JP2020200224A - Metal-carbon hybrid material and method for producing the same - Google Patents

Abstract

To provide a novel method for producing metal-carbon hybrid materials that enables mass production and/or reduction in production cost of the materials.SOLUTION: A method for producing metal-carbon hybrid materials, comprises a step of heat-treating a conjugated polymer having a structure of metal-containing π-conjugated polymer complex in its main chain, and an optically active substituent and an amide group in its side chain.SELECTED DRAWING: Figure 7

Description

The present invention relates to a method for producing a novel metal-carbon hybrid material. The present invention also relates to a metal-carbon hybrid material obtained by the above-mentioned production method.

A metal-containing polymer containing a metal produces metal nanoparticles when treated with heat or radiation. It has been clarified that the metal nanoparticles thus obtained have a catalytic function, electrical, magnetic, optical properties, etc., which have not been known in the past. The materials used are attracting attention as industrial technology.

The inventor of the present application has succeeded in synthesizing a phenylene ethynylene-based conjugated polymer having a platinum complex structure in a pyridine ligand type main chain and having optical activity. Further, the inventor of the present application has clarified that the phenylene ethynylene-based conjugated polymer forms a regular integrated structure in the solid (Non-Patent Document 1). However, detailed studies using such a phenylene ethynylene-based conjugated polymer have not been conducted so far.

By the way, various techniques have been reported so far as techniques for producing a metal-carbon hybrid material. For example, Non-Patent Documents 2 and 3 disclose a method for producing tetrahedral platinum nanoparticles having high catalytic activity by combining platinum nanoparticles and a carbon material such as graphene oxide. ..

Otaki et al., Chem. Lett., 45, 937-939, 2016 C. Yang et al., The Electrochem. Soc., 165 (14), B665, 2018 X. Jiang et al., Ind. Eng. Chem. Res., 57, 14544, 2018

However, the techniques described in Non-Patent Documents 2 and 3 have a problem that mass production of a metal-carbon hybrid material is difficult and a high production cost is required.

Therefore, one aspect of the present invention is aimed at realizing a method for producing a novel metal-carbon hybrid material, which solves the above-mentioned problems.

As a result of diligent studies to solve the above problems, the present inventor has performed heat treatment using a metal-containing conjugated polymer having a specific structure, so that the three-dimensional laminated structure is highly controlled metal-carbon. For the first time, he discovered that a hybrid material could be obtained, and completed the present invention. That is, one embodiment of the present invention includes the following configurations.
<1> A metal-carbon comprising a step of heat-treating a conjugated polymer having a metal-containing π-conjugated polymer complex structure in the main chain and an optically active substituent and an amide group in the side chain. Method for manufacturing hybrid materials.
<2> The method according to <1>, wherein each part of the metal and carbon in the main chain or the side chain is arranged substantially periodically in a planar geometrical and / or three-dimensional structure by the heat treatment. How to make metal-carbon hybrid materials.
<3><1> or <2>, which controls the matching sequence of each site of the main chain and the side chain in the conjugated polymer by changing the enantiomeric excess of the optically active substituent. The method for producing a metal-carbon hybrid material according to.
<4> The method for producing a metal-carbon hybrid material according to any one of <1> to <3>, wherein the conjugated polymer has a structure represented by the following formula (1):

(During the ceremony,
X is a metal complex site having at least one pyridine ring.
Y is a metal-containing π-conjugated polymer moiety having a structure represented by the following formula (2).

(In the formula, M is a metal element, A is a divalent aromatic hydrocarbon group, m is 1-10, and n is 1-1000), and Z. , A site having an optically active substituent and an amide group. ).
<5> The method for producing a metal-carbon hybrid material according to <4>, wherein the conjugated polymer has a structure represented by the following formula (3):

(In the formula, n is 1 to 1000.).
<6> The metal-carbon hybrid according to any one of <1> to <5>, wherein the heat treatment step raises the temperature of the conjugated polymer from room temperature to 900 ° C. in an Ar atmosphere. How to make the material.
<7> The method for producing a metal-carbon hybrid material according to any one of <1> to <6>, wherein the metal-carbon hybrid material is metal nanoparticles.
<8> A metal-carbon hybrid material obtained by the production method according to any one of <1> to <7>.

