JP2008161857A - Metal-containing colloidal grain-carrier, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a metal-containing colloidal grain carrier by an operation simpler than a conventional method for producing a metal-containing colloidal grain carrier where metal-containing colloidal grains are carried on a carrier substance, and to provide a metal-containing grain carrier obtained by the method. <P>SOLUTION: The metal-containing colloidal grain carrier is obtained by carrying one or more of metal-containing colloidal grains on an inorganic carrier substance, wherein the average grain diameter of the metal-containing colloidal grains carried on the carrier substance lies in the range of 2 to 200 nm. The method for producing a metal-containing colloidal grain carrier is characterized in that metal-containing colloidal grains with the average grain diameter of 2 to 200 nm are carried on a carrier substance in the presence of the fourth period element ions (selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge and As), the fifth period ions (selected from Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn and Sb) or the sixth period ions (selected from Hf, Ta, W, Re, Os, Pt, Au, Ir, Hg, TI, Pb and Bi). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a metal-containing colloidal particle-carrying carrier on which metal-containing colloidal particles are carried, and a metal-containing colloidal particle-carrying carrier obtained by the production method.

  Catalysts are used in various fields such as organic substance synthesis and purification of automobile exhaust gas, in addition to promoting reaction in fuel cells. As for such catalysts, most of them are porous materials such as oxides and carbons such as alumina, silica, etc., which support platinum, rhodium, etc., and multi-component catalysts in which a plurality of metals are supported. Are known. As the carrier material, silica, zeolite, silica-alumina composite, ceria and the like are used.

  As a typical method for producing a conventional catalyst in which colloidal particles containing a metal are supported on a support material, as a representative one, a carrier made of a porous metal oxide is coated with dinitrodiammine platinum, chloroplatinic acid, rhodium nitrate. A method of impregnating such a metal salt solution and firing in a reducing atmosphere is known. Also, for the multi-component catalyst, there is a production method in which a solution of a plurality of metal salts to be supported is prepared, a carrier is mixed with this, a plurality of metal ions are adsorbed on the carrier, and then dried and calcined. Are known.

  As a method for producing a catalyst in which colloidal particles containing a metal are supported on a carrier material, including the production method described above, Patent Document 1 discloses catalytic activity on the surface of fine carrier particles made of a metal oxide or the like. And depositing the carrier particles by irradiating the raw material with light having a wavelength matching an absorption band of at least one raw material for synthesizing the carrier, and depositing the carrier particles. The carrier particles and the raw material for depositing the metal particles having catalytic activity are simultaneously irradiated with light having a wavelength that matches the absorption band of the raw materials to deposit the metal particles on the surface of the carrier particles. There is disclosed a method for producing a catalyst comprising a step and a step of selectively collecting the deposited metal particles.

  In Patent Document 2, metal particles and / or metal compound particles are adsorbed and supported on a solid support together with an organic polymer compound having a number average molecular weight of 3,000 to 300,000 which protects the particles substantially individually and separately. Metal particles and / or metal compound particles characterized in that at least one of the polymer compound and the solid support does not have a functional group capable of acting to form a covalent bond and form a chemical bond therebetween. The supported composite and the method for producing the same include a dispersion medium, metal particles and / or metal compound particles, and an organic polymer compound having a number average molecular weight of 3,000 to 300,000 having a protective colloid particle action, and the particles are contained in the dispersion medium. Dispersing to form colloidal particles, and providing a colloidal particle dispersion comprising the polymer adsorbed on the particles and protecting the particles substantially individually and separately as protective colloidal particles. At least one of the polymer compound and the solid support does not have a functional group that can act to form a covalent bond and form a chemical bond therebetween, thus Metal particles characterized by forming a particle-supported complex formed by adsorbing the particles protected by the polymer compound to the solid support, and isolating the obtained complex from the dispersion medium, and A method for producing a metal compound particle-supported composite is disclosed.

In Patent Document 3, propargyl alcohol is added to a solution containing a carrier on which metal-containing ions and metal particles generated by reduction of the metal-containing ions are supported, and a reaction product of the metal-containing ions and propargyl alcohol is added to the carrier. After being supported on the substrate, the support is heat-treated in a reducing gas containing hydrogen gas to reduce a reaction product of metal-containing ions and propargyl alcohol on the support to metal-containing colloidal particles. A method for producing a highly dispersed metal-containing colloidal particle supported catalyst is disclosed.

  In Patent Document 4, in the presence of a solid substance serving as a carrier, a liquid having a reducing ability or a liquid in which a reducing substance is dissolved, containing a metal compound or ions, is irradiated with microwaves, or a metal compound. Alternatively, a metal-containing colloidal particle is attached to the surface, characterized by the presence of a solid substance serving as a carrier after microwave irradiation of a liquid containing a reducing ability or a liquid containing a reducing substance containing ions. A method for producing a metal-containing colloidal particle adhesion carrier is disclosed.

  Patent Document 5 contains at least one second element of Group 2B, Group 3B, Group 4B, Group 5B, Group 6B, and Group 8 of the Period 4 to Period 6 of the periodic table and gold. A metal particle carrier in which metal particles are supported on a carrier, and a production method comprising heat treating a carrier containing at least one of gold and its compound and at least one of a second element and its compound as a production method thereof A method is disclosed.

  In Patent Document 6, aluminum nitride particles are fired in the presence of air or oxygen to form an aluminum oxide layer on the surface of the aluminum nitride particles, and the nitride obtained by the aluminum oxide layer formation step. The aluminum particles are impregnated with an aqueous solution containing metal ions or metal particles and then dried to hold the metal catalyst on the aluminum nitride carrier, and the aluminum nitride carrier obtained in the holding step is air or oxygen A method for producing a catalyst in which a metal catalyst composed of a metal or a metal oxide is held on a carrier composed of aluminum nitride, which comprises a calcination step of calcination in the presence of the catalyst.

