JPH0214806A - Metallic phosphide carbon composite material and production thereof - Google Patents

Abstract

PURPOSE:To inactivate function of a composite material by coordinating a carbon high polymer compound, containing P atom and capable of coordination with one or more metals, such as Ti, V, Cr or Ni, and heat-treating the resultant coordination compound in an inert atmosphere at a specified temperature. CONSTITUTION:A high polymer compound, containing P atom in the backbone and/or side chain and capable of coordination is coordinated with one or more metals selected from the group consisting of Ti, V, Cr, Ni, Ta, W, Pt, etc., to form an organometallic high polymer compound, which is then kept in an inert atmosphere and heat-treated at 400-2000 deg.C temperature. In the process, an ultrafine particulate component of a metallic phosphide having <=5mum particle diameter is homogeneously dispersed and formed in the organometallic compound. Since carbon is a principal component, shapability is essentially excellent and catalyst, electrode functions, etc., are improved by homogeneous dispersion of the fine metallic phosphide particles. Thereby, function of the composite materials is activated.

Description

[Detailed description of the invention] [Industrial application field 1 The present invention relates to metal phosphide carbon composite materials.

More specifically, the present invention relates to a composite material whose main component is carbon material and highly dispersed metal phosphide ultrafine particles; This is what we provide.

[Prior Art and Problems to Be Solved] Currently, metal materials and carbon materials are being applied to a wide range of fields due to their diverse properties and abundance of resources. However, on the other hand,
Among these fields, there are fields where even higher performance and functionality are desired, and more highly active materials are expected due to more precise material design.

Regarding metal phosphide materials, there is a demand for materials that are more active as catalysts and have excellent operability, workability, and selectivity.

In addition to chemical stability, carbon materials have properties such as light weight, heat resistance, lubricity, good heat conductivity, and good electrical conductivity. There are activated carbons, etc. that can make use of the properties that give them properties. Such carbon fibers and activated carbon are not only effective in themselves, but also have great expectations for their secondary uses, such as their use as active sites, reinforcing materials, and the like.

Although a carbon material in which a metal compound is uniformly dispersed is considered to be useful, conventional techniques mainly involve metal coating on the surface of the carbon material, and there is no material in which the metal compound is uniformly dispersed inside the carbon material.・Furthermore, there has been no report on a method for creating a material in which metal phosphides are uniformly dispersed by decomposing raw materials.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive research to solve the above-mentioned problems.

That is, the present invention provides Ti, V, Cr, Mn% Fe sC
o, Ni, Cu, Zr, Nb, Mo
%Ru%Rh%Pd.

Ag, Hf, Ta, W, Re, 10s% Ir% P
The present invention provides a metal phosphide carbon composite material in which one or more metal phosphides selected from the group of t% Au are dispersed in a carbon matrix as ultrafine particles.

Preferably, these ultrafine particle components have a particle size of 5 μm or less to specifically exhibit uniformity as a material, surface smoothness, and functions as a metal phosphide, such as electrical conductivity, heat conductivity, and catalytic activity.

The present invention also provides a method for manufacturing such a metal phosphide carbon composite material, in which the particle size and particle size distribution of dispersed particles can be controlled according to the purpose.

A specific method for producing these metal phosphide carbon composite materials according to the present invention involves coordinating a metal to a polymer compound having an atomic group having coordination ability including Pg atoms in its main chain and/or side chain. The method is characterized in that the obtained organometallic polymer compound is heat-treated at a temperature of 400°C to 2000°C in an inert atmosphere. In addition, an organometallic polymer compound obtained by polymerizing an organometallic compound having a functional group containing a polymerizable P atom at 400°C or more in an inert atmosphere.
It is characterized by heat treatment at 2000°C.

Furthermore, the present invention is characterized in that these metal phosphide components are uniformly dispersed, and it is important that they are not aggregated, precipitated or concentrated on the material surface or matrix grain boundaries. It is.

According to the production method of the present invention, it is possible to stably produce a carbon material in which ultrafine metal phosphide particles are uniformly dispersed even if the particle size is 5 μm or less with good reproducibility. Especially 0.17
For ultrafine particles of 71!1 or less, #i production is possible even for metals that are extremely difficult to produce by other vapor phase methods. Taking advantage of this point, it can be widely used in the preparation of various supported metal catalysts, sintered materials, chemical sensors, etc.