According to one aspect of the present invention, it is possible to provide a manufacturing method that enables mass production and / or cost reduction of a metal-carbon hybrid material. Further, according to one aspect of the present invention, it is possible to provide a production method capable of providing a novel metal-carbon hybrid material to which improved catalytic activity, new functions and the like are added.

It is a figure which shows the result of TGA measurement of the conjugated polymer during sintering which concerns on one Embodiment of this invention. It is a figure which shows the result of Raman spectrum measurement of the conjugated polymer before and after sintering which concerns on one Embodiment of this invention. It is a figure which shows the result of XPS measurement of the conjugated polymer before and after sintering which concerns on one Embodiment of this invention. It is a figure which shows the result of XRD of the conjugated polymer before sintering which concerns on one Embodiment of this invention. It is a figure which shows the result of XRD of the conjugated polymer after sintering which concerns on one Embodiment of this invention. It is a figure which shows the result of FE-SEM of the conjugated polymer before sintering which concerns on one Embodiment of this invention. It is a figure which shows the result of FE-SEM of the conjugated polymer after sintering which concerns on one Embodiment of this invention. It is a figure which shows the model which the conjugated polymer which concerns on one Embodiment of this invention is arranged substantially periodically in a three-dimensional structure according to the stage of sintering.

An embodiment of the present invention will be described in detail below.

Unless otherwise specified in the present specification, "A to B" representing a numerical range means "A or more and B or less".

[1. Overview〕
The method for producing a metal-carbon hybrid material according to an embodiment of the present invention (hereinafter, referred to as "the production method of the present invention") has a metal-containing π-conjugated polymer complex structure in the main chain and has a side chain. A method for producing a metal-carbon hybrid material, which comprises a step of heat-treating a conjugated polymer having an optically active substituent and an amide group in a chain.

The present inventor has conducted a more detailed analysis of the previously obtained phenylene ethynylene-based conjugated polymer. Specifically, the possibility of obtaining a metal-carbon hybrid material by heat-treating a phenylene ethynylene-based conjugated polymer was investigated.

As a result, the present inventor has provided carbides of phenylene ethynylene-based conjugated polymers in which the metal and carbon sites in the main chain or side chains are arranged substantially periodically in planar geometry and / or three-dimensional structure. I succeeded in getting it for the first time.

The mechanism by which the phenylene ethynylene-based conjugated polymer arranges the metal and carbon sites in the main chain or side chain substantially periodically in planar geometry and / or three-dimensional structure by heat treatment is described below. (See Examples and Drawings). That is, the mechanisms shown in the following (a) to (c) are assumed.
(A) By heat treatment in a reducing atmosphere, only amide and pyridine are decomposed and volatilized from the conjugated polymer (Fig. 3), and several tens of polymer molecules (conjugated polymer) can be aggregated (Fig. 1). ..
(B) Platinum sites are cleaved by reductive elimination at 300 ° C to 400 ° C to separate and aggregate platinum (FIGS. 5 and 8).
(C) Further, the heat treatment up to 900 ° C. causes agglutination of platinum crystal particles and formation of a carbon network structure bonded to each other so that carbon atoms can be stabilized by separation of platinum (FIGS. 7 and 7). 8).

In FIG. 8, the conjugated polymer after heat treatment at 400 ° C. to 900 ° C. corresponds to the metal-carbon hybrid material in one embodiment of the present invention.