Patent Document 7 includes a step of producing a metal salt solution containing a metal salt of one or more transition metals, the metal salt solution, an organic substance, and one or more metal oxides. While dispersing a porous carrier in a solvent and forming a complex complex composed of one or more transition metal ions having 10 to 50000 atoms and an organic substance bonded to the transition metal ion, A method for producing a catalyst is disclosed which comprises a step of supporting on the porous support and a step of firing the support on which the composite complex is supported.
JP 61-268359 JP-A-5-293383 JP-A-6-31181 JP 2003-13105 A JP 2003-53188 A JP 2003-144933 A JP 2005-270883 A

In the above-described conventional technology, not only a firing process is necessary, but also the reproducibility of catalyst activity and catalyst performance is not always satisfactory because the firing process is performed.
For this reason, the object of the present invention is to support metal-containing colloidal particles on a carrier material by a simple operation as compared with the conventional method for producing a metal-containing colloidal particle-supported carrier on which metal-containing colloidal particles are supported. Another object of the present invention is to provide a method for producing a metal-containing colloidal particle carrier and a metal-containing colloidal particle carrier obtained by this method.

Under such circumstances, the present inventors have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by adopting the following configuration of the present invention.
[1] A metal-containing colloidal particle-supported carrier in which one or more kinds of metal-containing colloidal particles are supported on an inorganic carrier material, wherein the average particle diameter of the metal-containing colloidal particles supported on the carrier material is 2 to 200 nm A metal-containing colloidal particle-supporting carrier characterized by being in the range of.
[2] The metal-containing colloidal particle-supporting carrier according to [1], wherein 10 ² to 10 ¹⁷ metal-containing colloidal particles are present per unit area (m ² ) on the inorganic carrier material.
[3] The metal-containing colloidal particle carrier according to [1] to [3], wherein the ratio of the metal-containing colloidal particle carrier contained in the metal-containing colloidal particle carrier is 1 to 50% by mass.
[4] The metal-containing colloidal particle-supporting carrier according to [1], wherein the metal-containing colloidal particles are selected from the following (1) or (2).
(1) Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc, Ru,
Metal-containing colloidal particles selected from Rh, Pd, Ag or Au,
(2) Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc, Ru,
A composite metal-containing colloidal particle comprising two or more selected from Rh, Pd, Ag, Au, or Pt.
[5] The metal-containing colloidal particle support according to [1] to [4], wherein the inorganic carrier material contains one or more selected from Si, Al, C, Ti, Zr or Ce. Carrier.
[6] Fourth periodic element ions (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn
, Ga, Ge, or As), fifth periodic ion (however, selected from Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, or Sb) or sixth periodic ion In the presence of Hf, Ta, W, Re, Os, Pt, Au, Ir, Hg, TI, Pb or Bi, metal-containing colloidal particles having an average particle diameter of 2 to 200 nm are supported on the carrier material. A method for producing a metal-containing colloidal particle-supporting carrier, characterized by comprising: [7] The suspension of the carrier material contains 2 to 100 parts by weight of the fourth periodic element ion, the fifth periodic element ion or the sixth periodic element ion in terms of metal element with respect to 100 parts by weight of the carrier material. And 5 to 180 parts by weight of metal-containing colloidal particles having an average particle diameter of 2 to 200 nm are added to and mixed with the ion-containing suspension at 15 to 40 ° C. with respect to 100 parts by weight of the carrier substance. A method for producing a metal-containing colloidal particle-supporting carrier.
[8] The metal-containing colloidal particle according to [6] or [7], wherein the fourth periodic element ion, the fifth periodic element ion, or the sixth periodic element ion is Pt ion, Au ion, Sn ion, or Pd ion. A method for producing a carrier.
[9] The Pt ion, Au ion, Sn ion, and Pd ion are chloroplatinic acid, platinum chloride (IV
) Potassium acid, Sodium platinum chloride (IV), Tetranitroplatinum (II) potassium, Hexahydroxoplatinum (IV) sodium hydrate, Dinitrodiammine platinum nitrate, Dinitrodiammine platinum ammonia and Tetraammine dichloroplatinum hydrate One or more platinum compounds selected from the group consisting of chloroauric acid, sodium gold sulfite, potassium gold cyanide and sodium gold cyanide, one or more gold compounds, stannous sulfate One selected from the group consisting of one or more tin compounds selected from the group consisting of stannous oxide and stannous chloride, palladium chloride, palladium nitrate, palladium sulfate, palladium citrate, palladium acetate, etc. Alternatively, the metal content of [8], which is obtained from two or more palladium compounds A method for producing a carrier having colloidal particles.
[10] The method for producing a metal-containing colloidal particle-supporting carrier according to [6] to [9], wherein the carrier material contains one or more selected from Si, Al, C, Ti, Zr or Ce. .
[11] The metal-containing colloidal particle-supporting carrier according to [1] to [5], which is produced by the production method of [6] to [10].

  According to the production method of the present invention, metal-containing colloidal particles can be supported on a carrier material by a simple means without going through a firing step.

  Hereinafter, the metal-containing colloidal particle-supporting carrier and the production method thereof according to the present invention will be described in detail.

[Metal-containing colloidal particle support]
Inorganic carrier material The carrier material used in the present invention is not particularly limited as long as it is a material capable of supporting metal-containing colloidal particles. Usually, those containing one or more selected from Si, Al, C, Ti, Zr or Ce are used. This carrier material may be amorphous or crystalline, and may be either a synthetic material or a natural mineral. Normally, oxides are used for Si, Al, Ti, Ti, Zr, and Ce, and carbon is used for C. The oxide may be a complex oxide, and may further contain components such as Na, K, and Fe. Specific examples of such carrier materials include silica particles, silica-alumina particles, carbon particles, zeolite particles (Y-type, A-type, mordenite type, ZSM-5 type, etc., which may be natural products or synthetic products), ceria. (Cerium oxide) particles, kaolin particles, smectite particles, vermiculite particles, mica pieces and the like can be mentioned, but are not limited thereto.