In addition, in this specification, particle size refers to electron! It refers to the area average median diameter in 14 microscopic photographs.

That is, the composite material of the present invention has high electrical conductivity (σ-105 cm
In addition to containing highly reactive metal phosphide fine particles, it can adsorb organic molecules such as amines and alcohols, and can be used as a sensor by amplifying the current change at that time. In addition, because it has a carbon skeleton, it adsorbs various organic substances, and at the same time decomposes or reduces them using the reducing ability and catalytic effect of metal phosphides, making it a useful material as a deodorant. By selecting the metal species, it can be used as an excellent catalyst for the polymerization and isomerization reactions of unsaturated hydrocarbons such as olefins, dienes, and alkynes.
It can be used as a unique hydrogenation, dehydrogenation, and CO addition reaction catalyst.

In the gold scrap carbon composite material of the present invention, the content of metal components is 0.2 to 50! Volume % is preferable. If the amount is less than this range, the function of the metal component will be relatively small and the meaning of composite will be diminished, while if it exceeds this range, uniform dispersion will be difficult and the composite material targeted by the present invention will not be obtained. The content can be selected depending on the purpose, but even if the content exceeds this range, it can be prepared by, for example, performing slow oxidation as a post-treatment to partially remove the carbon portion, or by performing slow oxidation during composite material preparation. Such a method also makes it possible to make the surface porous, making it possible to apply it to many fields.

As mentioned above, the metal phosphide carbon composite material of the present invention is made by firing the organometallic polymer compound as a precursor, and the coordination compound of the coordinating polymer compound used and the metal is used as the raw material. It has become.

This coordinating polymer compound refers to the main chain and/or
I is a polymeric compound having an atomic group having coordination ability in its side chain, and is represented by the general formula as shown below.

-(-L-)n- or 4(-T-)n~The organometallic polymer compound formed by coordination to these metals is represented by the general formula below.

Here, L represents a group with coordination ability, M represents a metal or an ion, X represents an auxiliary ligand, n represents a repeating unit of a polymer chain, and m represents an auxiliary ligand. Represents the number of pieces. The polymer compound of the present invention has phosphorus (P) in any part of its structure.
Atoms exist. Therefore, the P atom may be present not only in L, X, but also in the main chain and other off-center parts of the polymer compound.

Also, the polymer compound may contain N and O atoms. This is because N or O does not remain in the matrix after firing. In addition, the L-M bond has π coordination, n coordination,
Contains bonds via σ-coordination, N or O.

a) An example of the above-mentioned polymer compound is a polymer compound in which an atomic group having Pg atoms is used as a ligand to coordinate with a metal, and specifically, as a coordination group, phosphonic acid, phosphoric acid, phosphine, diphosphine, etc. It is a polymer compound having atomic groups of More specifically, for example, poly[1-[4-(dialkyl7osphinonyl]ethylene 1, poly[1-[4-
(dialkylphosphinomethyl)phenyl]ethylene], poly(dialkyl 7-osphinoalkyl acrylate), poly(dialkylphosphinoalkyl methacrylate), poly[(1-dialkylphosphino)ethylene], poly[(1-dialkylphosphino) finoalkyl)ethylene], poly(p-phosphinostyrene), poly(phosphonomethoxydivinylbenzene), poly(vinyl dihydrogen phosphate), poly[1-[p-(phos7onoxymethyl)phenylacetylene], etc. Yes, these homopolymers and alternating polymer repeating units,
It includes block or random copolymers as well as polymeric compounds having some of these polymeric repeating units in the polymer. In addition to these mainly addition polymerization and ring-opening polymerization products, it also includes condensation polymer compounds such as unsaturated polyesters, phenolic resins, and nylon.

Another production method of the present invention is obtained by firing an organometallic polymer compound obtained by polymerizing an organometallic compound having a polymerizable functional group. Organometallic compounds having a polymerizable functional group are a group of compounds obtained by coordinating a metal to an organic compound consisting of a site with coordination ability and a site with polymerization ability, and the coordination format is as follows: It does not matter whether it is n-coordination, π-coordination, or σ-coordination.

