chromium, osmium, It is preferably at least one selected from the group consisting of ions of iridium, bismuth, cadmium and gallium.

In the present invention, the monolithic raw material porous material containing a polymer as a main component, which is modified with the functional group having a chelating group, is converted into a monolithic porous material containing a polymer as a main component. It is obtained by modifying with a compound containing a functional group having. The step of modifying the monolithic porous body containing a polymer as a main component with a compound containing a functional group having a chelate group can be performed, for example, as follows.

First, for example, a solution containing a compound containing a functional group having a chelate group is added to the monolithic porous body containing a polymer as a main component, and heated (for example, 20 to 90 ° C., preferably 30 to 80 ° C.). Shake for 2 to 24 hours. Examples of the solvent for the solution of the compound include water, methanol, ethanol, propanol, butanol, dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, acetone, and pyrrolidone. Thereafter, the porous body is washed with a solvent such as water, and the obtained porous body is dried at room temperature under reduced pressure. Thus, the step of modifying the monolithic porous body containing a polymer as a main component with a compound containing a functional group having a chelate group can be performed.

In the production method of the present invention, the compound containing a functional group having a chelate group includes an amine, a condensate of amine and ethylenediaminetetraacetic acid, a condensate of amine and epichlorohydrin, and a condensate of amine and iminodiacetic acid. And a condensate of amine and bromoacetic acid, a compound having a functional group such as phosphine, thiol and carbene. Examples of the amine, alkylamine, branched or linear polyethyleneimine [e.g., polyethylene amine of the formula _{_{_{H 2 N (CH 2 CH 2}}} NH) n H ( e.g., ethylene diamine (n = 1), diethylene triamine ( n = 2), triethylenetetramine (n = 3))], heterocyclic amines (for example, piperazine), polyallylamine, polyvinylamine and the like. When the compound containing a functional group having a chelate group is the condensate, for example, when the compound is a condensate of an amine and ethylenediaminetetraacetic acid, the monolithic porous body containing a polymer as a main component is first converted into an amine. Then, by condensing the amine and ethylenediaminetetraacetic acid, finally, a monolithic raw material porous body containing a polymer as a main component is modified with the functional group having the chelate group. Obtainable.

The monolithic porous body containing a polymer as a main component is miscible with water and dissolves the polymer in a liquid containing water and a poor solvent for the polymer excluding water. It is obtained by preparing a polymer solution, separating the polymer precipitate deposited from the polymer solution, and drying the polymer precipitate.

At this time, the polymer is
A homopolymer of esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
A copolymer containing esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
Homopolymers of methacrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of hydroxy, carboxyl, oxiranyl and halogen atoms, and methacrylic acid and hydroxy 1 or more selected from the group consisting of copolymers containing esters with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, a carboxyl group, an oxiranyl group and a halogen atom It is.

Examples of homopolymers of esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom include: , Homopolymers of hydroxymethyl ester of acrylic acid, homopolymers of carboxylic acid carboxyl ethyl ester, homopolymers of glycidyl acrylate, and homopolymers of chloromethyl ester of acrylic acid.

Examples of the copolymer containing an ester of acrylic acid and an ester of a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom, A copolymer of an acrylic acid and an ester of acrylic acid and an ester of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom, A copolymer of esters and methacrylic acid of acrylic acid and one or more lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom, Acrylic acid and hydroxy group, carboxyl group, Copolymers of esters and acrylate esters with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of silanyl groups and halogen atoms, acrylic acid and hydroxy groups, carboxyl groups And copolymers of esters and methacrylic esters with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an oxiranyl group and a halogen atom.

Examples of homopolymers of esters of methacrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom include: , Methacrylic acid hydroxymethyl ester homopolymer, methacrylic acid carboxyl ethyl ester homopolymer, glycidyl methacrylate homopolymer, methacrylic acid chloromethyl ester homopolymer, and the like.

Examples of the copolymer containing methacrylic acid and esters of a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom include A copolymer of esters and acrylic acid of methacrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom, A copolymer of methacrylic acid and an ester of methacrylic acid with a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom, Methacrylic acid and hydroxy group, carboxy A copolymer of an ester and an acrylate ester with a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, an oxiranyl group and a halogen atom, the methacrylic acid and a hydroxy group, Examples thereof include a copolymer of an ester with a lower alkyl alcohol having 1 to 6 carbon atoms and a methacrylic acid ester which may contain one or more selected from the group consisting of a carboxyl group, an oxiranyl group and a halogen atom. Copolymers of methacrylic acid and esters of methacrylic acid esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of hydroxy groups, carboxyl groups, oxiranyl groups and halogen atoms Examples include a copolymer of glycidyl methacrylate and methyl methacrylate.