  The shape of the carrier material is not particularly limited. The average particle size of the support material is not particularly limited as long as it is equal to or larger than the average particle size of the supported metal-containing colloidal particles. When the carrier substance is in the form of particles, for example, the average particle diameter measured by image analysis described later is preferably 30 nm to 10 μm, and more preferably 30 nm to 5 μm.

The average particle size of the carrier substance is preferably 5 times or more the average particle size of the metal-containing colloidal particles described later. A carrier substance having a particle size in the above range can be easily obtained, and the metal-containing colloidal particles can be easily uniformly supported on the surface by the production method of the present invention. If the secondary particle diameter is in the above range, the metal-containing colloidal particles can be used even in an aggregated state, but it is preferable that they are monodispersed as much as possible. Note that this is not the case when the carrier substance is not particulate. The specific surface area of the carrier material is not particularly limited, but is preferably 10 to 1000 m ² / g, and more preferably 180 to 900 m ² / g, for example. When the specific surface area of the support material is in the above range, a metal-containing colloidal particle-supported support having excellent catalytic activity can be obtained.

Metal-containing colloidal particles In the present invention, metal-containing colloidal particles are supported on the carrier material.
The average particle size of the metal-containing colloidal particles is an average particle size determined by image analysis described later, and is preferably in the range of 2 to 200 nm, more preferably in the range of 2 to 100 nm.

  When the average particle size of the metal-containing colloidal particles is within the above range, the metal-containing colloidal particles can be supported on the carrier material in a sufficiently dispersed state. On the other hand, when the average particle size is smaller than the lower limit, it is not easy to produce, and when the upper limit is exceeded, the carrier material may not be sufficiently dispersed and easily supported. The amount of metal-containing colloidal particles that cannot contribute to the reaction may increase.

  The metal-containing colloidal particles in the present invention are selected from a single metal or metal compound. Here, examples of the metal compound include metal oxides, composite metals, metal hydroxides, and the like. The metal species constituting the metal-containing colloidal particles are selected from those capable of preparing a metal-containing colloidal particle dispersion having an average particle diameter of 1 to 200 nm.

Specifically, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, T
Metal-containing colloidal particles selected from metals selected from c, Ru, Rh, Pd, Ag or Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc, Ru, Rh A composite metal-containing colloidal particle composed of two or more selected from Pd, Ag, Au or Pt is preferably used. The composite metal may be an alloy, an eutectic, or simply a mixture. In particular, colloidal particles containing Pd, Cu, Au, or Ag are recommended from the viewpoint of use. Also, colloidal particles containing Pd and Cu are preferably used.

Such metal-containing colloidal particles can be generally prepared by subjecting the metal salt, alkoxide, or complex to reduction treatment, hydrolysis treatment, or the like.
The proportion of the metal-containing colloidal particle-supported carrier contained in the metal-containing colloidal particle-supporting carrier varies depending on the type of metal, but is selected according to the requirements of the application to be used and is particularly limited. is not. Usually, it is desirable to be in the range of, for example, 1 to 50 mass%, preferably 3 to 20 mass%. When it is supported in this range, for example, the catalytic action due to the action of metal-containing colloidal particles tends to be at a practical level, which is excellent.

The metal-containing colloidal particles are 10 ² to 10 ² per unit area (m ² ) on the inorganic carrier material.
Desirably, 10 ¹⁷ / m ² , preferably 10 ³ to 10 ¹⁵ / m ² are present.
By being supported in such a range, the catalytic effect based on the metal-containing colloidal particles and the like can be easily expressed stably. On the other hand, when the amount is out of the range, the effect of supporting the metal-containing colloidal particles is not sufficiently exhibited, and the catalytic effect or the conductive effect may be weak. In addition, at most, the effect based on the metal-containing colloidal particles tends to saturate and is not necessarily required. In some cases, the pores of the support material may be blocked.

The size of the metal-containing colloidal particle-supported carrier of the present invention is substantially determined by the size of the inorganic carrier material.
The metal-containing colloidal particle-supporting carrier of the present invention may be formed into a desired shape such as a pellet or a honeycomb by a known method, if necessary.

The metal-containing colloidal particle-supported carrier according to the present invention is a metal-containing colloidal particle-supported carrier in which one or more metal-containing colloidal particles are supported on an inorganic carrier material having an average particle diameter in the range of 30 nm to 10 μm, The average particle diameter of the metal-containing colloidal particles supported on the support material is in the range of 2 to 200 nm, and the metal-containing colloidal particles are 10 ² to 10 ¹⁷ per unit area (m ² ) on the inorganic support material. A metal-containing colloidal particle-supported carrier characterized by being present is a preferred embodiment.

The metal-containing colloidal particle-supporting carrier according to the present invention is produced by the following production method of the present invention.
[Method for producing metal-containing colloidal particle-supported carrier]
The metal-containing colloidal particle-supported carrier of the present invention can be produced by supporting metal-containing colloidal particles having an average particle diameter of 1 to 200 nm on a carrier material in the presence of metal ions.

Preparation of carrier material suspension The carrier material used in the present invention is as described above.
In the present invention, the carrier material is usually used in a state suspended in water. A suspension of the carrier material can be obtained, for example, by adding deionized water to the carrier material and mixing at 95 ° C. for 1 hour. The amount of water used is preferably 900 to 99,900 parts by weight, more preferably 1,900 to 19,900 parts by weight with respect to 100 parts by weight of the carrier substance. The carrier material suspension thus obtained may be further diluted with water, if necessary, or may be concentrated by decantation. As the dilution water, deionized water is preferred. The carrier substance concentration of the suspension after dilution is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

Metal ions added next to the carrier material suspension, Period 4 element ions (where Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, selected from Ge or As), the 5 period ions (however, selected from Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn or Sb) or 6th period ions (however, Hf, Ta, W, Re, Os) , Pt, Au, Ir, Hg, TI, Pb or Bi). The content of metal ions is preferably 2 to 100 parts by weight, more preferably 3 to 80 parts by weight in terms of metal element, based on 100 parts by weight of the solid content of the carrier substance in the carrier substance suspension. When the content of the metal ions is less than the lower limit, even if the metal-containing colloidal particles are added, a sufficient supporting effect on the support substance cannot be obtained, and when the upper limit is exceeded, further improvement of the supporting effect cannot be obtained, Economically unfavorable.