The present inventor heat-treats a phenylene ethynylene-based conjugated polymer to provide carbides in which the metal and carbon sites in the main chain or side chains are arranged substantially periodically in planar geometry and / or three-dimensional structure. The reason why the phenylene ethynylene-based conjugated polymer used in the production method of the present invention can be obtained is that the phenylene ethynylene-based conjugated polymers are consistently arranged according to the combination of the features shown in the following (1) to (4). I conclude that there is.
(1) Flatness of the metal complex site in the metal-containing π-conjugated polymer complex structure in the conjugated polymer,
(2) Presence of optically active substituent in the side chain in the conjugated polymer,
(3) Hydrogen bonds between amide groups between conjugated polymers, and (4) π interactions between aromatic hydrocarbon groups and triple bonds at metal-containing π-conjugated polymer sites in conjugated polymers.

The above (1) means that the metal complex site of the conjugated polymer maintains the flatness of the metal complex site due to the high efficiency of the conjugate. For example, in the conjugated polymer having the structure represented by the above formula (3), the bipyrylidine-metal complex site forming the planar square molecular structure in the polymer main chain is an allylene ethinylene site such as phenylene ethynylene. Efficiently couples with and maintains high flatness.

The above (2) shows the regularity of the arrangement. For example, in a conjugated polymer having a structure represented by the above formula (3), the molecules are regularly arranged by the asymmetric inducing ability of an optically active substituent such as an amide group derived from alanine.

The above (3) means a hydrogen bond generated between amide groups existing in each conjugated polymer in a plurality of conjugated polymers.

In (4) above, the metal-containing π-conjugated polymer moiety of the conjugated polymer has an aromatic hydrocarbon group and a triple bond, and the π interaction occurs between the aromatic hydrocarbon group and the triple bond. This means that the flatness of the metal-containing π-conjugated polymer moiety is maintained.

Therefore, in one embodiment of the present invention, the production method of the present invention may be as follows.

A step of heat-treating a conjugated polymer having a metal-containing π-conjugated polymer complex structure in the main chain and an optically active substituent and an amide group in the side chain is included, and the heat treatment includes a step of heat-treating the conjugated polymer in the main chain or the side chain. A method for producing a metal-carbon hybrid material, which comprises arranging each part of metal and carbon substantially periodically in a planar geometrical and / or three-dimensional structure.

Further, in another embodiment of the present invention, the production method of the present invention may be as follows.

A method for producing a metal-carbon hybrid material, which comprises a step of heat-treating a conjugated polymer having a metal-containing π-conjugated polymer complex structure in the main chain and an optically active substituent and an amide group in the side chain.
The metal-containing π-conjugated polymer complex structure has a metal-containing π-conjugated polymer moiety having an aromatic hydrocarbon group and a triple bond and a metal complex moiety.
Here, by aligning the plurality of the conjugated polymers in accordance with the combination of the features shown in the following (1) to (4), each site of the metal and carbon in the main chain or the side chain after the heat treatment is performed. A method for producing a metal-carbon hybrid material, which comprises arranging the metal-carbon hybrid materials substantially periodically in plane geometry and / or three-dimensional structure:
(1) Flatness of the metal complex portion in the metal-containing π-conjugated polymer complex structure,
(2) Presence of optically active substituent in the side chain,
(3) Hydrogen bonds between the amide groups, and (4) π interaction between the aromatic hydrocarbon group and the triple bond at the metal-containing π-conjugated polymer moiety.

The manufacturing method of the present invention is a simple method that has never existed before, and has the effect of enabling mass production of a metal-carbon hybrid material and / or cost reduction. Further, in the production method of the present invention, as described above, by using a conjugated polymer having a specific structure, each part of the metal and carbon in the main chain or the side chain has a planar geometrical and / or three-dimensional structure. It is possible to obtain carbides arranged substantially periodically. Therefore, the metal-carbon hybrid material of the present invention is expected to exert effects such as improvement of catalytic activity and addition of new functions and the like.

[2. Conjugated polymer]
In one embodiment of the present invention, the conjugated polymer has a metal-containing π-conjugated polymer complex structure in the main chain and an optically active substituent and an amide group in the side chain.

