TW201545827A - Porous structure and method for producing same, and method for producing composite metal nanoparticle - Google Patents

Abstract

The present invention provides a porous structure containing at least two kinds of metal ions and an organic ligand, said porous structure being characterized in that the at least two kinds of metal ions are homogeneously mixed together at an atomic level.

Description

Porous structure, method for producing the same, and method for producing composite metal nanoparticle Technical field

The present invention relates to a composite metal nanoparticle, a porous structure, and a method for producing the same, and more specifically relates to a composite metal nanoparticle in which two or more metals, metal oxides or metal ions are uniformly mixed at an atomic level, and porous Sex structure and its manufacturing method.

In addition, in this specification, MOF and PCP are collectively referred to as "PCP".

Background technique

A porous structure containing two or more kinds of metals is conventionally known.

For example, Non-Patent Document 1 can synthesize a PCP composed of two metals (Zn, Mn) by using a Na salt (Na ₂ NO ₂ -ip) of an organic ligand and increasing the reaction rate of PCP formation (ZnxMn1-xCID- 5). The map images of the respective elements of Zn and Mn of the obtained PCP showed different distributions, and it was found from the images of the overlapped two that only the element distribution (green) from Mn was observed (Fig. S15). The results show that the distributions of Zn and Mn are completely different, and some of the fields of ZnCID-5 and MnCID-5 overlap. Further, since the raw material uses Na salt, impurities may be mixed in the synthesized PCP.

Prior technical literature Non-patent literature

Non-Patent Document 1: J. Am. Chem. Soc. 2012, 134, 13341-13347

Summary of invention

An object of the present invention is to provide a porous structure in which two or more kinds of metals are uniformly mixed, a method for producing the same, and a method for producing composite metal nanoparticles such as alloy nanoparticles or composite oxide nanoparticles.

The inventors of the present invention have repeatedly reviewed the above-mentioned problems, and as a result, it has been found that two or more kinds of metal ions and organic ligands have different speeds for forming a porous structure, and in particular, by adding the pores according to the timing of the speeds. A metal having a slow rate of the structure and then a metal having a high rate of formation of the porous structure can be obtained, and a porous structure in which two or more kinds of metals are uniformly mixed at the atomic level can be obtained. Since the Na salt of the organic ligand used in Non-Patent Document 1 rapidly forms a porous structure, the difference in velocity of each metal ion is small, and therefore the composition ratio of the entire porous structure of two or more kinds of metals can be reduced. It is uneven, but at the atomic level, variations in the distribution of metal ions of the porous structure still occur.

On the other hand, the present invention has found that in order to uniformly mix metal ions in a porous structure in an atomic level, the porous structure is heated in the presence or absence of oxygen to decompose the organic ligand to oxidize the alloy or metal. The material is converted into a metal ion, whereby composite metal nanoparticles such as alloy nanoparticles of two or more kinds of metal or composite oxide nanoparticles of two or more kinds of metals can be obtained, and the alloy/composite oxide nanoparticle Similarly to the porous structure, it is a nanoparticle in which two or more kinds of metals are uniformly mixed at an atomic level.

The present invention provides the following porous structure, a method for producing the same, and a method for producing a composite metal nanoparticle.

Item 1. A porous structure comprising two or more metal ions and an organic ligand, and characterized in that two or more metal ions are uniformly mixed at an atomic level.

The porous structure according to Item 1, wherein the porous structural system is a Porous Coordination Polymer (PCP) or a Metal-Organic Framework (MOF).

Item 3. A method for producing a composite comprising composite metal nanoparticles and carbon in which two or more metals are uniformly mixed at an atomic level, and the production method is characterized by comprising the steps of: decompressing under vacuum; Heating the porous structure according to Item 1 or 2 in a reducing gas atmosphere, an inert gas atmosphere or an oxidizing gas atmosphere to thermally decompose an organic ligand to generate carbon, and convert the metal ion into a composite metal. a composite metal nanoparticle; wherein the composite metal nanoparticle is an alloy nanoparticle, a composite metal oxide nanoparticle, or a nanoparticle comprising an alloy portion and a composite metal oxide portion, and the composite metal oxide portion is It is composed of two or more kinds of metal oxides.