  In order to contain the amount of metal ions in the above range, a solution containing the amount of metal ions in the above range in terms of metal element may be added to the support material suspension, or the above in terms of metal element An amount of a metal compound capable of forming a proportion of metal ions may be added to the support material suspension to generate metal ions in the suspension.

A solution containing metal ions can be prepared by dissolving a metal compound capable of forming metal ions in a solvent.
The valence of the metal ion is not particularly limited. Of the metal ions, Pt ions, Au ions, Sn ions, and Pd ions are particularly preferable. Here, the Pt ions may be any of Pt ²⁺ , Pt ⁴⁺ and Pt ⁶⁺ . The Sn ion may be Sn ²⁺ or Sn ⁴⁺ .

  The platinum compound capable of generating Pt ions is not particularly limited as long as it forms Pt ions in the carrier material suspension. For example, chloroplatinic acid, potassium chloroplatinate (IV), platinum chloride Examples include (IV) sodium acid, tetranitroplatinum (II) potassium, hexahydroxoplatinum (IV) sodium hydrate, dinitrodiammine platinum nitrate, dinitrodiammine platinum ammonia and tetraamminedichloroplatinum hydrate. These platinum compounds can be used individually by 1 type or in mixture of 2 or more types.

  Further, the compound capable of generating Au ions is not particularly limited as long as it forms Au ions in the above-mentioned carrier material suspension, and examples thereof include sodium gold sulfite, potassium gold cyanide and sodium gold cyanide. Can be mentioned. These gold compounds can be used alone or in combination of two or more.

  The compound capable of generating Pd ions is not particularly limited as long as it forms Pd ions in the carrier material suspension, and examples thereof include palladium chloride, palladium nitrate, palladium sulfate, palladium citrate, and palladium acetate. Etc. These palladium compounds can be used alone or in combination of two or more.

  The compound capable of generating Sn ions is not particularly limited as long as it forms Sn ions in the carrier material suspension. For example, stannous sulfate, stannous oxide, stannous chloride, etc. Is mentioned. These lead compounds can be used individually by 1 type or in mixture of 2 or more types.

The metal compound that generates metal ions is usually dissolved in a solvent and added to the suspension.
The solvent used for the solution containing a metal ion is not particularly limited as long as it does not show reactivity with the metal and can dissolve the metal compound.

Such solvents include
water;
Alcohols such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol;
Ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, cyclohexanone;
Amides such as N, N-dimethylformamide and N, N-dimethylacetamide;
Ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran;
Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether;
Glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate;
Esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Aliphatic hydrocarbons such as hexane, heptane, iso-octane, cyclohexane;
Halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene;
Sulfoxides such as dimethyl sulfoxide;
Examples thereof include pyrrolidones such as N-methyl-2-pyrrolidone and N-octyl-2-pyrrolidone.

  The temperature at which the solution or metal compound containing metal ions is added to the carrier material suspension is preferably 15 to 40 ° C. If the temperature is low, the metal-containing colloidal particles may not be sufficiently supported, and if the temperature is too high, further improvement in the supporting efficiency is not seen, which is not economically preferable. Further, after the addition, it is preferable that the suspension is stirred and sufficiently mixed while maintaining the temperature within the above range. In particular, when a solid metal compound is added, it is necessary to sufficiently perform operations such as stirring until the metal compound is sufficiently dissolved and metal ions are generated.

  In the present invention, the metal-containing colloidal particles can be supported better by mixing the metal-containing colloidal particles in the suspension of the carrier material in the presence of the metal ions compared to the case where the metal ions are not present. . This is because metal ions are adsorbed on the components constituting the carrier material, particularly on the surface of the carrier material, and a kind of primer layer is formed on the surface of the carrier material, and the action of the primer layer, that is, metal-containing colloidal particles and metal ions. It is presumed that an adsorption reaction occurs between the two. These metal ions are preferably removed by washing together with unreacted metal-containing colloidal particles.

Metal-containing colloidal particles Examples of the metal-containing colloidal particles used in the present invention include those described above. The metal-containing colloidal particles are usually used in the state of a metal-containing colloidal particle dispersion in a state of being dispersed in water or an organic solvent. The concentration of the metal-containing colloidal particles in the metal-containing colloidal particle dispersion is not particularly limited, but is preferably 0.01% by mass or more, for example.

The method for preparing such a metal-containing colloidal particle dispersion is not particularly limited, but can be usually prepared by subjecting the metal salt, alkoxide, or complex to reduction treatment, hydrolysis treatment, or the like.

  The added amount of the metal-containing colloidal particles is preferably 5 to 180 parts by weight, more preferably 10 to 180 parts by weight with respect to 100 parts by weight of the carrier substance. When the amount of the metal-containing colloidal particles is within the above range, the metal-containing colloidal particles can be supported on the carrier material in a sufficiently dispersed state. On the other hand, when the addition amount is less than 5 parts by weight, there is no problem with the loading of the metal-containing colloidal particles, but the loading amount of the metal-containing colloidal particles decreases, and sufficient effects such as catalytic action by the metal-containing colloidal particles cannot be obtained. Sometimes. Moreover, even if the addition amount exceeds 180 parts by weight, the loading amount is hardly increased, which is economically undesirable.

  Although the temperature at the time of adding and mixing a metal containing colloidal particle is not specifically limited, 15-40 degreeC is preferable. If it is less than 15 degreeC, a metal containing colloid particle may not fully be supported, and practicality may fall. If it exceeds 40 ° C., further improvement of the supporting effect is not recognized, which is economically undesirable.

