JPH026312A - Composite material of metallic sulfide carbon and production thereof - Google Patents

Abstract

PURPOSE:To disperse ultrafine particles of a sulfide of a metal such as Ti, V or Cr into a carbon matrix by coordinating a specific polymer compound having an atomic group containing sulfur atom with the metal to give a compound and heat-treating the compound under a given condition. CONSTITUTION:A polymer compound which is provided with an atomic group having coordination ability containing sulfur atom at a main chain and/or side chain and can be coordinated is prepared. The compound is coordinated with a metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, etc., to give an organometallic polymer compound. Then one or more of the compounds are polymerized to give a polymer or copolymer. Then a mixture of the polymers is heat-treated in an inert atmosphere at 400-2,000 deg.C. Consequently, a composite material of metallic sulfide carbon wherein a sulfide of the metal having <=5mum particle diameter is dispersed into a carbon matrix is obtained.

Description

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

More specifically, the present invention relates to a composite material in which carbon material is the main component and ultrafine metal sulfide particles are highly dispersed, and it is a composite material that can be used as a highly functional material such as a catalyst, conductive material, electrode material, etc. It provides:

[Prior Art and Problems to Be Solved] Current i'E metal compound materials and carbon materials are being applied to a wide range of fields due to their diverse properties and resource availability. However, on the other hand, there are fields where even higher performance and higher functionality is desired, and more precise bare-handed 4 designs are needed.
A more highly active material is awaited.

Regarding metal sulfide + 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 carbon materials in which metal compounds are uniformly dispersed are considered to be useful, conventional technology has not been able to produce carbon materials (4) in which the surface of the material is mainly coated with metal, and the carbon is uniformly dispersed within the material. Furthermore, there has been no report on a method for creating a material in which metal sulfides 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 in order to solve the above-mentioned problems.

That is, the present invention provides Ti, V, Cr, Mn, Fe, Co,
Ni.

Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, H
The present invention provides a metal sulfide carbon composite material in which a sulfide component of one or more metals selected from the group consisting of f, Ta, WRe, Os, and Ir is dispersed in a carbon matrix as ultrafine particles.

These ultrafine particle components preferably have a particle size of 5 μm or less (uniformity as a material, surface smoothness, and functions as a metal sulfide, such as electrical conductivity, thermal conductivity, catalytic activity, etc.) .

The present invention also provides a second method for producing such a metal sulfide 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 sulfide carbon composite materials according to the present invention involves coordinating a metal to a polymeric compound having a main chain and/or side chain containing an atomic group having a coordination ability including an S atom. This is characterized by heat-treating the obtained organometallic polymer compound at a temperature of 400°C to 2000°C under an inert atmosphere.Also, the functional group containing a polymerizable S atom is A metal polymer compound obtained by polymerizing a ff metal metal compound was polymerized under an inert atmosphere for 400 min.
It is unique in that it can be heat treated at temperatures between ℃ and 2000℃.

Furthermore, the present invention is characterized by the fact that these metal sulfide components are uniformly dispersed, and it is important that they do not aggregate, precipitate, or concentrate 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 sulfide particles are uniformly dispersed even if the particle size is 5 μm or less with good reproducibility. Especially 0.1μm
The following ultrafine particles can be prepared from metals that are extremely difficult to produce by Ike's vapor phase method. Taking advantage of this point, it can be widely used in the preparation of various supported metal catalysts, sintered materials, chemical sensors, etc. Incidentally, in this specification, the particle size refers to the area average diameter in an electron micrograph.

That is, the composite material of the present invention has high electrical conductivity (σ-!OScm
-' or higher) and also contains highly reactive metal sulfide fine particles or low-valent metal sulfide fine particles, so it can adsorb organic molecules such as amines and alcohols. It can be used as a sensor by amplifying the current change. In addition, it adsorbs various organic substances using its carbon skeleton, and at the same time decomposes or reduces them using the reducing ability and catalytic effect of metal sulfides, making it a useful material as a deodorant. Furthermore, 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, tsene, and alkynes. can do.

The metal-carbon composite material of the present invention contains a metal component!
It is desirable that n be 0.2 to 50% by weight. If the amount is less than this range, the function of the metal component will be relatively small, and the flavor of the composite will be weak. On the other hand, if it exceeds this range, it will be difficult to uniformly disperse the composite material, which is the object of the present invention. Not. The content can be selected depending on the purpose, but if the content exceeds this range, for example, slow oxidation can be performed as a post-treatment to partially remove the carphone portion, or slow oxidation can be performed during composite material preparation. Can be prepared. Such a method makes it possible to make the surface porous, making it possible to apply it to many fields.