Item 4. A method for producing a composite comprising alloy nanoparticles in which two or more kinds of metals are uniformly mixed at an atomic level, and carbon, and the method of producing the same It is characterized in that the porous structure according to Item 1 or 2 is heated under vacuum, in a reducing gas atmosphere or in an inert gas atmosphere to thermally decompose an organic ligand to generate carbon, and to convert the metal ions into a metal to obtain an alloy. Nano particles.

Item 5. A method for producing a composite comprising nano particles and carbon, wherein the nano particles comprise a composite metal oxide portion in which two or more metals are uniformly mixed at an atomic level; and the manufacturing method is characterized in that Heating the porous structure according to Item 1 or 2 under pressure or an oxidizing gas to thermally decompose an organic ligand to generate carbon, and converting the metal ion into a metal oxide to obtain a composite metal oxide portion Rice particles.

Item 6. The production method according to Item 5, wherein the nanoparticle containing the composite metal oxide moiety is composed of a composite metal oxide.

Item 7. The production method according to Item 5, wherein the nanoparticle containing the composite metal oxide portion comprises an alloy portion and a composite metal oxide portion composed of two or more metal oxides.

Item 8. The production method according to any one of items 3 to 7, wherein the heating temperature is from 400 ° C to 600 ° C.

Item 9. A method for producing a porous structure according to Item 1 or 2, wherein the production method is characterized by a rate at which a porous structure is formed from each metal ion and an organic ligand. The timing of the addition of the metal ions is adjusted, whereby two or more kinds of metal ions are uniformly mixed at the atomic level.

The porous structure according to any one of items 3 to 9, wherein the two or more metals are selected from the group consisting of gold, platinum, silver, copper, rhodium, and tin. , palladium, rhodium, ruthenium, osmium, nickel, cobalt, zinc, iron, bismuth, A group consisting of magnesium, manganese, titanium, zirconium, hafnium and molybdenum.

The nanoparticle of the alloy or the composite oxide obtained by the production method of the present invention is not only a composition ratio of two or more kinds of metals as a whole, but also a nanoparticle having a uniform homogeneity evenly mixed in the atomic level in each nanoparticle. Therefore, it is expected to have excellent performance as a catalyst, a hydrogen absorbing material, an optical material, a magnetic material, and the like.

Simple description of the schema

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view schematically showing the structure of Co-Ni alloy nanoparticles prepared by the production method of the present invention.

Figure 2 shows the yield versus time for Co-MOF-74 and Ni-MOF-74. Synthesis speed: Co-MOF-74>Ni-MOF-74.

Fig. 3 is a view showing the steps for producing a MOF 74 in which Co and Ni are uniformly mixed in atomic order, depending on the result of the reaction rate of formation of MOF-74 of Fig. 2.

Figure 4 shows the XRD pattern of CoNi-MOF-74.

Figure 5 shows the STEM-EDS analysis of CoNi-MOF74. Co and Ni are homogeneously distributed in MOF74.

Figure 6 shows the XRD pattern of CoNi alloy nanoparticles.

Fig. 7 is a graph showing the particle size distribution of CoNi alloy nanoparticles (430-24h) determined by TEM image. Monodisperse nanoparticles were observed.

Figure 8 shows a HAADF-STEM image of CoNi alloy nanoparticle (430-24h).

Figure 9 is an enlarged view showing a portion of the CoNi alloy nanoparticle (430-24h) of Figure 8.

Figure 10 is a HAADF-STEM EDS analysis showing CoNi alloy nanoparticle (430-24h). It was confirmed that CoNi solid solution alloy nanoparticles were formed.

Form for implementing the invention

The composite metal nanoparticle obtained by the production method of the present invention is a nanoparticle in which two or more kinds of metals are uniformly mixed at an atomic level (Fig. 1).