In the mixing, it is desirable to stir usually for 5 minutes or longer, preferably for 10 minutes or longer. If necessary, the stirring may be performed for usually up to about 3 hours, preferably up to about 1 hour.
After the mixing operation, the suspension containing the metal-containing colloidal particle-supporting carrier may be diluted with water as necessary. Usually, it can be diluted with up to about 250,000 parts by weight of water with respect to 100 parts by weight of the metal-containing colloidal particle-supporting carrier. Further, the metal-containing colloidal particle-supported carrier diluted with water is usually centrifuged, and washing is preferably repeated three times or more to remove remaining ions, and the metal-containing colloidal particle-supported carrier is separated and purified. Thereafter, the separated metal-containing colloidal particle-supported carrier is preferably dried usually at 80 to 100 ° C. for 1 to 20 hours.

  According to the production method of the present invention, the amount of metal-containing colloidal particles supported is 1 to 50% by mass with respect to the whole metal-containing colloidal particle-supported carrier, and the metal-containing colloidal particles are very well dispersed on the surface of the carrier material. A colloidal particle-containing carrier can be obtained. The amount of the metal-containing colloidal particles supported is adjusted by appropriately adjusting the production conditions such as the temperature at which the metal ions are contained, the content of the metal ions, the temperature at the time of mixing the metal-containing colloidal particles, and the amount of the metal-containing colloidal particles mixed. Can be controlled. In particular, the supported amount is preferably 5 to 30% by mass.

  In the production method of the present invention, since the metal-containing colloidal particles already in the metal state are used, a metal-containing colloidal particle-supported carrier can be obtained simply by being supported on a carrier material. For example, in the ion adsorption reduction method, it is necessary to cause Pt ions to be present on a carrier and to calcinate and reduce them to form platinum metal. However, the production method of the present invention is simpler than this. I can say that.

  The obtained metal-containing colloidal particle-supported carrier may be formed into a desired shape such as a pellet or a honeycomb by a known method, if necessary. In addition, the carrier substance to be dispersed in the suspension may be used after being formed into a desired shape.

  The metal-containing colloidal particle-supported carrier of the present invention exhibits high catalytic activity when used, for example, as a catalyst comprising a metal-containing colloidal particle-supported carrier, and has good reproducibility of catalyst performance. Moreover, as a use other than the catalyst, it can be applied as a material in which metal-containing colloidal particles are favorably dispersed on a carrier and used in an application utilizing electric characteristics or magnetic characteristics.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all.

[1] Specific surface area measurement sample by BET method (Zeolite) 50 ml of a dispersion of HNO ₃ was adjusted to pH 3.5, 40 ml of 1-propanol was added, and the sample was dried at 110 ° C. for 16 hours. A sample for measurement was obtained by firing in an oven at 500 ° C. for 1 hour. And the specific surface area was measured by the BET 1-point method from the amount of adsorption | suction of nitrogen using the nitrogen adsorption method (BET method) using the specific surface area measuring apparatus (The product made from Yuasa Ionics, model number multisorb 12).

  Specifically, 0.5 g of a sample is put in a measurement cell, degassed for 20 minutes at 300 ° C. in a mixed gas stream of 30% by volume of nitrogen and 70% by volume of helium, and then the sample is mixed with the above mixed gas stream. The liquid nitrogen temperature is maintained in the sample, and nitrogen is allowed to equilibrate to the sample. Next, the sample temperature was gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that time was detected, and the specific surface area of the sample (zeolite) was measured using a calibration curve prepared in advance.

[2] Measurement of the number of metal-containing colloidal particles per unit area Obtained by photographing a sample (metal-containing colloid-carrying carrier) at a magnification of 250,000 using a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.) The number of metal-containing colloidal particles supported on the surface of 40 nm square is measured for any 50 particles in the photographic projection figure, and the metal per unit area [m ² ] is calculated from the average value. The number of contained colloidal particles was determined.

[3] Composition analysis sample of metal-containing colloidal particle-supported carrier (metal-containing colloid-supported carrier) was fired at 600 ° C., the residue was melted with an alkaline melting agent, and then dissolved in 28% (mass)% aqueous hydrochloric acid The solution was diluted with pure water, and then measured with an ICP inductively coupled plasma emission spectrometer SPS1200A (manufactured by Seiko Electronics Co., Ltd.).

[4] Method for measuring average particle diameter by image analysis The average particle diameter of metal-containing colloidal particles or carriers was measured by the following method.
With a scanning electron microscope (manufactured by Hitachi, Ltd., H-800), the particle diameter is measured for any 50 particles in a photograph projection view obtained by photographing a sample particle at a magnification of 250,000 times, The average value was obtained.

[Synthesis Example 1A]
Carbon black 0.2g Preparation solids weight of the activated carbon suspension (Lion Co., Ltd., trade name: Ketjenblack EC, DBP oil absorption: 360 cm ^3/100 g, a specific surface area: 850 meters ² / g, primary particle (Diameter: 39.5 nm) was dispersed in water boiled at 95 ° C. to obtain a dispersion of 7% by mass (solid content) of carbon black. This dispersion was diluted with deionized water and stirred to prepare a carbon black suspension (carbon black solid content 5 mass%).

[Synthesis Example 1B]
Synthesis of palladium-copper colloidal particle dispersion A solution in which 122 g of ferrous sulfate as a reducing agent was dissolved in 219 g of an aqueous citric acid solution (concentration: 30% by mass) was prepared. Then, 341 g of this solution was added to a mixed aqueous solution of 39 g of an aqueous palladium nitrate solution (concentration 20% by mass) and 26 g of an aqueous copper nitrate solution (concentration 20% by mass) at room temperature and mixed thoroughly to obtain palladium-copper fine particles (average A dispersion having a particle diameter of 3 nm) was prepared.