Examples of compounds consisting of a site with coordination ability and a site with polymerization ability are as follows: b) The site with ligand ability has an atomic group having a pH of 9. , phos7onic acid, phosphoric acid, phosphine, diphosphine, etc., and more specific examples include vinyl phosphate, p-dialkylphosphinostyrene,
p-Dialkylphosphinomethylstyrene, dialkylphosphinoalkyl acrylate, dialkylvinylphosphine, dialkylphosphinoalkyl methacrylate, dialkyl-2-propenylphosphine, p-phosphinostyrene, phos7onomethoxydivinylbenzene, hinyldihydrogenphos7 ate, p-phosphotmethylstyrene, and the like.

Coordination to these metals is applicable to general organometallic complex synthesis methods, whether the ligand side is a high molecular compound as shown in a) or a low molecular compound as shown in b). A method can be used. Namely, direct metallization reaction by substitution reaction of metal, substitution reaction with halide, metal salt using metal salt.
In addition to hydrogen exchange reactions, metal-halogen exchange reactions with organometallics, and ligand exchange reactions, direct coordination of metals, metal salts, organometallic compounds, etc. is also possible. Specific examples of the metal compound according to the present invention include, in addition to the metal itself, T i Cl 4+ Z r Cl 41 N
b Cl 6 + T a CI B 1M0CIs
, W C16, CuC12, CoC14, N i C1
2, FeC12, FeCl3. Ti(OR), metal halides such as nickel acetylacetonate, metal alkoxides, metal acetylacetonates, and N1(Co
), , C0(Co)s, Fe(Go)s, [RhCI(
Go) zlz, PLclx (1,5-cyclooctene>-), PdCtz (1,5-cyclooctadiene)
, RhCI (cyclooctene) 2°N1 (PPhs)
Examples include organic metal compounds such as P d (P hs).

Polymers or copolymers of these polymerizable organometallic compounds, copolymers or crosslinked polymers of these compounds and polymerizable monomers, or mixtures of these polymers, copolymers, or crosslinked polymers is used as a precursor organometallic polymer compound in the present invention. Polymerizable monomers that can be used with the polymerizable organometallic compound include compounds that are not coordinated with the metal of the ligand having a polymerizable functional group used in the polymerizable organometallic compound, and general A seven-pointer can be used.

That is, common olefins include ethylene, propylene, butenes, isobutylene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, etc., and acetylenes include acetylene,
Examples include methylacetylene, propylacetylene, and phenylacetylene.

Further, halogenolefins include vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc., as well as vinyl esters such as vinyl acetate, styrene, α-methylstyrene, divinylbenzene, chlorostyrene, aminostyrene, and hydroxyl. Styrene, etc., aromatic vinyl compounds such as vinylnaphthalene, vinylanthracene, acenaphthylene, vinyl salicylate, ethyl vinyl ether,
Alkyl and aromatic vinyl ethers such as phenyl vinyl ether and propyl vinyl ether; acrylic acid and acrylic esters such as α-cyanoacrylic acid ester and α-halogenoacrylic ester; methacrylic acid and methacrylic acid esters such as methyl methacrylate; In addition to nitriles and isonitriles such as acrylonitrile, methacrylonitrile, adiponitrile, vinylidene cyanide, acrylonitrile, and isonitrile, acrylamides such as acrylamide, methacrylamide, and diacetone acrylamide, vinyl ketones such as methyl vinyl ketone and phenyl hinyl ketone, Examples include vinylpyridine and vinylimidazole.

The metal phosphide carbon composite material of the present invention is made by firing organometallic organic polymer compounds obtained by the three methods described above, and the metal components forming these are Ti, V, and Cr. , Mn, Fa.

Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, P
d, Ag, HLT a, W, Re, Os
+ I r + P L can be used.

In these coordination compounds, metal coordination causes detachment or rearrangement of hydrogen ions in the ligand, redox of the ligand itself, etc., resulting in new electron configurations in the molecule or coordination. Although the valence and ionicity of the metal may vary, such metals can also be used as starting materials for the metal phosphide carbon composite material of the present invention. Some of such coordination compounds are also shown in the above examples.