Here, "two or more kinds of metals are uniformly mixed at the atomic level" means that two or more kinds of metal atoms (metal ions, metal atoms of metal or metal oxides) are uniformly present in the nanoparticles, and the distribution of each metal atom is not present. deviation.

The porous structure of the present invention contains two or more kinds of metal ions and is composed of the metal ions and organic ligands. The porous structure may also contain a relative anion. Examples of the porous structure include a porous coordination polymer (PCP), a metal-organic structure (MOF), and the like. The following exemplifies the relationship between the representative porous structure of different metal ions and the metal ions which may be contained therein.

MOF-74: Mg, Mn, Fe, Co, Ni, Cu, Zn

HKUST-1: Cu, Fe, Cr, Zn, Mo, Ru

UiO-66: Zr, Hf, Ti

MIL53: Al, Cr, Fe

MIL-88: Cr, Fe

MIL101: Al, Cr

ZIF-8: Zn, Co, Cu

In addition to the above, a porous structure containing a plurality of metal ions is also widely included in the porous structure of the present invention.

The preferred porous structure of the present invention has a structure of MOF-74, HKUST-1, UiO-66, MIL53, MIL-88, MIL101, and ZIF-8.

The metal atom (metal ion, metal or metal atom of metal oxide) of the porous structure, the alloy, and the composite metal oxide may, for example, be gold, platinum, silver, copper, ruthenium, tin, palladium, iridium, ruthenium or osmium. , nickel, cobalt, zinc, aluminum, chromium, iron, molybdenum, niobium, magnesium, manganese, titanium, zirconium, hafnium, etc., and copper, bismuth, nickel, cobalt, zinc, aluminum, chromium, iron, molybdenum, magnesium, Manganese, titanium, zirconium, hafnium, etc. are preferred.

The number of metals contained in the alloy or the composite oxide is two or more, for example, two to four, and preferably two to three. The combination of Co and Ni is particularly good.

In the present invention, composite metal nanoparticles comprising two or more metal/metal oxides can be obtained. The alloy/composite metal oxide nanoparticle of the present invention can exhibit behavior such as other single metals by changing the composition ratio of the metal, or even a metal combination which is usually difficult to become an alloy, close to the metal due to being fixed in the porous structure The alloy nanoparticles can also be easily fabricated by the position of the ions.

The preferred blend ratio (Morby ratio) of the present invention is shown below.

The molar ratio of the metal is, for example, 10:1 to 1:10, and is preferably 5:1 to 1:5, preferably 4:1 to 1:4, more preferably 3:1 to 1: 3, and the best is 2:1 to 1:2.

When the metal is three kinds, the lower limit of the blending amount of each metal is preferably 5 mol%, and more preferably 10 mol%.

Preferred ligands constituting the porous structure include, for example, benzene, naphthalene, anthracene, phenanthrene, anthracene, decane, anthracene, anthracene, 1,4-dihydronaphthalene, tetrahydronaphthalene, extended biphenyl, and benzene. a compound in which two, three or four carboxyl groups are bonded to an aromatic ring such as phenanthrene, ethylene naphthalene or ethane naphthalene (the aforementioned ligand may also be substituted with 1, 2 or 3 of the following substituents, and the substituent includes : halogen atom of F, Cl, Br, I, etc., nitro group, amine group, decylamino group, etc., cyano group, hydroxy group, methylenedioxy group, ethylenedioxy group, methoxy group, a linear or branched alkoxy group having 1 to 4 carbon atoms, such as an ethoxy group, a linear or branched carbon number such as a methyl group, an ethyl group, a propyl group, a tertiary butyl group or an isobutyl group. An alkyl group of 1 to 4, an SH group, a trifluoromethyl group, a sulfonic acid group, an amine methyl sulfonyl group, an alkylamino group such as a methylamino group, a dialkylamine group such as a dimethylamino group, etc.), fumaric acid An unsaturated divalent carboxylic acid such as maleic acid, citraconic acid or itaconic acid, which can be pyridinated And a nitrogen-containing aromatic compound (which may be substituted by 1, 2 or 3, with the above substituent) in which 2 or more of 4,4'-bipyridine or diazapine are coordinated to the nitrogen atom in the ring. When the ligand is neutral, it has the opposite anion required to neutralize the metal ion. Such relative anions may, for example, be chloride ions, bromide ions, iodide ions, sulfate ions, nitrate ions, phosphate ions, trifluoroacetate ions, methanesulfonate ions, toluenesulfonic acid ions, benzenesulfonate ions, Chlorate ion, etc.