[Example 1]
15 g of a ferrous chloride aqueous solution having a Fe ion concentration of 1 mass% was added to 100 g of the carbon black suspension prepared in Synthesis Example 1A, and the mixture was stirred at 20 ° C. for 5 minutes. To this mixed suspension, 16.6 g of palladium copper colloidal particle dispersion obtained in Synthesis Example 1B (average particle size: 3 nm, 0.5 g in terms of palladium-copper) was added. The pH of the mixed suspension after addition of palladium-copper colloidal particles was 2.5.

The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. By removing the palladium copper colloidal particles, chlorine ions, Fe ions, etc. remaining in the suspension by repeating the centrifugation and washing operations three times, and then drying the obtained solid at 90 ° C. for 10 hours. Carbon supported by palladium-copper colloidal particles having an average particle diameter of 3 nm was obtained. The number of palladium-copper colloid particles present per unit area of carbon was 10 ⁷ particles / m ² .

[Example 2]
15 g of an aqueous palladium nitrate solution having a Pd ion concentration of 1% by mass was added to 100 g of the carbon black suspension prepared in Synthesis Example 1A and stirred at 20 ° C. for 5 minutes. To this mixed suspension, 16.6 g of palladium copper colloidal particle dispersion obtained in Synthesis Example 1B (average particle size: 3 nm, 0.5 g in terms of palladium-copper) was added. The pH of the mixed suspension after addition of palladium-copper colloidal particles was 2.5.

The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. After removing the palladium copper colloid particles, nitrate ions, Pd ions, etc. remaining in the suspension by repeating the centrifugation and washing operations three times, the obtained solid is dried at 90 ° C. for 10 hours. Carbon supported by palladium-copper colloidal particles having an average particle diameter of 3 nm was obtained. The number of palladium-copper colloidal particles present per unit area of carbon was 10 ⁹ / m ² .

[Example 3]
To 100 g of the carbon black suspension prepared in Synthesis Example 1A, 15 g of an aqueous copper nitrate solution having a Cu ion concentration of 1% by mass was added and stirred at 20 ° C. for 5 minutes. To this mixed suspension, 16.6 g of palladium copper colloidal particle dispersion obtained in Synthesis Example 1B (average particle size: 3 nm, 0.5 g in terms of palladium-copper) was added. The pH of the mixed suspension after addition of palladium-copper colloidal particles was 2.5.

The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. After removing the palladium copper colloid particles, nitrate ions, Cu ions, etc. remaining in the suspension by repeating the centrifugation and washing operations three times, the obtained solid is dried at 90 ° C. for 10 hours. Carbon supported by palladium-copper colloidal particles having an average particle diameter of 3 nm was obtained. The number of palladium-copper colloidal particles present per unit area of carbon was 10 ¹² particles / m ² .

[Example 4]
15 g of a chloroplatinic acid aqueous solution having a Pt ion concentration of 1% by mass was added to 100 g of the carbon black suspension prepared in Synthesis Example 1A and stirred at 20 ° C. for 5 minutes. To this mixed suspension, 16.6 g of palladium copper colloidal particle dispersion obtained in Synthesis Example 1B (average particle size: 3 nm, 0.5 g in terms of palladium-copper) was added. The pH of the mixed suspension after addition of palladium-copper colloidal particles was 2.5.

The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. Repeat the centrifugation and washing operations three times to remove palladium copper colloid particles, chlorine ions, Pt ions, etc. remaining in the suspension, and then dry the resulting solid at 90 ° C. for 10 hours. As a result, carbon supported by palladium-copper colloidal particles having an average particle diameter of 3 nm was obtained. The number of palladium-copper colloid particles present per unit area of carbon was 10 ⁷ / m ² .

[Example 5]
15 g of a tin chloride aqueous solution having a Sn ion concentration of 1% by mass was added to 100 g of the carbon black suspension prepared in Synthesis Example 1A and stirred at 20 ° C. for 5 minutes. To this mixed suspension, 16.6 g of palladium copper colloidal particle dispersion obtained in Synthesis Example 1B (average particle size: 3 nm, 0.5 g in terms of palladium-copper) was added.

The pH of the mixed suspension after addition of palladium-copper colloidal particles was 2.5.
The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. By removing the palladium copper colloid particles, chlorine ions, Sn ions, etc. remaining in the suspension by repeating the centrifugation and washing operations three times, and then drying the obtained solid at 90 ° C. for 10 hours. Carbon supported by palladium-copper colloidal particles having an average particle diameter of 3 nm was obtained. The number of palladium-copper colloidal particles present per unit area of carbon was 10 ⁸ particles / m ² .

[Example 6]
15 g of a chloroauric acid aqueous solution with an Au ion concentration of 1% was added to 100 g of the carbon black suspension prepared in Synthesis Example 1A, and the mixture was stirred at 20 ° C. for 5 minutes. To this mixed suspension, 16.6 g of palladium copper colloidal particle dispersion obtained in Synthesis Example 1B (average particle size: 3 nm, 0.5 g of palladium copper alloy content) was added.

The pH of the mixed suspension after addition of palladium-copper colloidal particles was 2.5.
The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. By removing the palladium copper colloidal particles, chlorine ions, Au ions, etc. remaining in the suspension by repeating the centrifugation and washing operations three times, and then drying the obtained solid at 90 ° C. for 10 hours. Carbon supported by palladium-copper colloidal particles having an average particle diameter of 3 nm was obtained. The number of palladium-copper colloidal particles present per unit area of carbon was 10 ⁹ / m ² .

[Synthesis Example 2A]
Preparation of zeolite suspension The zeolite suspension used in the examples and comparative examples was prepared as follows. Ultrastable Y-type zeolite (powder, average particle size = 2 μm, SiO ₂ / Al ₂ O ₃ (molar ratio) = 5, Na ₂
5% by mass of O, 5.0% by mass of NFA (aluminum out of lattice), specific surface area of 600 m ² / g, lattice constant of 24.57 mm, and 12-membered ring structure) were prepared, and a dry weight of 100 g was collected. After adding 833 g of water, stirring with a three-one motor for 5 minutes, and then crushing with a homogenizer, an ultrastable Y-type zeolite suspension (hereinafter referred to as “USY zeolite suspension”) was prepared. Next, deionized water was added so that the zeolite solid content concentration was 10% by mass.