Such organometallic compounds have excellent shapeability, and the precursor polymer can be molded into the shape required for the final metal phosphide carbon composite material using various molding methods. In addition to general molding methods such as pressure molding, extrusion molding, and injection molding as a bulk body, spinning by controlling the molecular weight,
Can be made into sheets and thin films.

The metal phosphide carbon composite material of the present invention can be obtained by firing the metal-containing precursor polymer obtained as described above under temperature conditions suitable for each metal.

Firing is usually performed at normal pressure in an inert gas atmosphere such as nitrogen or argon, but depending on the oxidizing properties and reactivity of the organometallic, reducing gas such as hydrogen may be used, or
Firing is required under pressure of around 000 at or reduced pressure.

The firing temperature is usually preferably 400 to 2000°C. Furthermore, since the organic matter is fired, it is necessary to control the temperature increase during thermal decomposition. Particularly during this temperature raising process, thermal decomposition of the matrix may be accompanied by polymerization, so it is necessary to avoid abnormally generated heat. For this reason, the heating rate should be set to 0.01~
b. It is desirable to do it within the following range.

Furthermore, productivity may be improved by performing pressure molding after heat treatment to the carbonization initial temperature range and heat treatment again.

The constant temperature holding time at the final treatment temperature is 0.5 hours or more5
Preferably up to 0 hours. The structure and composition of the metal-carbon composite material obtained as described above were identified and confirmed. That is, the raw material polymer compounds and organometallic compounds can be analyzed using infrared spectrophotometer (IR), nuclear magnetic resonance (NMR), elemental analysis, and ultraviolet spectrometry (which is used to determine the structure of general organic compounds and organometallic compounds). The structure was determined by spectroscopic methods such as UV).

Thermogravimetric analysis was performed during the firing process to observe the weight loss accompanying the thermal decomposition process. To identify metal-containing chemical species in the fired product, powder X-ray diffraction (XRD) measurement, selected area electron diffraction (SAD), or electron microbeam diffraction (M
BD) was used. Mössbauer spectroscopy was also used to identify iron phosphides. The macroscopic distribution and dispersion state of metal phosphides in the fired product were examined using a scanning electron microscope (SE).
M) image and X-ray microanalyzer (EPMA) image.

Furthermore, the microscopic distribution of metal phosphide, the dispersion state, and the state of carbon in the matrix were observed using transmission electron microscopy (TEM) images, and the distinction between metal phosphide and carbon in the matrix was made using an energy dispersive X-ray diffraction device (EDX). ) according to

[Example 1] The present invention will be explained in more detail with reference to Examples below, but the following examples are merely examples, and the scope of the present invention is not limited thereby.

(Example 1) 4-chloromethylstyrene (10 mol%), styrene (
90 mol%) in benzene with AIBN as initiator, 75
The resulting copolymer was reacted with diphenylphosphinolithium (LiPPhz) in THF by a conventional method to obtain a copolymer having methylene diphenylphosphine. This was dissolved in methylene chloride, and palladium chloride-1°5-cyclooctadiene complex (PdC4
i(COD)) in methylene chloride was added. After the reaction was completed, it was concentrated and precipitated with hexane to obtain a Pd-coordinated polymer. After calcining the obtained compound at 400°C, 1
When fired at 000°C, a black composite material could be obtained with a residual carbon content of 32%. Observation of the obtained composite material using a TEM image (FIG. 1) revealed that ultrafine particles with a particle size of 30 nm or less were uniformly dispersed. Also, this T
The black part in the EM image was found to be composed of Pd and P by EDX analysis. The XRD pattern of the fired product (Fig. 2) revealed that the ultrafine particles were phosphides of Pd and P.

(Example 2) Commercially available crosslinked polystyrene consisting of 4-chloromethylstyrene (10 mol%), styrene (89 mol%), and divinylbenzene (1 mol%) was treated with THFHF fudiphenylphosphinolithium. When a phosphorus polymer was reacted with PtC(12(1°5-cyclooctadiene) dissolved in methylene chloride at 30°C, a polymer in which PtC(1,) was bonded to a phosphorus ligand was obtained.

This polymer was fired at 1000° C. in an inert gas to obtain a carbon composite material containing platinum. The H and N content of this product was less than 1%. A weight loss of 75% was observed upon firing. EDX analysis accompanying TEM (Figure 3)
The existence of pt and P is confirmed by this. Similarly, Pd,
A composite material of metal phosphide and carbon was also obtained for Rh and Co. TEM images of the carbon material containing Pd and CO phosphides are shown in FIGS. 4 and 5, respectively.