The metal sulfide carbon composite material of the present invention is obtained by firing the organometallic polymer compound as a precursor as described above,
The raw material is a coordination compound of the polymer compound that can be used and a metal.

This coordinating polymer compound refers to the main chain and/or
Alternatively, it refers to a polymer compound with an atomic group having a coordination ability including an S atom in a side chain, and is represented by the general formula as shown below.

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

Here, L represents a group with coordination ability containing an S atom, M is a metal or ion, X is an auxiliary ligand, n is a repeating unit of the polymer chain, and m is an auxiliary ligand. represents the number of g. The polymer compound of the present invention only needs to have a sulfur (S) atom in any part of its structure. Although the S atom is generally present in L for water-trapping purposes, it may also be present in the polymer chain or in the auxiliary ligand (X).

The LM bond includes a π-coordination, an n-coordination, and a σ-coordination. Examples of such coordinating polymer compounds are as follows.

a) It is a polymer compound that uses an atomic group that coordinates the S atom as a ligand that coordinates with a metal. Specifically, it is a polymer compound that uses diol, aromatic diol, nothiol, sulfite, disulfide, sulfoquinodo, diocarponyl, etc. as a ligand. It is a polymer compound that filters atomic groups, and more specifically, for example, poly[1-(p-mercaptophenyl)ethylene], poly[+-(p-mercaptomethylphenyl)ethylene],
poly(imino 2-oxo-2-mercabutoethylene),
Poly[1[1-oxy-3-mercapto-5-deapendyl]ethylene], Poly[1(-p-(2,5-didiapendyl)phenyl]ethylene], Poly[1-[p-[
2(Tunorboquinoethyl)thio]phenyl]ethylene]
etc., these homopolymers, alternating, block or random copolymers of these polymerized repeating units, and further these polymerized repeating units]7 units in the polymer, -Jfl￥
Contains high molecular weight compounds. 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 manufacturing method of the present invention is to obtain the organic gold I by firing an organic gold I-open molecular compound obtained by polymerizing a metal compound having a polymerizable functional group. The metal compound forming the polymerizable functional group has a site containing an S atom and a coordination ability, and a polymerization ability. :J() is a compound formed by distributing a metal to an rf mechanical compound consisting of
It does not matter whether the configuration is σ-coordination or not.

To give an example of a compound consisting of a site having a coordination ability containing an S atom and a site having a polymerization ability, 1)) What does the site having a ligand ability do with an atomic group having an S atom? It is an organic compound in which the coordination atomic group is an atomic group such as thiol, aromatic thiol, nothiol, sulfite, nosulfite, sulfoxide, thiocarbonyl, etc. More specific examples include mercaptostyrene, mercaptomethylated styrene. , cysteine, methionine, p-mercaptostyrene, p-mercaptomethylstyrene, 2
-Mercapto-4-diobudyl vinyl ether, p-(
2-carboxyethyldio)styrene and the like.

For coordination to these metals, the ligand side is a high molecular compound shown in a), a low molecular compound shown in [)), and a general (j° mechanical metal). Complex synthesis methods can be used, i.e., direct metallization reaction by metal substitution reaction, substitution reaction with halides, metal-hydrogen exchange reaction using metal salts, metal-halogen exchange reaction with TT metals, In addition to phase exchange reactions, direct coordination of metals, metal salts, metal carbonyls, ￥T (a metals, etc.) is possible.

Specific examples of the metal compounds according to the present invention include metals, T + CI 4 , Z r Cl
4. N b Cl 5TaC15, MOc+5. W
CIO, CLIC12, cOc L, NiCl2, Fe
Cl2. FeCl3. Ti(OR)4. Metal halides such as nickel acedelacetonate, metal alkoxides,
Metal acedelacetonate and N1(Co)4゜Co
2(CO)8. Re(CO)s, [RhCI(Co)z
]-, PtCf2 (1,5-tuta-tetraoctane), P
dC12 (1.

5-tuta-tetraoctane), RhCI (cyclooctene)2. N i(P P h3)a, P d(P P
There are organometallic compounds such as tL+)i.