In the production method of the present invention, by using a conjugated polymer having the above-mentioned characteristic structure, after heat treatment of the conjugated polymer, each part of the metal and carbon in the main chain or the side chain is planar geometry. Allows for approximately periodic arrangement of targets and / or three-dimensional structures.

In the present specification, the metal-containing π-conjugated polymer complex structure means a structure composed of a metal-containing π-conjugated polymer moiety and a metal complex moiety. Since the conjugated polymer has a specific metal-containing π-conjugated polymer complex structure in the main chain, the above (1) (that is, the flatness of the metal complex site in the metal-containing π-conjugated polymer complex structure in the conjugated polymer). Is guaranteed.

In one embodiment of the present invention, the conjugated polymer has a structure consisting of the following three sites.

In the above formula (1), X and Y form the main chain, and Z constitutes the side chain.

(Metal-containing π-conjugated polymer site)
In the above formula (1), Y is a metal-containing π-conjugated polymer moiety.

In the present specification, the metal-containing π-conjugated polymer moiety means a π-conjugated polymer containing a metal. Since the conjugated polymer has a metal-containing π-conjugated polymer moiety having a specific structure, the above (4) (that is, between the aromatic hydrocarbon group and the triple bond in the metal-containing π-conjugated polymer moiety in the conjugated polymer Π interaction) is guaranteed.

In one embodiment of the present invention, the metal-containing π-conjugated polymer moiety contains a metal element and an aromatic hydrocarbon group, and the metal element and the aromatic hydrocarbon group are linked by a single bond and a triple bond. Is preferable.

In one embodiment of the present invention, the metal-containing π-conjugated polymer moiety has, for example, a structure represented by the following formula (2).

In the above formula (2), M is a metal element.

In one embodiment of the present invention, the metal element may be a transition metal element of the tenth group, for example, platinum, palladium, nickel, and preferably platinum.

In the above formula (2), A is a divalent aromatic hydrocarbon group.

In one embodiment of the present invention, the divalent aromatic hydrocarbon group is not particularly limited as long as it is a divalent hydrocarbon group having at least one aromatic ring. In one embodiment of the present invention, the aromatic hydrocarbon group is, for example, a phenylene group, a naphthylene group, an anthracenylene group, a pyrenylene group, a phenanthrenyl group or the like, and is preferably a phenylene group.

In the above formula (2), m is, for example, 1 to 10, preferably 1 to 3, and more preferably 1.

In the above formula (2), n is, for example, 1 to 1000, preferably 10 to 100.

(Metal complex site)
In the above formula (1), X is a metal complex site. In the present specification, the metal complex site means a site forming a complex with a metal-containing π-conjugated polymer site.

In one embodiment of the present invention, the metal complex moiety is a structure capable of forming a complex with the metal-containing π-conjugated polymer moiety, and is not particularly limited as long as it has a structure having at least one pyridine ring. In one embodiment of the invention, the metal complex site has, for example, the structure shown below.

(Optically active substituent and amide group)
In the above formula (1), Z is a site having an optically active substituent and an amide group.

As used herein, the term optically active substituent has the meaning commonly used in the art and represents an optically active (optically active) substituent.

As used herein, the amide group has a meaning commonly used in the art and represents a substituent having a chemical bond formed by dehydration condensation of a carboxylic acid and an amine. When the conjugated polymer has an amide group in the side chain, the above (3) (that is, a hydrogen bond between the amide groups in the conjugated polymer) is ensured.

In one embodiment of the invention, the amide group can be, for example, a substituent derived from a bond between amino acids (eg, a bond between glycine and alanine, a bond between valine and leucine) and the like.

In one embodiment of the present invention, Z is not particularly limited as long as it has a structure having an optically active substituent and an amide group. In one embodiment of the invention, Z is, for example, the structure shown below.