The polymerization method for producing the polymer is not limited, and may be radical polymerization, ionic polymerization, or the like. In the case where the polymer is a copolymer, the monomer composition ratio is not limited, but examples include a polymer whose solubility in water is low. For example, in the case of a copolymer of methyl methacrylate and glycidyl methacrylate, the molar ratio of glycidyl methacrylate is preferably 5 mol% to 50 mol%. The monomer sequence of the polymer may be random, block or the like. Further, although the molecular weight of the polymer is not limited, for example, the number average molecular weight (Mn) is 1,000 to 100,000,000, preferably 2,000 to 50,000,000, more preferably 3 , 20,000 to 20,000,000. Further, for example, the weight average molecular weight (Mw) is 1,000 to 150,000,000, preferably 2,000 to 80,000,000, more preferably 3,000 to 40,000,000. is there. The molecular weight distribution is generally measured by size exclusion chromatography. Examples of size exclusion chromatography include gel permeation chromatography (GPC) and gel filtration chromatography (GFC). Using chloroform or THF as the mobile phase of GPC and a polystyrene gel column as the column, the number average molecular weight and the like can be determined in terms of polystyrene.

As described above, the monolithic porous body containing a polymer as a main component is miscible with water and contains a poor solvent for the polymer excluding water and a liquid containing water. Is dissolved to prepare a polymer solution, the polymer precipitate deposited from the polymer solution is separated, and the polymer precipitate is dried. In the present application, the poor solvent means a solvent having a small ability to dissolve the polymer. Specifically, it means that 50 g or more, preferably 30 g or more, more preferably 10 g or more of the polymer does not dissolve with respect to 1 L of the poor solvent. The poor solvent is miscible with water and excludes water.

Examples of the poor solvent include aliphatic alcohols. Examples of the aliphatic alcohol include an aliphatic alcohol containing an aliphatic hydrocarbon having 1 to 8 carbon atoms and having 1 or more hydroxyl groups, preferably an aliphatic alcohol having 1 to 3 carbon atoms and having 1 to 6 carbon atoms. Examples thereof include aliphatic alcohols containing hydrocarbons, more preferably aliphatic alcohols containing aliphatic hydrocarbons having 1 to 3 carbon atoms and having 1 hydroxyl group. Specifically, the aliphatic alcohol includes methanol, ethanol, n-propanol, i-propanol, n-butanol, 2-butanol, i-butanol, t-butanol, n-pentanol, t-amyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, ethylene glycol, propylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, 2- Examples include ethoxyethanol and 2-methoxyethanol.

The liquid contains, for example, an aliphatic alcohol and water, preferably an aliphatic alcohol containing an aliphatic hydrocarbon having 1 to 8 carbon atoms having one or more hydroxyl groups, and water, more preferably a hydroxyl group. And an aliphatic alcohol containing an aliphatic hydrocarbon having 1 to 6 carbon atoms and 1 to 6 carbon atoms, and water, more preferably ethanol or i-propanol and water.

The ratio of the poor solvent and water contained in the liquid is not particularly limited, but the ratio of the poor solvent / (water + the poor solvent) is, for example, 30 to 99%, preferably 50 to 97%, and more preferably. May be 60-95%.

In the present invention, the temperature at which the polymer and the liquid are mixed and the polymer is dissolved in the liquid is not particularly limited, but is, for example, 10 to 80 ° C., preferably 15 to 75 ° C., more preferably 20 to It may be 70 ° C.

In the present invention, when the polymer and the liquid are mixed and the polymer is dissolved in the liquid, physical stimulation may be applied. Examples of the physical stimulation include stirring, shaking, ultrasonic treatment, and the like.

According to such a process, a metal ion-containing porous body that is monolithic and thicker than the membrane can be obtained. The shape of the metal ion-containing porous body is not limited, but the shortest of the three directions of the vertical and horizontal heights of the metal ion-containing porous body is referred to as thickness for convenience. The thickness of the metal ion-containing porous body is, for example, 0.5 mm or more, preferably 0.7 mm or more, more preferably 1 mm or more. The pore size of the metal ion-containing porous body is, for example, 0.01 μm to 5 μm, preferably 0.03 μm to 3 μm, and the skeleton diameter of the pore is, for example, 0.01 μm to 5 μm, preferably 0.03 μm to 3 μm.

As described above, the method for producing a metal-containing porous body according to the present invention includes a chelate group and a metal ion of a raw material porous body that is modified with a functional group having a chelate group and that includes a polymer as a main component. It includes a step of performing a reduction treatment on the metal ion-containing porous body coordinated and obtaining a metal-containing porous body.

The step of reducing the metal ion-containing porous material can be performed, for example, as follows. The metal ion-containing porous material is added to the reducing agent solution and shaken at room temperature (eg, 0 to 50 ° C., preferably 20 to 30 ° C.) for 1 to 72 hours. Examples of the reducing agent include hydrogen, sodium borohydride, ammonium borohydride, aldehyde, hydrazine, dimethylaminoborane, reducing sugar, alcohol and the like. Examples of the solvent for the pre-reducing agent solution include water, methanol, ethanol, 1-propanol, 2-propanol, butanol, dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, acetone, pyrrolidone and the like. Examples of the concentration of the reducing agent solution include 0.05 to 2M. Thereafter, the porous body is washed with a solvent such as water, and the obtained porous body is dried at room temperature under reduced pressure. In this manner, a step of reducing the metal ion-containing porous body to convert the metal ions into a metal to obtain a metal-containing porous body can be performed.