The organic ligand constituting the porous structure of MOF, PCP or the like also contains a single-site ligand. When the proportion of the single-seat ligand becomes large, the size of the porous structure can be reduced, and the size of the resulting composite can be reduced. The single-seat ligand can be a carboxy-containing ligand such as benzoic acid, pyridine, A ligand having one coordinating nitrogen atom such as imidazole is exemplified, but is not limited thereto.

The porous structural system used in the present invention has two or more kinds of metal metal ions uniformly mixed at the atomic level. When two or more kinds of metal ions and organic ligands constituting the porous structure are simply mixed in a solvent such as water, a portion (for example, very small particles) rich in the porous structure of each metal ion is formed. When a porous structure is formed by equal aggregation, the distribution of each metal ion in the structure has an atomic level deviation, and when the porous structure having such uniformity is heat-treated, the composite metal is not uniformly mixed at the atomic level. Rice particles.

The inventors of the present invention conducted a review to obtain a composite metal nanoparticle having a uniform atomic distribution on a metal atomic level, and as a result, found that the reaction rate of the porous structure obtained by precipitating a solution containing each metal ion and an organic ligand in a solvent was measured. By changing the timing of the addition of metal ions according to the reaction rate, a porous structure in which "metal ions are uniformly mixed at the atomic level" can be obtained. When two or more kinds of metal ions in the porous structure are uniformly mixed at a metal atom level, that is, when they are distributed very uniformly, it is found that the composite metal nanoparticles obtained by heating them are also in the alloy/composite metal oxide. Nanoparticles uniformly mixed at a metal atomic level. Nanoparticles uniformly mixed at the atomic level of the metal can be confirmed by HAADF-STEM EDS analysis.

The metal ion can be supplied by dissolving a soluble salt of a metal such as a sulfate, a nitrate, an acetate, a carbonate, a fluoride, a chloride, a bromide, an iodide, a perchlorate or a hydroxide in a solvent. The solvent may, for example, be a lower alcohol such as water, methanol, ethanol or propanol, or a water-mixed polar solvent such as DMF, DMSO, dimethylacetamide or N-methylpyrrolidone, THF, or the like. An ether such as diethyl ether or diisopropyl ether; a ketone such as ethylene oxide, acetone or methyl ethyl ketone; an ester such as ethyl acetate; chloroform, chloromethane, carbon tetrachloride, dichloroethane, etc. Chlorine hydrocarbons, etc.

For example, Figure 2 shows the relationship between the yield of Co-MOF-74 and Ni-MOF-74 and the reaction time, showing that Co-MOF-74 is formed relatively quickly, while Ni-MOF-74 is relatively slow to form. Thus, in such a case, it is preferable to mix Ni ions (nickel nitrate in Fig. 3) and an organic ligand first, and later (after 18 hours in Fig. 3), Co ions (cobalt nitrate in Fig. 3) are added. Although the Ni ion and the organic ligand form a coordination bond in the case where the Ni ion and the organic ligand are initially mixed, the next metal ion (Co ion) is added before the partial structure of the porous structure is formed, A part of the structure of the porous structure is formed while maintaining a uniform distribution and arrangement of Ni ions and Co ions. Therefore, the finally obtained porous structure becomes a structure in which metal ions are uniformly mixed.