(Example 3) The same reaction and heat treatment as in Example 5 were performed on the copolymerization ratio of 4-chloromethylstyrene and styrene used in Example 1, which was 2798.33:67 (both molar ratios). Regarding the particle size of the palladium phosphide ultrafine particles of the obtained palladium phosphide carbon composite material, TE
As a result of observation with M, it was found that under similar heat treatment conditions, the metal in the composite material with a higher metal content had a larger particle size. However, none of them exceeded 5 μm.

(Example 4) 4-chloromethylstyrene (10 mol%), styrene (
90 mol %) was polymerized in the same manner as in Example 5 to obtain a copolymer having methylene diphenylphosphine in the side chain. Pde12x (COD) was added to a methylene chloride solution of this copolymer.
, [RhCl2(G 0)ilt, cOi(CO)a.

Pt1 (COD), each metal is 1/8 to phosphine
They were added in equivalent amounts to cause a coordination reaction. After drying the obtained polymer, it was similarly calcined at 400°C, and then fired at 1000°C in the same manner as above. Observation of the obtained metal-carbon composite material using a TEM image (FIG. 6) revealed that ultrafine particles with a particle size of 10 nm or less were uniformly dispersed. The black part of the TEM image in the figure shows PL, Pd,
It was found that it consists of Rh, Co and P (Fig. 7).

A weight loss of 60-70% was observed during firing. H and N
The content of CO was 1% or less, and it was confirmed by the IR spectrum that the CO groups were completely eliminated.

(Example 5) 4-chloromethylstyrene (10 mol%), styrene (
90 mol%) in benzene with AIBN as M initiator, 75
The resulting copolymer was reacted with L i P P hz in THF by a conventional method to obtain a copolymer containing methylene diphenylphosphine. This was dissolved in methylene chloride and di-μm chlorotetracarbonylrhodium ([RhcI2(co)
ilt) To react. Concentrate and precipitate with hexane.
A metal polymer compound coordinated with h was obtained. The obtained black compound was calcined at 400°C and then fired at 1000°C to obtain a black rhodium phosphide carbon composite material.

The obtained metal phosphide carbon composite material was observed using a TEM image (FIG. 8). As a result, it was found that ultrafine particles with a particle size of 10 nm or less were uniformly dispersed.

Further, when the black part in the photograph was analyzed by EDX (FIG. 9), it was found that the black part was composed of Rh and P. Similar results were obtained with Co instead of the Rh complex.

It was also obtained for Pt. TEM image and E of Co
The DX spectra are shown in FIG. 1O and FIG. 11, respectively.

(Example 6) Diphenylphosphino groups were added to the copolymer used in Example 5 in which the copolymerization ratios of 4-chloromethylstyrene and styrene were 2:98 and 33:67 (both molar ratios) in THF. Attached by substitution reaction. Each of these was reacted with di-μm tarorochitracarbonyl rhodium to obtain an organometallic polymer compound. These were calcined at 400°C and then fired at 1000°C to obtain a black Rh carbon composite material. This TEM image is shown in FIGS. 12 and 13.

(Example 7) 4-chloromethylstyrene (10 mol%), styrene (
90 mol%) in benzene with 1 MI initiator,
Polymerization was carried out at 75°C, and the resulting copolymer was treated with TH by a conventional method.
A copolymer having methylene diphenylphosphine was obtained by reacting with LiPPh in F.

This was dissolved in methylene chloride and reacted with PtCl2 (COD) in the same manner as in Example 1.5. It was precipitated with hexane to obtain a Pt-coordinated metal polymer compound. The obtained black compound was calcined at 400°C and then fired at 1000°C to obtain a black platinum phosphide carbon composite material. From the XRD pattern (FIG. 14), it is thought that the platinum-containing chemical species is PtP.

(Comparative Example 1) A Pd-coordinated polymer compound consisting of the styrene copolymer having diphenylphosphine side chains obtained in Example and palladium-1,5-cyclooctadiene was heated under a nitrogen stream for 30 minutes.
It was fired at 00°C. The fired product did not completely turn black, and the presence of organic groups was confirmed in the IR spectrum, indicating that carbonization was not completed.