In the method for producing a metal-containing porous body, as described above, the metal ion-containing porous body is a monolithic raw material porous body modified with a functional group having a chelate group and containing a polymer as a main component. And metal ions are contacted, and the chelate group of the raw material porous body and the metal ions are coordinated and obtained,
The monolithic raw material porous material modified with a functional group having a chelate group and containing a polymer as a main component is a monolithic porous material containing a polymer as a main component. Obtained by modifying with a compound containing,
The monolithic porous body containing a polymer as a main component is miscible with water and dissolves the polymer in a liquid containing water and a poor solvent for the polymer excluding water. It is obtained by preparing a polymer solution, separating the polymer precipitate deposited from the polymer solution, and drying the polymer precipitate.

Monolithic raw material porous body containing polymer as main component, modified with functional group having chelate group, monolithic porous body containing polymer as main component, and functional group having chelate group The metal ion-containing porous body in which the chelate group of the raw material porous body containing a polymer as a main component and the metal ion are coordinated and bonded is a monolith-like porous body modified with the method for producing a metal porous body of the present invention A monolithic raw material porous material containing a polymer as a main component, a monolithic porous material containing a polymer as a main component, and the chelating group modified with a functional group having the chelating group Metal ions containing monolithic, functionally modified, raw material porous material containing polymer as a main component and coordinated with chelating groups and metal ions It can be obtained in the same manner as porous bodies.

According to such a production method of the present invention, a metal-containing porous body that is monolithic and thicker than the film can be obtained. The shape of the metal-containing porous body is not limited, but the shortest of the three directions of the vertical and horizontal heights of the metal-containing porous body is referred to as thickness for convenience. The metal-containing porous body has a thickness of, for example, 0.5 mm or more, preferably 0.7 mm or more, and more preferably 1 mm or more. The pore diameter of the metal-containing porous body is, for example, 0.01 μm to 5 μm, preferably 0.03 μm to 3 μm, and the skeleton diameter of the pore is, for example, 0.01 μm to 5 μm, preferably 0.03 μm to 3 μm. Such a metal-containing porous body is useful as a catalyst, a sensor, a luminescent material, and a disinfectant.

The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited by the following examples.
The following abbreviations are used in the description of the present specification.
MMA: Methyl methacrylate GMA: Glycidyl methacrylate PEI: Polyethyleneimine EDTA: Ethylenediaminetetraacetic acid p (GM): MMA-GMA copolymer DMSO: Dimethyl sulfoxide

In this specification, the following devices were used as measuring devices.
NMR (Nuclear Magnetic Resonance): Bruker DPX 400
GPC (Gel Permeation Chromatography): TOSOH DP-8020 pump, TOSOH RI-8020 RI detector, TOSOH SD-8020 degasser, TOSOH CO-8020 column oven, TOSOH AS-8020 autosampler, TOSOH TSK gel Measurement was performed by connecting two columns of GMH-M and TOSOH TSK gel GMH-N.

Bio Shaker: MBR-022UP (TAITEC)
Differential thermal thermogravimetric simultaneous measurement device (TG-DTA): Seiko Instruments Inc., SSC / 5200 (TG / DTA220)
EDX (Energy Dispersive X-ray Spectroscopy) Hitachi Tabletop Microscope: Miniscope TM3000
Scanning electron microscope SEM: Hitachi S-3000N (manufactured by Hitachi High-Technologies Corporation)
Ion sputtering: Hitachi E-1010
BET (specific surface area measurement): Micromeritics Tristar 3000 (Shimadzu Corporation)
Conductivity measurement: SANWA Digital Multimeter CD770
Furnace under hydrogen atmosphere: Horizontal atmosphere tubular furnace (manufactured by Asahi Rika Seisakusho)
In this specification, the pore diameter and the skeleton diameter were determined from images taken using a scanning electron microscope (SEM).

<SEM observation>
The porous body was subjected to sputtering for 150 s with a discharge current of 15.0 mA, and then subjected to SEM observation at an applied voltage of 15.0 kV to 25.0 kV.

<BET specific surface area measurement>
The porous body was degassed for 240 minutes at 40 ° C. under reduced pressure using a sample degasser, and then the specific surface area was measured by the BET three-point method.

<Conductivity>
Terminals were applied to both ends of a measurement sample molded to a width of 1 mm, and the minimum and maximum values were measured when measured twice at three locations, top, bottom, left and right.