[Synthesis Example 2B]
Synthesis of colloidal palladium particle dispersion A metal salt aqueous solution obtained by dissolving 25 g of palladium nitrate (10 g in terms of platinum metal) in 100 g of pure water was reduced with 596 g of a trisodium citrate aqueous solution having a concentration of 30% by mass as a complexing stabilizer. As an agent, 332 g of an aqueous ferrous sulfate solution having a concentration of 25% by mass was added and stirred and mixed at 20 ° C. in a nitrogen atmosphere to obtain a palladium loid solution in which palladium fine particles were dispersed in water. After this palladium colloidal particle dispersion was purified by ultrafiltration membrane washing, the concentration was adjusted to obtain a palladium colloidal particle dispersion having a concentration of 3% by mass in terms of platinum metal. The average particle diameter of the palladium colloid particles was 3 nm.

[Example 11]
2 g of the above USY zeolite suspension (zeolite solid content concentration 10% by mass) is weighed, and 14 g of chloroauric acid aqueous solution (containing 1% by mass of Au ions in the chloroauric acid aqueous solution) is added to the zeolite suspension. And stirred at 25 ° C. for 5 minutes.

Next, 6.7 g (solid content 0.2 g, average particle diameter 3 nm) of palladium colloid particle dispersion was added. The pH after the addition was 1.95. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes. Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Au ions, and the like, thereby preparing zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles present per unit area was 10 ¹⁴ particles / m ² .

[Example 12]
10 g of a chloroauric acid aqueous solution (Au ion was contained at 1 mass% in the chloroauric acid aqueous solution) was added to the same USY zeolite suspension as in Example 11, and the mixture was stirred at 25 ° C. for 5 minutes. Next, 47 g of palladium colloidal particle dispersion (solid content: 0.2 g, average particle diameter: 3 nm) was added.

The pH after the addition was 2.80. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes. Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Au ions, and the like, thereby preparing zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles present per unit area was 10 ¹⁴ particles / m ² .

[Example 13]
6 g of a chloroauric acid aqueous solution (containing 1 mass% of Au ions in the chloroauric acid aqueous solution) was added to the same USY zeolite suspension as in Example 11, and the mixture was stirred at 25 ° C. for 5 minutes. Next, 47 g (solid content 0.2 g, average particle diameter 3 nm) of palladium colloid particle dispersion was added. The pH after the addition was 3.54. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes. Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Au ions, and the like, thereby preparing zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles present per unit area was 10 ¹⁴ particles / m ² .

[Example 14]
2 g of a chloroauric acid aqueous solution (containing 1 mass% of Au ions in the chloroauric acid aqueous solution) was added to the same USY zeolite suspension as in Example 11, and the mixture was stirred at 25 ° C. for 5 minutes. Next, 47 g (solid content 0.2 g, average particle diameter 3 nm) of palladium colloid particle dispersion was added. The pH after the addition was 4.01. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes.

Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Au ions, and the like, thereby preparing zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles present per unit area was 10 ¹³ particles / m ² .

[Example 15]
14 g of a chloroplatinic acid aqueous solution (containing 1% by mass of Pt ions in the chloroplatinic acid aqueous solution) was added to the same USY zeolite suspension as in Example 11, and the mixture was stirred at 25 ° C. for 5 minutes. Next, 47 g (solid content 0.2 g, average particle diameter 3 nm) of palladium colloid particle dispersion was added. The pH after the addition was 2.01. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes.

Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Pt ions, and the like to prepare zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles per unit area was 10 ¹² particles / m ² .

[Example 16]
10 g of a chloroplatinic acid aqueous solution (containing 1 mass% of Pt ions in the chloroplatinic acid aqueous solution) was added to the same USY zeolite suspension as in Example 11, and the mixture was stirred at 25 ° C. for 5 minutes. Next, 47 g of palladium colloidal particle dispersion (platinum solid content 0.2 g, average particle diameter 3 nm) was added. The pH after the addition was 2.01. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes.

Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Pt ions, and the like to prepare zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles present per unit area was 10 ¹¹ particles / m ² .

[Example 17]
6 g of a chloroplatinic acid aqueous solution (containing 1 mass% of Pt ions in the chloroplatinic acid aqueous solution) was added to the same USY zeolite suspension as in Example 11, and the mixture was stirred at 25 ° C. for 5 minutes. Next, 47 g (solid content 0.2 g, average particle diameter 3 nm) of palladium colloid particle dispersion was added. The pH after the addition was 3.55. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes.

Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Pt ions, and the like to prepare zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles per unit area was 10 ¹⁰ particles / m ² .

[Example 18]
2 g of a chloroplatinic acid aqueous solution (containing 1 mass% of Pt ions in the chloroplatinic acid aqueous solution) was added to the same USY zeolite suspension as in Example 11, and the mixture was stirred at 25 ° C. for 5 minutes. Next, 47 g (solid content 0.2 g, average particle diameter 3 nm) of palladium colloid particle dispersion was added. The pH after the addition was 4.03. After stirring at 25 ° C. for 40 minutes, solid-liquid separation was performed with a centrifuge, and 500 g of water was further added, followed by washing for 3 minutes. Centrifugation and washing were repeated three times to remove remaining palladium colloid particles, Cl ions, Pt ions, and the like to prepare zeolite with palladium colloid particles supported on the surface. The solid was dried at 90 ° C. for 5 hours to obtain palladium colloidal particle-supported zeolite. The number of metal-containing colloidal particles present per unit area is 10 ⁹
Pieces / m ² .