2 and 3 illustrate a method for producing a porous structure (Co/Ni-MOF-74) in which Ni ions and Co ions are uniformly mixed in atomic order with respect to Co-MOF-74 and Ni-MOF-74, However, if it is a person having ordinary knowledge in the technical field, a porous structure containing a uniform atomic level of two or more metal ions can be easily obtained by referring to the description.

The porous structure is heated under the vacuum, under reduced pressure, in an inert gas atmosphere, under a reducing gas atmosphere (in an air environment, in an oxygen-containing gas environment, or in an ozone-containing environment) to thermally decompose the organic ligand to generate carbon. The composite body can be produced, and the composite body comprises composite metal nanoparticles such as alloy nanoparticles in which two or more metals are uniformly mixed in atomic order, composite oxide nanoparticles, and carbon.

The carbon obtained by thermally decomposing the organic ligand can be nitrogen doped in the case where the organic ligand contains nitrogen. Further, in the case of thermal decomposition in an oxidizing gas environment, oxygen doping can be performed. The doping amount of the hetero atom such as nitrogen or oxygen in the carbon is 10% or less by mass, and preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

The inert gas atmosphere can be exemplified by a gaseous environment such as nitrogen, argon, helium or carbon dioxide. The reducing gas environment can be exemplified by a hydrogen gas environment. The oxidizing gas environment can be exemplified by an ozone environment, an oxygen gas environment, and an atmospheric environment. The ozone environment and the oxygen gas atmosphere may be ozone or oxygen, or may be ozone or oxygen in a gaseous atmosphere of 100%, and the ozone or oxygen may be contained in an amount of 1 ppm or more, 10 ppm or more, 100 ppm or more, 1000 ppm or more, or 10000 ppm or more. The oxygen content in the gaseous environment can be adjusted by decompression.

In the case where the porous structure is heated under vacuum under a reduced pressure, an inert gas atmosphere, or a reducing gas atmosphere, the organic ligand is thermally decomposed to become carbon, and two or more metal ions in the porous structure are formed. The nanoparticles of the alloy are formed by reduction, and thus a composite comprising the composite metal nanoparticles and carbon is obtained. On the other hand, in an oxidizing gas atmosphere (a gaseous environment in which oxygen or ozone exists, for example, an atmospheric environment), a composite of nano particles and carbon containing a composite metal oxide of two or more kinds of metal atoms can be obtained. In the case where the oxygen concentration in the gas atmosphere is low, or in the case where it is difficult to oxidize the metal, there is also a structure in which, for example, the composite metal oxide is formed only on the surface while maintaining the alloy, and the degree of oxidation is low (oxygen to metal ratio) The state of the state lower than the theoretical metal oxide. In addition, depending on the type of metal, such as precious metals, it is also heated in an oxidizing gas environment (a gaseous environment in which oxygen or ozone is present). The situation of gold.

The composite metal nanoparticles of the present invention comprise nanoparticles comprising such incomplete metal oxide moieties.

The organic ligand of the porous structure is decomposed into carbon during the heat treatment, and then the decomposition residue can be separated by the composite metal nanoparticle by washing or separation according to specific gravity (for example, centrifugation, sedimentation).

Although the heating temperature for producing the composite metal nanoparticle varies depending on the porous structure, it may be, for example, about 400 to 1000 ° C, and preferably about 400 to 600 ° C, preferably about 400 to 500 ° C, and It is preferably about 400 to 450 °C. Although the heating time varies depending on the heating temperature, it is usually exemplified by about 1 to 200 hours. The heating can be carried out under reduced pressure, in an inert gas atmosphere, in a reducing gas atmosphere, in an oxidizing gas atmosphere, preferably under a vacuum atmosphere. The pressure under reduced pressure at the time of heating reaction may be about 1000 Pa or less, and is preferably about 100 Pa or less, particularly about 5 to 100 Pa.