<Mn and Mw>
Mn (number average molecular weight), Mw (weight average molecular weight) and Mw / Mn (molecular weight distribution) were measured at 40 ° C. with a chloroform solvent using GPC (gel permeation chromatography). The molecular weight of the obtained polymer was converted from polystyrene equivalent molecular weight to polystyrene equivalent by the universal method.

<Manufacture of Ni metal porous body>
A Ni metal-containing porous body and a Ni metal porous body were produced according to the following scheme 1.

(1) Production of MMA-GMA copolymer (hereinafter referred to as p (GM)) In a 200 mL eggplant flask containing a stirrer, methyl methacrylate (152 mmol, 30 g, manufactured by Wako Pure Chemical Industries), glycidyl methacrylate (15.2 mmol) 4.65 g, manufactured by Nacalai tex), azobisisobutyronitrile (0.1 mmol, 0.0301 g, manufactured by Wako Pure Chemical Industries) and toluene (120 mL, manufactured by Nacalai tex) were added. The mixed solution was heated at 80 ° C. with stirring in an oil bath placed on a stirrer. After 6 hours, the heating was stopped and reprecipitation was performed in 2 L of methanol (manufactured by Kishida), whereby a white solid was obtained. The obtained solid was collected by suction filtration and dried under reduced pressure at 50 ° C. and 10 Torr. The molecular weight of the product was confirmed by GPC (developing solvent: chloroform, calibration curve toluene) to be Mn = 99,400, Mw = 272,000, and Mw / Mn = 2.74. The polymerization ratio was confirmed by NMR to be MMA: GMA = 89: 11.

(2) Production of monolithic raw material porous body containing p (GM) as a main component (hereinafter referred to as “p (GM) raw material porous body”) Ethanol in a 5 mL sample tube containing a stirrer (Shinwa Alcohol Sangyo Co., Ltd.): p (GM) (Mw = 272,000) was added to a mixed solution of water (80:20 vol%) at a concentration of 120 mg / mL, and dissolved by heating at 60 ° C. with stirring. . Thereafter, the stir bar was taken out from the mixed solution and cooled in a bioshaker at 20 ° C. for 8 hours to induce phase separation to obtain a white solid. The obtained solid was in the shape of a sample tube (columnar). This was solvent-replaced with 10 mL of water for 2 hours, the operation of discarding the water after solvent replacement and replacing it with new water was performed twice, followed by drying at room temperature under reduced pressure for 8 hours at 10 Torr and p (GM) Raw material porous body (dimension: diameter 10 mm, thickness 12 mm, substantially cylindrical shape, 120 mg) was obtained. The obtained p (GM) raw material porous body had a BET specific surface area of 7.50 m ² / g. The results of elemental analysis of the obtained raw material porous material of p (GM) were C: 59.2% and H9.43% (theoretical values were C: 65.2%, H9.43%). . The SEM image of the obtained raw material porous body of p (GM) is shown in FIG. As shown in FIG. 1, the raw material porous material of p (GM) was confirmed to be a porous material having a co-continuous structure with a skeleton diameter of 1 to 2 μm and a pore diameter of 1 to 2 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The obtained raw material porous material of p (GM) did not show conductivity.

(3) Production of a raw material porous body modified with a functional group having a chelate group and containing p (GM) as a main component, a raw material of p (GM) obtained in advance in Example 1 (2) The porous body (120 mg) was immersed in ethanol for 8 hours. Add 5 mL of ethanol mixture solution of 75 wt% branched polyethyleneimine (Mw = 300, Nippon Shokubai) by mass ratio and porous material of p (GM) material to the sample tube, and heat at 40 ° C. with stirring for 8 hours with a bioshaker. did. The product was solvent-replaced with 10 mL of water for 2 hours, and the operation of discarding the water after solvent replacement and replacing it with new water was performed twice, followed by drying at room temperature under reduced pressure for 8 hours at 10 Torr to form PEI. In addition, a raw material porous material of p (GM) (hereinafter referred to as “PEI raw material porous material”) (200 mg) was obtained. The obtained PEI raw material porous body had a BET specific surface area of 5.00 m ² / g. The results of elemental analysis of the obtained PEI-formed raw material porous body were C: 50.7%, H8.58%, and N10.1%. The SEM image of the obtained PEI-formed raw material porous body is shown in FIG. As shown in FIG. 2, it was confirmed that the PEI material porous body was a porous body having a co-continuous structure having a skeleton diameter of 1 to 2 μm and a pore diameter of 1 to 2.5 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples.