These polymerizable rT metal metal compound polymers or copolymers, or copolymers or crosslinked polymers of the compound and jF polymerizable monomers, or polymers, copolymers, or crosslinked polymers thereof The mixture of i? Use as a thing. Examples of polymerizable hexamers that can be used with the polymerizable a-metal compound include compounds in which the ligand having a polymerizable functional group used in the polymerizable a-metal compound is not coordinated with the metal. In addition, - a commercially available monomer can be used.

That is, - As a boat-fishing olefin, Ejilene Ten,
Examples include cyclopentene, cyclohexene, cyclopentene, nocrooctene, etc., and acetylenes include acetylene, methylacetylene, propylacetylene, phenylacetylene, etc.

Furthermore, halo/7", + olefins include vinyl chloride, vinyl chloride λ", vinyl bromide, vinyl fluoride, etc., and vinyl esters such as vinyl acetate, styrene, α-methylstyrene, and novinylbenzene. Aromatic vinyl compounds such as ゛2no, talolostyrene, aminostyrene, hydrogynostyrene, etc., vinylnaphthalene, vinylanthracene, acenaphthylene, and hinyl salicylate, alkyl and aromatic vinyl ethers such as ethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. , acrylic acid and acrylic esters such as α-cyanoacrylic acid ester and α-halochenoacrylic ester, methacrylic acid and methacrylic acid esters such as methyl methacrylate, acrylonitrile, methachloronitrile, adiponitrile, vinylidene nitrile and Examples include isonitriles, acrylamides such as acrylamide, methacrylamide, and noacetone acrylamide, vinyl ketones such as methyl vinyl ketone and phenyl vinyl ketone, vinyl birinone, and vinyl imidazoles.

The metal sulfide carbon composite material of the present invention is made by firing organometallic organic polymer compounds obtained by two methods as described above, and includes metal components forming these and
- is 'I''i, V, Cr. Mn, FeCo, Ni, C
u, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf
T, +, W, Itt! , Os, I r, l"t can be used.

In our coordination compounds, the coordination r・
Due to the detachment and rearrangement of hydrogen ions in the molecule, and the oxidation-reduction of the ligand itself, the electron configuration in the molecule may be changed, and the valence and ionicity of the metal being arranged may change. However, such compounds can be used as starting materials for the metal sulfide carbon composite material of the present invention. In the above examples, some coordination compounds are shown.

Such organometallic compounds have excellent shapeability and can be used as precursors and L.
The composite can be molded into the desired shape of the final metal sulfide 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, sorting, and thin film formation are also possible.

- The metal-containing surface polymer obtained as described above is fired 4 times by selecting temperature conditions suitable for each metal.
From this, the metal sulfide carbon composite material of the present invention can be obtained.

Firing is usually carried out under an atmosphere of an inert gas such as nitrogen or argon at normal pressure. Depending on the oxidizing properties and reactivity of the organometallic, a ternary gas such as hydrogen may be used, or in some cases I Calcination under pressure or reduced pressure after 000 atm+ii7 is required.

The firing temperature is usually preferably 400 to 2000°C. In addition, since 11 objects will be fired, it will be necessary to control the temperature rise during thermal decomposition. In particular, this heating process may involve thermal decomposition or polymerization of the matrix, so it is necessary to avoid abnormally generated heat. For this reason, the heating rate was set to 0.01
It is desirable to perform within the range of ~b.

Furthermore, productivity may be improved (or reduced) by heat-treating to the carbonization initial temperature range, then performing pressure molding, and then heat-treating again.

The constant temperature holding time at the final treatment temperature is 0.5 hours or more.
Preferably up to an hour. The structure and composition of the metal-carbon composite material obtained in the following manner were identified and confirmed. That is, the original t-
F's high molecular compounds and high-quality metal compounds can be measured using infrared spectrophotometer (rI'l), nuclear magnetic resonance (NMR), elemental analysis, and ultraviolet rays, which are used to determine the structures of general organic compounds and organometallic compounds. minute) and molecule J? The structure is determined by spectroscopic methods such as (UV).

During the firing process, thermal analysis was conducted to observe the decrease in Ti1 due to the thermal decomposition process. Powder X-ray diffraction (XRD) measurement, selected area electron diffraction (SAD), or electron microheam diffraction (M13D) was used to identify metal-containing chemical species in the fired product. For the identification of iron sulfides, Mössbauer spectroscopy was used in combination. The macroscopic distribution and dispersion state of metal sulfides in the fired product can be determined using scanning electron microscope (SEM) images and X-ray microanalyzer (EPMA) images.
) images were analyzed.