[Nitrate nitrogen treatment performance test]
61.3 g of sodium nitrate (manufactured by Kanto Chemical Co., Ltd .: special grade) was dissolved in pure water to prepare 25 kg of nitrate nitrogen-containing water. At this time, the content of nitrate nitrogen was 400 ppm as N. Next, nitrate nitrogen-containing water is put into a water tank of an ultrafine bubble reducing gas generator (manufactured by Skillkit Co., Ltd .: Microbubble generator), and a catalyst sample 1000 g is circulated while circulating the nitrate nitrogen-containing water. Was dispersed. At this time, the dispersion concentration of the catalyst sample in the nitrate nitrogen-containing water is 3.8% by mass.

Subsequently, ultrafine bubbles of hydrogen gas were blown in to treat the nitrate-containing water.
At this time, the liquid temperature was maintained at 25 ° C., and the water tank was stirred at 200 rpm. The microbubble generator has a liquid circulation rate of 70 L / min, a liquid pressure of 0.45 MPa, a hydrogen pressure of 0.45 MPa,
The flow rate of hydrogen was injected at a condition of 0.37 NL / min, and during the treatment of nitrate nitrogen, the pH of the nitrate nitrogen-containing water was adjusted to a range of 5 to 6 with sulfuric acid having a concentration of 1% by mass. A treatment solution was collected every 5 minutes after the start of supply of hydrogen ultrafine bubbles, and a nitrogen analyzer (Blanlube Co., Ltd. product: AAS-III) was collected.
) To analyze nitrate nitrogen (NO ₃ + NO ₂ ) and NH ₃ .

The reduction of nitrate nitrogen was completed in 130 minutes (when NO ₃ + NO ₂ became 0 ppm), and the concentration of by-product NH ₃ , the amount of N ₂ produced, and the hydrogen unused rate were measured.
When the carbon supported by the palladium-copper colloidal particles having an average particle diameter of 3 nm prepared in Example 1 was used as the catalyst sample, N ₂ production amount 48.8%, NH _{3 by-} product production amount 10.0%, unused 41.2% Met.

When the catalyst sample was [carbon loaded with palladium-copper colloidal particles prepared by a method not using metal ions], the amount of N ₂ produced was 37.1%, the amount of NH _{3 by} -product was 9.8%, Usage was 53.1%.

Claims (11)

  A metal-containing colloidal particle-supported carrier in which one or more kinds of metal-containing colloidal particles are supported on an inorganic carrier material, wherein the average particle diameter of the metal-containing colloidal particles supported on the carrier material is in the range of 2 to 200 nm. A metal-containing colloidal particle-supporting carrier characterized by being. ^2. The metal-containing colloidal particle-supporting carrier according to claim 1, wherein 10 ² to 10 ¹⁷ metal-containing colloidal particles are present per unit area (m ² ) on the inorganic carrier material.   The metal-containing colloidal particle carrier according to any one of claims 1 to 3, wherein a ratio of the metal-containing colloidal particle carrier contained in the metal-containing colloidal particle carrier is 1 to 50% by mass. The metal-containing colloidal particle-supporting carrier according to claim 1, wherein the metal-containing colloidal particle is selected from the following (1) or (2).
(1) Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc, Ru,
Metal-containing colloidal particles selected from Rh, Pd, Ag or Au,
(2) Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc, Ru,
A composite metal-containing colloidal particle comprising two or more selected from Rh, Pd, Ag, Au, or Pt.   The metal-containing colloidal particle-supporting carrier according to any one of claims 1 to 4, wherein the inorganic carrier material contains one or more selected from Si, Al, C, Ti, Zr, or Ce.   Fourth periodic element ions (however, selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge or As), fifth periodic ions (however, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn or Sb) or sixth periodic ion (however, Hf, Ta, W, Re, Os, Pt, Au, Ir, Hg, TI, Pb or Bi) A metal-containing colloidal particle-carrying carrier, wherein the carrier material is loaded with metal-containing colloidal particles having an average particle diameter of 2 to 200 nm.   In the suspension of the carrier material, the fourth periodic element ion, the fifth periodic element ion or the sixth periodic element ion is contained in an amount of 2 to 100 parts by weight in terms of a metal element with respect to 100 parts by weight of the carrier substance. Metal containing colloidal particles having an average particle diameter of 2 to 200 nm added to and mixed with ion containing suspension at 5 to 180 parts by weight with respect to 100 parts by weight of support material. A method for producing a colloidal particle-supporting carrier.   The metal-containing material according to claim 6, wherein the fourth periodic element ion, the fifth periodic element ion, or the sixth periodic element ion is a Pt ion, an Au ion, a Sn ion, or a Pd ion. A method for producing a colloidal particle-supporting carrier. The Pt ion, Au ion, Sn ion, and Pd ion are chloroplatinic acid, potassium platinum (IV) chloride, sodium chloroplatinate (IV), potassium tetranitroplatinum (II), sodium hexahydroxoplatinum (IV). One or more platinum compounds selected from the group consisting of Japanese, dinitrodiammine platinum nitrate, dinitrodiammine platinum ammonia and tetraamminedichloroplatinum hydrate, chloroauric acid, sodium gold sulfite, potassium gold cyanide and cyanide One or more gold compounds selected from the group consisting of gold sodium, one or more tin compounds selected from the group consisting of stannous sulfate, stannous oxide and stannous chloride, palladium chloride , Palladium nitrate, palladium sulfate, palladium citrate and palladium acetate One or manufacturing method of a metal-containing colloidal particles supporting carrier according to claim 8, characterized in that is obtained from two or more palladium compounds barrel.   The method for producing a metal-containing colloidal particle-carrying carrier according to any one of claims 6 to 9, wherein the carrier material contains one or more selected from Si, Al, C, Ti, Zr or Ce. .   Support material containing one or more selected from Si, Al, C, Ti, Zr or Ce, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc , A metal-containing colloidal particle-supporting carrier on which metal-containing colloidal particles containing a metal selected from Ru, Rh, Pd, Ag or Au are supported, wherein the content of the metal-containing colloidal particles is 1 to 50% by mass The metal-containing colloidal particle-supporting carrier according to claim 7, wherein the carrier is in the range of