To a 10 mL sample tube, add 5 mL of a 0.5 M ethylenediaminetetraacetic acid dianhydride (manufactured by Tokyo Chemical Industry) dimethyl sulfoxide (DMSO, Wako Pure Chemical Industries) solution and 200 mg of PEI raw material porous material, and use a bioshaker for 24 hours And heated at 40 ° C. with shaking. After the reaction, the obtained porous body was washed with DMSO, 0.1 M aqueous sodium hydroxide solution (manufactured by Wako Pure Chemical Industries), and water in this order. The porous body was dried at room temperature under reduced pressure for 8 hours at 10 Torr to obtain a raw material porous body converted to EDTA-PEI (hereinafter referred to as “EDTA-PEI converted raw material porous body”) (230 mg). The resulting EDTA-PEI raw material porous body had a BET specific surface area of 3.70 m ² / g. The results of elemental analysis of the obtained EDTA-PEI raw material porous material were C: 50.9%, H 7.27%, and N 5.72%. The obtained EDTA-PEI raw material porous material did not show conductivity.

(4) Production of metal ion-containing porous material in which the chelate group of the raw material porous material and Ni ions are coordinated and bonded EDTA-PEI raw material porous material (120 mg) previously obtained in Example 1 (3) ) Was immersed in ethanol for 8 hours. Nickel chloride (anhydrous) (8 mmol, 1.03 g) was dissolved in 10 mL of water to prepare a 0.8 M nickel chloride aqueous solution. To a 10 mL sample tube, 5 mL of 0.8 M nickel chloride aqueous solution and the EDTA-PEI raw material porous material (230 mg) obtained in Example 1 (3) were added, and shaken with a bioshaker at room temperature for 24 hours. After the reaction, it is washed with water, dried at room temperature under reduced pressure for 8 hours at 10 Torr, and a metal ion-containing porous body (hereinafter referred to as “Ni ion-containing”) in which the chelate group of the raw material porous body and Ni ions are coordinated. (Referred to as “porous body”) (275 mg). The results of elemental analysis of the obtained Ni ion-containing porous material were C: 4.39%, H26.3%, and N2.51%. The resistance value of the obtained Ni ion-containing porous body was 20 × 10 ⁶ Ω, and the Ni ion-containing porous body did not exhibit conductivity. The Ni ion-containing porous body had a thickness of 2 cm, a pore diameter of 0.6 μm to 1.2 μm, and a pore skeleton diameter of 0.5 μm to 1.0 μm.

(5) Manufacture of a metal-containing porous body obtained by converting Ni ions into metal Sodium borohydride (10 mmol, 0.0378 g, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 10 mL of methanol, and 1M sodium borohydride methanol. The solution was adjusted. To a 10 mL sample tube, 5 mL of a 1M sodium borohydride methanol solution and the Ni ion-containing porous material (275 mg) obtained in Example 1 (4) were added, and the mixture was shaken with a bioshaker at room temperature for 24 hours. After the reaction, it was washed with water and dried at room temperature under reduced pressure for 8 hours at 10 Torr to obtain a Ni metal-containing porous body in which Ni ions were converted to metal. The SEM image of the obtained Ni metal containing porous body is shown in FIG. As shown in FIG. 3, the Ni metal-containing porous body was confirmed to be a porous body having a co-continuous structure with a skeleton diameter of 1 to 2 μm and a pore diameter of 1 to 2.5 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The thickness of the Ni metal-containing porous body was 2 cm.

(6) Manufacture of Ni metal porous body Ni metal containing porous body (10 mg) obtained in Example 1 (5) was baked at a rate of 10 ° C / min while flowing air to make a Ni metal porous body. (25 mg) was obtained. In the obtained Ni metal porous body, the presence of Ni was confirmed by an EDX apparatus. The results of elemental analysis of the obtained Ni metal porous body were C: 1.44%, H0.52%, N0.13% (theoretical values were C: 0%, H0%, N0%). . It can be estimated that the obtained Ni metal porous body is substantially composed of Ni metal. The SEM image of the obtained Ni metal porous body is shown in FIG. As shown in FIG. 4, it was confirmed that the Ni metal porous body was a porous body having a co-continuous structure with a skeleton diameter of 0.05 μm to 0.4 μm and a pore diameter of 0.4 μm to 1 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The obtained Ni metal porous body had a resistance value of 50Ω, and the Ni metal porous body exhibited conductivity. The thickness of the Ni metal porous body was 0.5 mm.

<Manufacture of Au metal porous body>
An Au metal-containing porous body and an Au metal porous body were produced according to the following scheme 2.

(1) Production of metal ion-containing porous material in which the chelate group of the raw material porous material and Au ions are coordinated and bonded EDTA-PEI raw material porous material (20 mg) previously obtained in Example 1 (3) ) Was immersed in ethanol for 8 hours. H [AuCl ₄ ] (2 mmol, 0.68 g) was dissolved in 5 mL of water to prepare a 0.4 M H [AuCl ₄ ] aqueous solution. To a 10 mL sample tube, add 5 mL of 0.4 M H [AuCl ₄ ] aqueous solution and the porous EDTA-PEI raw material (20 mg) obtained in Example 1 (3), and shake with a bioshaker at room temperature for 24 hours. That ’s it. After the reaction, the substrate is washed with water, dried at room temperature under reduced pressure for 8 hours at 10 Torr, and a metal ion-containing porous body in which the chelate group of the raw material porous body and Au ions are coordinated (hereinafter referred to as “Au ion-containing”). (Referred to as “porous body”) (23 mg). The Au ion-containing porous body had a thickness of 2 cm, a pore diameter of 0.8 μm to 1.5 μm, and a pore skeleton diameter of 0.3 μm to 1.0 μm.