[Brief explanation of the drawing]

1 and 2 are a transmission electron microscope (TEM) image photograph and an X-ray diffraction diagram showing the particle structure of the palladium phosphide (PdsPz) carbon composite material obtained in Example 1, respectively. Figures 3, 4 and 5 are an EDX diagram of a carbon material containing platinum phosphide, a TEM image photograph showing the particle structure of a carbon material containing palladium phosphide, obtained in Example 2, respectively;
TEM showing the particle structure of carbon material containing cobalt phosphide
This is a photograph of the statue. 6 and 7 are a TEM image photograph and an E image showing the particle structure of the metal alloy phosphide composite material obtained in Example 4, respectively.
It is a DX diagram. Figures 8 and 9 are a TEM image photograph and an EDX diagram showing the particle structure of the carbon material containing rhodium phosphide obtained in Example 5, respectively, and Figures 1O and 11 are the same <Example 5 FIG. 2 is a TEM image photograph and an EDX diagram showing the particle structure of the cobalt phosphide carbon composite material obtained in FIG. FIGS. 12 and 13 are TEM photographs showing the particle structure of the metal phosphide carbon composite material obtained in Example 6, respectively. FIG. 14 is an XRD pattern of the metal phosphide carbon composite material obtained in Example 7.

Claims (1)

[Claims] 1. In a metal phosphide carbon composite material in which a metal phosphide component is dispersed in a carbon material containing carbon as a main component, the metal component is Ti, V, Cr, Mn, Fe, Co, Ni. , Cu
, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf,
A metal phosphide carbon composite material that is ultrafine metal phosphide particles made of one or more metal phosphides selected from the group consisting of Ta, W, Re, Os, Ir, and Pt. 2. Ti, V
, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb,
Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re
, Os, Ir, and Pt, an organometallic polymer compound obtained by coordinating one or more metals selected from the group consisting of , Os, Ir, and Pt is heat-treated at a temperature of 400°C to 2000°C in an inert atmosphere. A method for producing a metal phosphide carbon composite material according to claim 1. 3. P that has a polymerizable functional group and can coordinate to a metal
Ti, V, Cr, Mn, Fe, Co in atomic groups containing atoms
, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd,
A polymer obtained by polymerizing one or more organometallic compounds coordinated with one or more metals selected from the group consisting of Ag, Hf, Ta, W, Re, Os, Ir, and Pt. or a copolymer, or a mixture of these polymers or copolymers at 400°C or higher and 2000°C under an inert atmosphere.
2. The method for producing a metal phosphide carbon composite material according to claim 1, wherein the metal phosphide carbon composite material is heat-treated at a temperature of: 4. P that has a polymerizable functional group and can coordinate to metals
Ti, V, Cr, Mn, Fe, Co in atomic groups containing atoms
, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd,
Can be copolymerized with one or more organometallic compounds coordinated with one or more metals selected from the group consisting of Ag, Hf, Ta, W, Re, Os, Ir, and Pt. A mixture of a copolymer or a crosslinked polymer obtained by copolymerizing with a polymerizable monomer is heated at 400°C or higher for 20 minutes in an inert atmosphere.
The method for producing a metal phosphide carbon composite material according to claim 1, characterized in that the heat treatment is performed at a temperature of 00°C or less. 5, Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, T
One or more metals selected from the group consisting of a, W, Re, OS, Ir, and Pt are bonded to the polymer chain via σ- or π-bonding carbon, or N, O, forming a polymer chain. Under an inert atmosphere, a polymer containing P atoms other than the metal coordination site of 4
The method for producing a metal phosphide carbon composite material according to claim 1, characterized in that the heat treatment is carried out at a temperature of 00°C or more and 2000°C or less. 6, Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, T
One or more metals selected from the group consisting of a, W, Re, Os, Ir, and Pt are bonded to the polymer chain via σ- or π-bonding carbon or N, O, and the metal is auxiliary. 2. The metal phosphide according to claim 1, wherein the polymer in which at least one of the ligands is bonded to a metal via a P atom is heat-treated at a temperature of 400° C. to 2000° C. in an inert atmosphere. Method for manufacturing carbon composite materials.