In one embodiment of the invention, Z may further have any substituent at the end opposite to the main chain. Such a substituent is not particularly limited, but is, for example, a hydrocarbon group, for example, an aliphatic hydrocarbon group (for example, an alkyl group having 1 or more carbon atoms), an alicyclic hydrocarbon group, an aromatic hydrocarbon. A group (for example, a substituent containing a monocyclic aromatic hydrocarbon group, a polycyclic aromatic hydrocarbon group, a condensed aromatic hydrocarbon group, etc.) and the like. The hydrocarbon group may be linear or branched. In addition, some or all of the hydrogen atoms of the hydrocarbon group are alkyl groups, halogen atoms (chlorine, fluorine, iodine, or bromine), oxygen-containing substituents, nitrogen-containing substituents, phosphorus-containing substituents, and sulfur. It may be substituted with a substituent containing.

In one embodiment of the present invention, the production method of the present invention is a method of controlling the matching sequence of each site of the main chain and the side chain in the conjugated polymer by changing the enantiomeric excess of the optically active substituent. ..

As used herein, the enantiomeric excess of an optically active substituent has the meaning commonly used in the art and represents the optical purity of an optically active compound.

As a mechanism that can control the matching arrangement of each site of the main chain and the side chain in the conjugated polymer by changing the mirror image excess ratio of the optically active substituent, the optically active substituent existing in the side chain of the conjugated polymer is used. It is considered that the difference in the excess ratio of the mirror image causes a change in the twisting method when the conjugate polymer forms the secondary structure, and as a result, the three-dimensional structure after sintering also changes.

The method for changing the enantiomeric excess of the optically active substituent is not particularly limited, and examples thereof include a method in which the ratio of optical isomers is changed and added at the time of synthesizing a conjugated polymer. That is, in one embodiment of the present invention, "controlling the matching sequence of each site of the main chain and the side chain in the conjugated polymer by changing the enantiomer excess ratio of the optically active substituent" is "the conjugated polymer". By adding different ratios of optical isomers during the synthesis of the above, the matching sequence of each site of the main chain and the side chain in the conjugated polymer is controlled. "

In one embodiment of the present invention, the conjugated polymer has a structure represented by the following formula (1).

(During the ceremony,
X is a metal complex site having at least one pyridine ring.
Y is a metal-containing π-conjugated polymer moiety having a structure represented by the following formula (2).

(In the formula, M is a metal element, A is a divalent aromatic hydrocarbon group, m is 1-10, and n is 1-1000), and Z. , A site having an optically active substituent and an amide group. ).

Further, in one embodiment of the present invention, the conjugated polymer has a structure represented by the following formula (3).

In one embodiment of the present invention, the conjugated polymer having the structure represented by the above formula (3) has a platinum complex structure in the main chain of the pyridine ligand type and an optically active substituent in the side chain. It can also be expressed as a phenylene ethynylene-based conjugated polymer having an amide group.

In one embodiment of the present invention, the method for producing a conjugated polymer is not particularly limited. Taking a phenylene ethynylene-based conjugated polymer as an example, it can be produced by, for example, the following scheme 1 described in Examples.

In addition, in the above scheme 1, compound 1 and compound 2 can be synthesized according to Y. Otaki et al., Chem. Lett. 45, 937, 2016.

In one embodiment of the invention, the conjugated polymer may be in the form of a powder or a film. It can be used properly according to the purpose.

[3. Heat treatment (sintering)]
In the production method of the present invention, heat treatment conditions such as heat treatment temperature, temperature rise rate, atmospheric gas, and pressure can be appropriately set according to the purpose. That is, the conditions of the heat treatment are that, in the production method of the present invention, after the conjugated polymer is heat-treated, each part of the metal and carbon in the main chain or the side chain is substantially periodic in planar geometry and / or three-dimensional structure. The conditions may be such that the carbides arranged in the above can be obtained.

In one embodiment of the present invention, the heat treatment temperature under sintering conditions is, for example, 300 ° C. to 1300 ° C., preferably 900 ° C.