(2) Production of metal-containing porous material by converting Au ions to metal Sodium borohydride (0.5 mmol, 19 mg, manufactured by Wako Pure Chemical Industries) was dissolved in 5 mL of methanol, and 100 mM of sodium borohydride methanol. The solution was adjusted. To a 10 mL sample tube, 5 mL of a 100 mM sodium borohydride methanol solution and an Au ion-containing porous material (23 mg) obtained in Example 2 (1) were added, and the mixture was shaken with a bioshaker at room temperature for 24 hours. After the reaction, it was washed with water and dried at room temperature under reduced pressure for 8 hours at 10 Torr to obtain Au metal-containing porous material in which Au ions were converted to metal. The SEM image of the obtained Au metal containing porous body is shown in FIG. As shown in FIG. 5, the Au metal-containing porous body was confirmed to be a porous body having a co-continuous structure with a skeleton diameter of 1 to 2 μm and a pore diameter of 1 to 2.5 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The thickness of the Au metal-containing porous body was 2 cm.

(3) Production of Au metal porous body Au metal-containing porous body (23 mg) obtained in Example 2 (2) was baked at a rate of 2 ° C / min while flowing air, and Au metal porous body (4.3 mg) was obtained. In the obtained Au metal porous body, the presence of Au was confirmed by an EDX apparatus. The SEM image of the obtained Au metal porous body is shown in FIG. As shown in FIG. 6, the Au metal porous body was confirmed to be a porous body having a co-continuous structure having a skeleton diameter of 0.1 μm to 0.3 μm and a pore diameter of 0.8 μm to 1 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The obtained Au metal porous body had a resistance value of 0.75Ω, and the Au metal porous body exhibited electrical conductivity. The thickness of the Au metal porous body was 0.5 mm.

<Manufacture of Cu metal porous body>
A Cu metal-containing porous body and a Cu metal porous body were produced according to the following scheme 3.

(1) Production of metal ion-containing porous material in which the chelate group of the raw material porous material and Cu ions are coordinated and bonded EDTA-PEI raw material porous material (50 mg) previously obtained in Example 1 (3) ) Was immersed in ethanol for 24 hours. CuCl ₂ (20 mmol, 0.34 g) was dissolved in 100 mL of water to prepare a 0.2 M aqueous CuCl ₂ solution. To a 10 mL sample tube, 100 mL of 0.2 M CuCl ₂ aqueous solution and the porous EDTA-PEI material (50 mg) obtained in Example 1 (3) were added, and shaken with a bioshaker at room temperature for 24 hours. After the reaction, it is washed with water, dried at room temperature under reduced pressure for 8 hours at 10 Torr, and a metal ion-containing porous body in which the chelate group of the raw material porous body and Cu ions are coordinated (hereinafter referred to as “Cu ion-containing”). (Referred to as “porous body”) (64 mg). The Cu ion-containing porous body had a thickness of 1.2 cm, a pore diameter of 0.7 μm to 1.4 μm, and a pore skeleton diameter of 0.5 μm to 1.0 μm.

(2) Production of a metal-containing porous material obtained by converting Cu ions into metal Sodium borohydride (2.0 mmol, 75 mg, manufactured by Wako Pure Chemical Industries) was dissolved in 20 mL of methanol, and 100 mM of sodium borohydride methanol. The solution was adjusted. To a 10 mL sample tube, 20 mL of a 100 mM sodium borohydride methanol solution and Cu ion-containing porous material (64 mg) obtained in Example 2 (1) were added, and the mixture was shaken with a bioshaker at room temperature for 24 hours. After the reaction, it was washed with water and dried at room temperature under reduced pressure for 8 hours at 10 Torr to obtain a Cu metal-containing porous body in which Cu ions were converted to metal. The SEM image of the obtained Cu metal containing porous body is shown in FIG. As shown in FIG. 7, it was confirmed that the Cu metal-containing porous body was a porous body having a co-continuous structure having a skeleton diameter of 1 to 2 μm and a pore diameter of 1 to 2.5 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The thickness of the Cu metal-containing porous body was 1.2 cm.

(3) Production of Cu metal porous body Cu metal-containing porous body (30 mg) obtained in Example 3 (2) was baked at a rate of 2 ° C / min while flowing air to form a Cu metal porous body. (5.5 mg) was obtained. In the obtained Cu metal porous body, the presence of Cu was confirmed by an EDX apparatus. The SEM image of the obtained Cu metal porous body is shown in FIG. As shown in FIG. 8, it was confirmed that the Cu metal porous body was a porous body having a co-continuous structure having a skeleton diameter of 0.4 to 1 μm and a pore diameter of 0.8 to 2 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The thickness of the Cu metal porous body was 2.0 mm.