Furthermore, the microscopic distribution of metal sulfides, their dispersion state, and the state of carbon in the matrix are observed using transmission electron microscopy (TEM) images, and the distinction between metal sulfides and 7-trix carbon is performed using energy dispersive X-ray diffraction. According to the equipment (E[)X).

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

(Example 1) a) Synthesis of poly[(mercaptophenyl)ethylene] Borisdylene was synthesized with tetramethylethylenediamine ti (E
Below, it was reacted with rope tyrridium in isoclohexane (12 hours). To the resulting dark red poly[(lithhiophenyl)ethylene], 0.5 mole equivalent m/monomer unit of sulfur was added and stirred for 12 hours. After hydrolysis with 2N hydrochloric acid, the crude product was reprecipitated using T I-IF / water, THF / methanol, and 'r HF / hexante, and the crude product was suspended again in T HF + : L + A L H
By adding 4, the partially generated S-8 crosslinking also -
Reduction to SH groups gave the title polymer. Elemental analysis revealed that mercapto group substitution on the benzene ring was 13%.

11) Dissolve the polystyrene containing the mercapto group (-Sl-() obtained in the previous section in THF under an argon atmosphere. To this, carefully add the mercapto group and the metal sodium strips. Sodium salt was gradually formed with evolution of I-12 gas. When the sodium pieces disappeared, FeC12 was added. After stirring at 40° C. for 24 hours, hexane was added and the resulting polymer was thoroughly washed with water and dried to obtain a polymer complex having Fe-8 bonds.

TlC14, NbC15, Cr instead of FT3012
Cl3, MOCI3, CoClt, NiClt, A
Thiolate polymers of each metal were obtained in the same manner using gC1. When the above S-M-3 (M-metal) crosslinked polymer was thermally decomposed at 1000°C in an argon stream (average temperature increase rate: 0.30°C/min, held at 1 OOOoC for 2 hours), the calcination yield was 7. A black residue was obtained at -38%.

From the XRD measurement of the fired product, it was found that metal sulfides were generated. The carbon matrix was partially graphitized in iron, cobalt, and nickel systems, but was amorphous in other metal systems. As a result of analysis using XMA and 'I'' EM, the average particle size of each metal sulfide was within the range of 11-400n, and the dispersibility in the carbon matrix was good.

(Example 2) Polystyrene sulfate potassium salt was dissolved in a minimum volume of water that had been degassed and replaced with argon. This saturation N i (
N O), add an aqueous solution (S:N1=20:I)-
SO3"N +""'"03S-Nickel insolubilized by crosslinking; body polymer precipitated. This was centrifuged and the supernatant liquid was discarded. After washing with water and centrifuging three times, it was washed with ethanol and dried. The polymer containing nickel-sulfonate thus obtained was calcined at 1000°C in an argon stream (held for 2 hours, average temperature increase rate 0.30°C).
As a result, ultrafine NiS particles were extremely uniformly dispersed in the carbon matrix. Nickel sulfide/
A carbon composite material was obtained. The electrical conductivity of this carbon material containing nickel sulfide is 102 s/cm, and this value is equal to the electrical conductivity 1 (I" 87 cm 4 orders of magnitude larger.

Claims (1)

[Claims] 1. In a metal sulfide carbon composite material in which a metal sulfide component is dispersed in a carbon material containing carbon as a main component, the metal sulfide component is Ti, V, Cr, Mn, Fe, Co. , Ni, C
u, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hr
, Ta, W, Re, Os, and Ir. 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 sulfide carbon composite material according to claim 1. 3. S 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,
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 these copolymers, or mixtures of these polymers or copolymers at 400°C or higher in an inert atmosphere.
2. The method for producing a metal sulfide carbon composite material according to claim 1, wherein the heat treatment is performed at a temperature of 000° C. or less. 4. S 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.
2. The method for producing a metal sulfide carbon composite material according to claim 1, wherein the heat treatment is performed at a temperature of 00° C. or lower. 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 a σ- or π-bonding carbon, forming a metal coordination site of the polymer chain. In addition to S
Polymers containing atoms are heated at 400℃ or higher at 200℃ or higher in an inert atmosphere.
Claim 1 characterized in that the heat treatment is performed at a temperature of 0°C or lower.
The method for manufacturing the metal sulfide carbon composite material described. 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 carbons, and in the auxiliary ligand of the metal. The metal sulfide carbon composite material according to claim 1, wherein the polymer in which at least one of the metals is bonded to a metal via an S atom is heat-treated at a temperature of 400°C to 2000°C in an inert atmosphere. Production method.