In one embodiment of the present invention, the heating rate under sintering conditions is, for example, 1 ° C./min to 100 ° C./min, preferably 10 ° C./min.

In one embodiment of the present invention, the atmospheric gas under the sintering conditions is, for example, Ar, H ₂ , O ₂ , He, etc., preferably Ar.

In one embodiment of the present invention, the sintering conditions may be, for example, the sintering conditions described in the examples (heat treatment temperature: 900 ° C., heating rate: 10 ° C./min, atmospheric gas: Ar).

[4. Metal-carbon hybrid material]
In one embodiment of the present invention, the metal-carbon hybrid material obtained by the production method of the present invention (hereinafter, referred to as “the metal-carbon hybrid material of the present invention”) is provided.

As described above, in the production method of the present invention, by using a conjugated polymer having a specific structure, each part of the metal and carbon in the main chain or the side chain has a planar geometrical and / or three-dimensional structure. Carbides arranged substantially periodically can be obtained. Therefore, the metal-carbon hybrid material of the present invention is expected to exert effects such as improvement of catalytic activity and addition of new functions and the like.

In one embodiment of the present invention, the new function includes, for example, improvement of product selectivity.

Further, as described above, the production method of the present invention is also a method of controlling the matching sequence of each site of the main chain and the side chain in the conjugated polymer by changing the enantiomeric excess of the optically active substituent. Therefore, the metal-carbon hybrid material obtained by such a production method is also expected to have effects such as improvement of catalytic activity and addition of new functions and the like.

The metal-carbon hybrid material obtained by the production method of the present invention is not particularly limited as long as it is a composite containing metal and carbon obtained by the production method of the present invention. Examples of the metal-carbon hybrid material include metal nanoparticles, carbon fiber reinforced metal, carbon fiber coating material, and the like.

The metal-carbon hybrid material obtained by the production method of the present invention can be used in various fields such as industrial plants, automobile industry, aerospace base materials, construction / civil engineering materials, sports / leisure goods, and the like.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

〔measuring equipment〕
¹ H (400 MHz) NMR, ¹³ C (100 MHz) NMR and ³¹ P (162 MHz) spectra were measured using the JEOL LNM-ECS400 spectometer (JEOL) and JEOL JNM-ECZ400 spectrometer (JEOL). did. The number average molecular weight (M _n ), weight average molecular weight (M _w ) and dispersion ratio (D) are SEC [(Shodex KF-805L × 3, JASCO RI-4030, JASCO UV-4075, JASCO PU-4180, JASCO DG). -980-50, CO-4060, LC-NetII / ADC, AS-2055 Plus, TSK gel <α-M, GMHXL, THF solution, polystyrene conversion>) and (Shodex KF-805L × 3, JASCO RI-930, Measurement was performed using JASCO UV-2075 Plus, JASCO PU-980, JASCO DG-980-50, CO-965, TSK gel <α-M, GMHXL, DMF solution, polystyrene conversion>). The TGA measurement was performed under an argon air flow using the Shimadzu thermogravimetric analyzer TGA-50. In addition, the device was used in the synthesis of carbides of conjugated polymers by heat treatment. The Raman spectrum was measured using a 3D microlaser Raman spectroscope Nanofiber30 (manufactured by Tokyo Instruments) and an NRS-5100 type laser Raman spectrophotometer (manufactured by JASCO Corporation). XPS measurement was performed using PHI 5000 Versa Probe III (manufactured by ULVAC-PHI). XRD was measured using a D2 Phaser (manufactured by BRUKER) ((source is CuKa line). FE-SEM was measured using JSM-6330FII (manufactured by JEOL).

〔reagent〕
Commercially available products were used without purification unless otherwise specified. The solvent used in the reaction under Ar was dehydrated by adding Molecular Sieves 4A 1/16 (manufactured by Wako Pure Chemical Industries, Ltd.) and degassed by Ar gas bubbling.