The organic ligand reduces the metal ion, and then slowly loses hydrogen to change into a decomposition product such as carbon. By heating the porous structure, the small composite metal nanoparticles grow slowly, and then become large metal nanoparticles. Therefore, by controlling the heating conditions, the size of the composite metal nanoparticle can be controlled. Although the composite metal nanoparticles obtained by the production method of the present invention are, for example, monodisperse nanoparticles as shown in FIG. 7, two or more kinds of composite metal nanoparticles may be mixed to form polydisperse nanoparticles. .

The composite metal nanoparticles (alloy nanoparticles, composite oxide nanoparticles) of the present invention have an average particle diameter of about 1 to 100 nm, and preferably about 1 to 20 nm, more preferably about 1 to 10 nm, particularly 1 To about 6nm. Compound gold The average particle diameter of the nanoparticles can be confirmed by a microscope photograph of TEM or the like. The shape of the composite metal nanoparticle is not particularly limited, and may be any shape such as a spherical shape, an elliptical shape, a rod shape, a column shape, or a scale shape.

When the composite metal nanoparticles have a low oxygen concentration in a gas atmosphere during heating or a short-time heat treatment, a mixture of composite metal nanoparticles may be formed or composite metal nanoparticles having a low degree of oxidation may be formed. Also included in the "composite metal nanoparticle" of the present invention.

Example

Hereinafter, the present invention will be described in more detail based on the examples, but the invention is of course not limited to the examples.

Production Example 1: Modulation of a single metal PCP porous structure

In a 50 ml eggplant-shaped flask, 20 ml of DMF-ethanol-water (1:1:1 by volume) was used as a solvent, and Ni(NO ₃ ) _{2 was added} . 6H ₂ O (291 mg, 1 mmol) or Co(NO ₃ ) ₂ . 6H ₂ O (291 mg, 1 mmol), 2,5-dihydroxy terephthalic acid (H ₄ dhtp, 59 mg), followed by stirring at 100 ° C for 6 hours, 12 hours, 18 hours, 24 hours, 48 hours, 72 hours It was reacted in 96 hours and 120 hours. The porous metal structure (Ni ₂ (dhtp) or Co ₂ (dhtp)) of the precipitated single metal was recovered by suction filtration, and then washed with methanol or water. Subsequently, it was dried at 25 ° C for 24 hours under reduced pressure to obtain a single metal porous structure (Ni ₂ (dhtp) or Co ₂ (dhtp)). The porous structure in which a single metal is obtained can be confirmed by powder X-ray structure analysis. The yield of Ni ₂ (dhtp) or Co ₂ (dhtp) for each reaction time is shown in Fig. 2 .

Production Example 2: Modulation of PCP porous structure

In a 3000 ml eggplant-shaped flask, 1500 ml of DMF-ethanol-water (by volume: 1:1:1) was used as a solvent, and Ni(NO ₃ ) _{2 was added} . 6H ₂ O (1.8 g), 2,5-dihydroxy terephthalic acid (H ₄ dhtp, 0.375 g), followed by stirring at 100 ° C for 18 hours to further react, and further adding Co(NO ₃ ) ₂ . 6H ₂ O (1.8 g) was allowed to react for 6 hours. The precipitated porous structure (CoNi-MOF-74) was recovered by suction filtration, and then washed with methanol or water. Subsequently, it was dried at 25 ° C for 24 hours under reduced pressure to obtain a desired porous structure (CoNi-MOF-74). The resulting porous structure can be confirmed by powder X-ray structural analysis (Fig. 4). Further, the obtained CoNi-MOF-74 was analyzed by HAADF-STEM (High Angle Scattering Loop Dark Vision Scanning Electron Microscope). The results are shown in Figure 5. As is clear from the results of FIG. 5, it is a porous structure in which carbon ions (C), Ni, Co, and the like are uniformly mixed in the atomic order.