<Manufacture of another Ni metal porous body>
Another Ni metal-containing porous body and Ni metal porous body were produced according to Scheme 4 below.

(1) Production of metal ion-containing porous material in which chelate group of Ni material and Ni ion are coordinated and bonded PEI material porous material (100 mg) obtained in Example 1 (3) in advance Soaking in ethanol for 24 hours. Nickel chloride (anhydrous) (10 mmol, 1.26 g) was dissolved in 50 mL of water to prepare a 0.2 M nickel chloride aqueous solution. To a 10 mL sample tube, 50 mL of 200 mM nickel chloride aqueous solution and the PEI raw material porous material (100 mg) obtained in Example 1 (3) were added, and shaken with a bioshaker at room temperature for 24 hours. After the reaction, it is washed with water, dried at room temperature under reduced pressure for 8 hours at 10 Torr, and a metal ion-containing porous body (hereinafter referred to as “Ni ion-containing”) in which the chelate group of the raw material porous body and Ni ions are coordinated. (Referred to as “porous body”) (142 mg). The Ni ion-containing porous body had a thickness of 2 cm, a pore diameter of 0.6 μm to 1.2 μm, and a pore skeleton diameter of 0.5 μm to 1.0 μm.

(2) Manufacture of a metal-containing porous body in which Ni ions are converted to metal Sodium borohydride (5 mmol, 188 mg, manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 50 mL of methanol, and a methanol solution of 100 mM sodium borohydride is added. It was adjusted. To a 10 mL sample tube, 50 mL of a 100 mM sodium borohydride methanol solution and the Ni ion-containing porous material (50 mg) obtained in Example 4 (1) were added and shaken with a bioshaker at room temperature for 24 hours. After the reaction, it was washed with water and dried at room temperature under reduced pressure for 8 hours at 10 Torr to obtain a Ni metal-containing porous body in which Ni ions were converted to metal. The SEM image of the obtained Ni metal containing porous body is shown in FIG. As shown in FIG. 9, the Ni metal-containing porous body was confirmed to be a porous body having a co-continuous structure having a skeleton diameter of 0.6 to 1.0 μm and a pore diameter of 0.8 to 1.0 μm. . In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples.

(3) Manufacture of Ni metal porous body Ni metal containing porous body (60 mg) obtained in Example 4 (2) was baked at a rate of 2 ° C./min while flowing air to make a Ni metal porous body. (9 mg) was obtained. In the obtained Ni metal porous body, the presence of Ni was confirmed by an EDX apparatus. The SEM image of the obtained Ni metal porous body is shown in FIG. As shown in FIG. 10, the Ni metal porous body was confirmed to be a porous body having a co-continuous structure with a skeleton diameter of 0.05 μm to 0.4 μm and a pore diameter of 0.4 μm to 1 μm. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples. The thickness of the Ni metal ion-containing porous body was 0.6 mm. The obtained Ni metal porous body had a resistance value of 90Ω, and the Ni metal porous body exhibited conductivity.

<Manufacture of another Ni metal porous body>
A Ni metal porous body was produced according to the following scheme 5.

(1) Production of metal porous body by converting Ni ions to metal Ni ion-containing porous body (95 mg, thickness 9.1 mm) obtained in Example 4 (1) was mixed with argon and hydrogen (argon: hydrogen (volume The mixture was fired to 250 ° C. at a rate of 10 ° C./min while flowing a mixed gas of ratio 2: 1), and then heated to 450 ° C. at a rate of 2 ° C./min. After maintaining the temperature for 2 hours as it was, heating was stopped and the mixture was allowed to cool to convert Ni ions into metal, thereby obtaining a Ni metal porous body (5.5 mg). In the obtained Ni metal porous body, the presence of Ni was confirmed by an EDX apparatus. The SEM image of the obtained Ni metal porous body is shown in FIG. As shown in FIG. 11, the Ni metal porous body had a skeleton diameter of 0.05 μm to 0.4 μm and a pore diameter of 0.2 μm to 1 μm. The thickness of the Ni metal porous body was 2 mm, the resistance value was 45Ω (at a width of 2 mm), and the Ni metal porous body exhibited conductivity. In addition, it can be estimated from the fact that the pores have the same or similar shape in the SEM photographs of a plurality of porous body samples.

Various types of porous metal bodies can be obtained by the method of the present invention. Such a metal porous body may be applicable as a catalyst, battery material, sensor material, deodorizing material and the like. Moreover, various types of metal-containing porous bodies can be obtained by the method of the present invention. Such a metal-containing porous body may be applicable as a catalyst, a sensor, a luminescent material, a bactericidal agent, and the like.