[Instrument]
A platinum pan φ6 × 2.5 nm was used. The platinum pan used for sintering the conjugated polymer was used again by raising the temperature from room temperature to 1000 ° C. (heating rate = 10 ° C./min) and heating at 1000 ° C. for 1 hour using an electric furnace. ..

[Image analysis]
For image analysis, the size of the particle size was determined using image analysis software Image J (published by the National Institutes of Health NIH, version 1.51). As a condition, all particles that could be identified as particles were measured, and particles smaller than 15 nm (magnification 20000) were truncated. In addition, those with a distorted shape were truncated if the ratio (aspect ratio) of the major axis to the minor axis when the spheroid was formed was more than 2.

[Synthesis of phenylene ethynylene-based conjugated polymer]
A phenylene ethynylene-based conjugated polymer (hereinafter, simply referred to as “conjugated polymer”) was synthesized according to Scheme 1 below. In Scheme 1 below, Compound 1 and Compound 2 were synthesized according to Y. Otaki et al., Chem. Lett. 45, 937, 2016.

1 (44.9 mg, 0.11 mol), 2 (58.8 mg, 0.11 mol) and CuI (2.1 mg, 0.011 mol) were charged in the reaction vessel, degassed and replaced with argon, and then chloride with a syringe. Methylene (5.5 ml) and diisopropylamine (5.5 ml) were added. The mixture was then reacted at room temperature for 6 hours. After completion of the reaction, the solvent was distilled off with a rotary evaporator. The polymerization mixture was dissolved in a small amount of chloroform and charged into a large amount of hexane. The resulting precipitate was filtered off to give a conjugated polymer as an orange solid (91.2 mg, 95.5%).
IR (KBr tablet method): 1618 , 1652, 2107, 24.89, 2566, 2722, 2759, 2853, 2925, 2963, 3054, 3310, 3674, 3744. 1 H-NMR (400 MHz, CDCl 3): δ 0.86- 1.49 (m, 44H, 2 × -C (CH ₃ ) ₃ , -CH (CH ₃ )-, -NHCH ₂ (CH ₂ ) ₁₀ CH ₃ , 3.08-3.42 (m, 2H, -NHCH _2- ), 4.66 -4.69 (br, 1H,> CH-), 7.00-7.03 (br, 2H, 2 × -NH-), 7.41-7.99 (br, 7H, Ar), 9.59-9.63 (br, 2H, Ar). Mn 6,500, D 1.7 (determined by SEC tablets with DMF calibrated by polystyrene standards), Mn 2,400, D 1.1 (determined by SEC tablets with THF calibrated by polystyrene standards).
[Synthesis of carbides of conjugated polymers]
20 mg of the conjugated polymer was placed in a Pt pan, and the temperature was raised from room temperature to 900 ° C. (heating rate = 10 ° C./min) in an Ar atmosphere using TGA-50 / 50H to react. After completion of the reaction, a slightly glossy black solid was obtained (mass after sintering / mass before sintering = 5.8 / 15.6 × 100 = yield 37%). The obtained carbide was degassed with a desiccator, sealed with Ar, and stored.

[TGA measurement]
The TGA of the conjugated polymer being sintered was measured using the equipment described in the above [Measuring equipment]. The results are shown in FIG.

From FIG. 1, it was found that the mass was significantly reduced when the temperature was raised from 300 ° C. to 400 ° C. It is considered that the conjugated polymer contains a large amount of nitrogen and oxygen heteroatoms such as amide groups and pyridines in the molecule, and pyrolysis volatile components are generated during sintering, resulting in a small mass residue.

[Raman spectrum measurement]
The Raman spectrum of the conjugated polymer before and after sintering was measured using the equipment described in the above [Measuring equipment]. The results are shown in FIG.