Example 1

The CoNi-MOF-74 obtained in Production Example 2 was heated under vacuum at 350 ° C, 400 ° C or 430 ° C for 24 hours to obtain a composite of CoNi alloy nanoparticles and carbon. The results of measuring the XRD pattern of the obtained CoNi alloy nanoparticle and carbon composite are shown in Fig. 6, and the results of measuring the particle diameter according to the TEM image are shown in Fig. 7. The average particle diameter of the CoNi alloy nanoparticles prepared by the present invention is 4.1 ± 0.7 nm, and thus it is known that the particle diameter distribution is very narrow. In addition, a HAADF-STEM image of the CoNi alloy nanoparticle and carbon composite (Fig. 8), a partial enlarged view of the CoNi alloy nanoparticle and carbon composite of Fig. 8 (Fig. 9), CoNi alloy Nai HAADF-STEM EDS analysis of rice particles (Fig. 10).

As shown in FIGS. 8 to 10, it can be seen that the composite system of the composite metal nanoparticle of the present invention is adjacent to the metal ion collection inside the porous structure/ Aggregate and grow into composite metal particles and produce nanoparticles to obtain a composite of carbon and nanoparticles produced by thermal decomposition of organic ligands. This suggests that the distribution of two or more kinds of metal atoms of the obtained nanoparticle is the same as the distribution of the metal ions of the porous structure.

Claims (10)

A porous structure comprising two or more metal ions and an organic ligand, and characterized in that two or more metal ions are uniformly mixed at an atomic level. The porous structure according to claim 1, wherein the porous structural system is a Porous Coordination Polymer (PCP) or a Metal-Organic Framework (MOF). A method for producing a composite comprising composite metal nanoparticles and carbon in which two or more metals are uniformly mixed at an atomic level, and the production method is characterized by comprising the steps of: reducing under vacuum, under reduced pressure, and under reduced pressure Heating in a gaseous environment, in an inert gas atmosphere or in an oxidizing gas atmosphere, the porous structure of claim 1 or 2 generates carbon by thermally decomposing an organic ligand, and converts the metal ion into a composite metal to obtain a composite metal naphthalene. a rice particle; wherein the composite metal nanoparticle is an alloy nanoparticle, a composite metal oxide nanoparticle, or a nanoparticle comprising an alloy portion and a composite metal oxide portion, and the composite metal oxide portion is composed of two The above metal oxide is composed. A manufacturing method of a composite body comprising alloy nanoparticles and carbon in which two or more metals are uniformly mixed in an atomic order, and the manufacturing method is characterized in that it is heated under a vacuum, a reducing gas atmosphere or an inert gas atmosphere. The porous structure of claim 1 or 2 thermally decomposes an organic ligand to generate carbon, and converts the metal ion into a metal to obtain an alloy nano particle. A method for producing a composite comprising nano particles and carbon, and the nano particles comprise a composite metal oxide portion in which two or more metals are uniformly mixed at an atomic level; the manufacturing method is characterized by under reduced pressure or The porous structure according to claim 1 or 2 is heated in an oxidizing gas atmosphere to thermally decompose the organic ligand to generate carbon, and to convert the metal ion into a metal oxide to obtain a nanoparticle having a composite metal oxide portion. The method of claim 5, wherein the nanoparticle containing the composite metal oxide portion is composed of a composite metal oxide. The method of claim 5, wherein the nanoparticle containing the composite metal oxide portion comprises an alloy portion and a composite metal oxide portion composed of two or more metal oxides. The manufacturing method according to any one of claims 3 to 7, wherein the heating temperature is from 400 ° C to 600 ° C. A method for producing a porous structure according to claim 1 or 2, wherein the method of production is characterized in that the rate of formation of the porous structure by each metal ion and organic ligand is adjusted The timing of the metal ions is added, whereby two or more metal ions are uniformly mixed at the atomic level. The porous structure of claim 1 or 2, wherein the two or more metals are selected from the group consisting of gold, platinum, silver, copper, ruthenium, tin, palladium, and the production method according to any one of claims 3 to 9. A group consisting of ruthenium, osmium, iridium, nickel, cobalt, zinc, iron, lanthanum, magnesium, manganese, titanium, zirconium, hafnium and molybdenum.