Claims

A method for producing a porous metal body,
The manufacturing method includes:
Reduction treatment and sintering to a metal ion-containing porous body in which a chelate group and a metal ion of a raw material porous body modified with a functional group having a chelate group are monolithic and containing a polymer as a main component. Including performing a process simultaneously or sequentially to obtain a porous metal body,
The metal ion-containing porous body is modified with a functional group having a chelate group, the monolithic raw material porous body containing a polymer as a main component is brought into contact with metal ions, and the chelate group of the raw material porous body Obtained by coordination bond with the metal ion,
The monolithic porous material containing a polymer as a main component, modified with a functional group having a chelate group, is converted into a monolithic porous material containing a polymer as a main component, and a functional group having a chelate group. Obtained by modifying with a compound containing,
The monolithic porous body containing a polymer as a main component,
A polymer solution is prepared by dissolving the polymer in a liquid containing water and a poor solvent for the polymer, which is miscible with water and excluding water, and water.
Separating the polymer precipitate deposited from the polymer solution;
Obtained by drying the polymer precipitate,
The polymer is
A homopolymer of esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
A copolymer containing esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
Homopolymers of methacrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of hydroxy, carboxyl, oxiranyl and halogen atoms, and methacrylic acid and hydroxy 1 or more selected from the group consisting of copolymers containing esters with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, a carboxyl group, an oxiranyl group and a halogen atom The manufacturing method which is.
The compound containing a functional group having a chelate group is an amine, a condensate of amine and ethylenediaminetetraacetic acid, a condensate of amine and epichlorohydrin, a condensate of amine and iminodiacetic acid, an amine and bromoacetic acid. The production method according to claim 1, which is at least one selected from the group consisting of a condensate and a compound having a functional group of phosphine, thiol and / or carbene.
The metal ions are gold, silver, platinum, palladium, nickel, copper, manganese, rhodium, cobalt, ruthenium, rhenium, molybdenum, tin, zinc, iron, titanium, vanadium, chromium, osmium, iridium, bismuth, cadmium and gallium. The production method according to claim 1, wherein the production method is one or more selected from the group consisting of ions.
The metal ion-containing porous body is subjected to reduction treatment and sintering treatment simultaneously or sequentially to obtain a metal porous body,
Sintering the metal ion-containing porous body in a hydrogen atmosphere, or
Reducing the metal ion-containing porous body with a reducing agent to convert the metal ions to metal and then sintering in an oxygen atmosphere,
The production method according to any one of claims 1 to 3, which is carried out by any of the methods.
5. A porous metal body obtained by the production method according to claim 1, wherein the skeleton diameter is in the range of 0.001 μm to 5 μm.
A method for producing a metal-containing porous body,
The manufacturing method includes:
The metal ion-containing porous body in which the chelate group and metal ion of the raw material porous body modified with a functional group having a chelate group, which is monolithic, and containing a polymer as a main component is coordinated, is subjected to a reduction treatment, Including a step of obtaining a metal-containing porous body,
The metal ion-containing porous body is modified with a functional group having a chelate group, the monolithic raw material porous body containing a polymer as a main component is brought into contact with metal ions, and the chelate group of the raw material porous body Obtained by coordination bond with the metal ion,
The monolithic porous material containing a polymer as a main component, modified with a functional group having a chelate group, is converted into a monolithic porous material containing a polymer as a main component, and a functional group having a chelate group. Obtained by modifying with a compound containing,
The monolithic porous body containing a polymer as a main component,
A polymer solution is prepared by dissolving the polymer in a liquid containing water and a poor solvent for the polymer, which is miscible with water and excluding water, and water.
Separating the polymer precipitate deposited from the polymer solution;
Obtained by drying the polymer precipitate,
The polymer is
A homopolymer of esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
A copolymer containing esters of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a hydroxy group, a carboxyl group, an oxiranyl group and a halogen atom;
Homopolymers of methacrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of hydroxy, carboxyl, oxiranyl and halogen atoms, and methacrylic acid and hydroxy 1 or more selected from the group consisting of copolymers containing esters with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, a carboxyl group, an oxiranyl group and a halogen atom The manufacturing method which is.
The compound containing a functional group having a chelate group is an amine, a condensate of amine and ethylenediaminetetraacetic acid, a condensate of amine and epichlorohydrin, a condensate of amine and iminodiacetic acid, an amine and bromoacetic acid. The production method according to claim 6, which is at least one selected from the group consisting of a condensate and a compound having a functional group of phosphine, thiol and / or carbene.
The metal ions are gold, silver, platinum, palladium, nickel, copper, manganese, rhodium, cobalt, ruthenium, rhenium, molybdenum, tin, zinc, iron, titanium, vanadium, chromium, osmium, iridium, bismuth, cadmium and gallium. The production method according to any one of claims 6 to 8, wherein the production method is at least one selected from the group consisting of ions.
9. A metal-containing porous material obtained by the production method according to claim 6, wherein the skeleton has a skeleton diameter in the range of 0.001 μm to 5 μm.