From FIG. 2, changes in Raman peak were clearly observed before and after sintering. Specifically, after sintering, D and G bands peculiar to graphene-type carbon materials were observed near 1300 and 1600 cm ^-1, respectively, suggesting the formation of a carbon network. Further, since the strength of the D band attributed to CC stretching vibration or non-crystalline carbon was higher than that of the G band attributed to C = C stretching vibration of crystalline carbon, the residual alkyl group and The existence of lattice defects was suggested.

[XPS measurement]
The XPS of the conjugated polymer before and after sintering was measured using the equipment described in the above [Measuring equipment]. The results are shown in FIG.

From FIG. 3, the peak of nitrogen that existed before sintering disappeared after sintering, suggesting that the amide group and pyridine in the conjugated polymer are decomposed by thermal decomposition. It was.

[XRD]
The XRD of the conjugated polymer before and after sintering was measured using the equipment described in the above [Measuring equipment]. The results are shown in FIGS. 4 and 5.

From FIGS. 4 and 5, five diffraction peaks derived from platinum that were not observed before sintering (2θ = 40.2, 46.7, 68.1, 81.9, 86.4 °, 2.2 each). (Corresponding to 1.9, 1.4, 1.2, 1.1 Å) is observed after sintering and is attributed to (111), (200), (220), (311), (222). .. This suggests that the sintered platinum particles form a face-centered cubic structure.

[FE-SEM]
The FE-SEM of the conjugated polymer before and after sintering was measured using the equipment described in the above [Measuring equipment]. The magnification of surface observation was 20000 times. The results are shown in FIGS. 6 and 7.

From FIGS. 6 and 7, platinum particles that were not observed before sintering could be confirmed on the entire surface after sintering. The average diameter of the carbide particles of the conjugated polymer after sintering was 50 nm.

That is, it was suggested that after sintering, platinum atoms aggregated to form platinum particles.

The manufacturing methods of the present invention enable mass production and / or cost reduction of metal-carbon hybrid materials in various fields in which metal-carbon hybrid materials are used (eg, industrial plants, automobile industry, aviation and aviation. It can be suitably used in space base materials, construction / civil engineering materials, sports / leisure goods, etc.). Further, since the metal-carbon hybrid material produced by the production method of the present invention is expected to have effects such as improvement of catalytic activity and addition of new functions, it is suitable as a new metal-carbon hybrid material in various fields. It can be used.

Claims (8)

A metal-carbon hybrid material comprising a step of heat-treating a conjugated polymer having a metal-containing π-conjugated polymer complex structure in the main chain and an optically active substituent and an amide group in the side chain. Production method. The metal according to claim 1, wherein each portion of the metal and carbon in the main chain or the side chain is arranged substantially periodically in planar geometry and / or three-dimensional structure by the heat treatment. Method of manufacturing carbon hybrid material. The metal according to claim 1 or 2, characterized in that the matching sequence of each site of the main chain and the side chain in the conjugated polymer is controlled by changing the enantiomeric excess of the optically active substituent. Manufacturing method of carbon hybrid material. The method for producing a metal-carbon hybrid material according to any one of claims 1 to 3, wherein the conjugated polymer has a structure represented by the following formula (1):
(During the ceremony,
X is a metal complex site having at least one pyridine ring.
Y is a metal-containing π-conjugated polymer moiety having a structure represented by the following formula (2).
(In the formula, M is a metal element, A is a divalent aromatic hydrocarbon group, m is 1-10, and n is 1-1000), and Z. , A site having an optically active substituent and an amide group. ). The method for producing a metal-carbon hybrid material according to claim 4, wherein the conjugated polymer has a structure represented by the following formula (3).
(In the formula, n is 1 to 1000.). The production of the metal-carbon hybrid material according to any one of claims 1 to 5, wherein the heat treatment step raises the temperature of the conjugated polymer from room temperature to 900 ° C. in an Ar atmosphere. Method. The method for producing a metal-carbon hybrid material according to any one of claims 1 to 6, wherein the metal-carbon hybrid material is metal nanoparticles. A metal-carbon hybrid material obtained by the production method according to any one of claims 1 to 7.