CN103372408B - With while gasification prepare the method for core-carbon complex and prepared core-shell structure metall-carbon complex - Google Patents

Abstract

The present invention relates to a method for preparing a metal-carbon composite having a core-shell structure in which metal particles form the core and carbon forms the shell, in the form of powder and supported on a carrier, using a simultaneous vaporization method, and the core prepared thereby ‑shell-structured metal‑carbon composites. According to the preparation method of the present invention, since it uses simultaneous vaporization technology, it can simultaneously vaporize metal and organic precursors including carbon to synthesize metal-carbon core-shell structure composites, so there is no need to carry out additional steps like previous projects. Advantages of postprocessing. Moreover, the composite prepared in this way, because the carbon shell covers part or all of the surface of the metal core, is suitable for high temperature, long time, strong acid and alkaline and other harsh reaction engineering, and metal ions will not condense or fall off. And corrosion phenomenon, so as to have high performance and durability.

Description

Method for preparing core-carbon composite by simultaneous vaporization method and prepared core-shell structure metal-carbon composite

technical field

The invention relates to a metal-carbon composite with a core-shell structure and a preparation method thereof, in particular to a metal with a core-shell structure in which metal particles are used to form the core and carbon is used to form the shell in the form of powder or supported on a carrier. - A method of carbon composites, whereby core-shell structured metal-carbon composites are prepared.

Background technique

Due to the recent problem of depletion of noble metal resources, a great deal of research has been directed to noble metal catalysts having various functions while providing durability. The noble metal catalyst itself has excellent catalytic activity compared with other metal catalysts, but the preparation cost is expensive. Therefore, the technology of nano-sized and highly dispersed noble metal particles is being developed. On the other hand, with the increase of the catalytic reaction temperature, the metal particle phase Agglomeration, and during the catalytic process, metal particles are detached from the composite, and thus a serious problem of durability degradation occurs, so that research to solve these problems is underway.

As the best method to solve the above problems, the present invention uses the simultaneous vaporization method to synthesize expensive metals such as precious metals into nanoparticles while synthesizing a core-shell structure that forms a carbon layer on the surface of the precious metal particles. Therefore, in the high-temperature catalytic process, Aggregation of particles does not occur, and catalyst particles do not corrode or fall off during the reaction, so catalyst durability can be remarkably improved.

Tao Zheng etc. have prepared platinum-carbon composites by carbonizing the mixture of platinum (Pt) complex salts, surfactants, water, and ethanol, and tested their performance under the oxidation reaction of carbon monoxide (refer to the literature [Colloids and Sufraces A: Physicochem. Eng. Aspects 262 (2005) 52-56, onic surfactant-mediated synthesis of Pt nanoparticles/nanoporous carbons composites]). However, this method uses a solution method, and the carbocycle of the precursor solution needs to be carried out at high temperature, so the preparation cost increases, and it needs to go through multiple steps to produce the Pt/C composite, so there are disadvantages of complicated procedures.

In addition, Korean Laid-Open Patent No. 10-2011-0139994A also discloses a technique for preparing lithium manganese oxide-carbon nanocomposites by mixing them in an ionic solution state. The above-mentioned patents require multiple steps such as solution reaction, crystal growth, chemical treatment with strong acid/strong base for template removal, and heat treatment for alloying in order to synthesize the composite.

Contents of the invention

The purpose of the present invention is to provide a method for preparing metal-carbon composites with a core-shell structure that does not change due to production scale changes, is suitable for mass production, and uses simpler simultaneous vaporization engineering than previous technologies.

Another object of the present invention is to provide a kind of high-performance steel sheet that is suitable for severe reaction processes such as high temperature, long time, strong acidity and alkalinity, and will not cause metal particles to agglomerate or fall off, and will not cause corrosion. And high-durability core-shell metal-carbon composites.

Another object of the present invention is to provide a method for preparing metal-carbon composites with a core-shell structure, which is prepared by a simultaneous vaporization method that does not change due to changes in production scale and is suitable for mass production, and includes a variety of carbon Materials, aluminum, silicon, zeolite, zirconia, titania, etc. are used as supports, so that they can be effectively applied to most catalytic processes that previously used heterogeneous catalysts (heterogeneous catalysis), and have high performance/high durability.

Another object of the present invention is to provide a high-performance metal-carbon composite with excellent performance and durability, which includes the surface and interior of various carbon materials, aluminum, silicon, zeolite, cobalt oxide, titanium oxide and other carriers. The core-shell nanocomposite in the stomata can be effectively applied to most catalytic engineering using previous heterogeneous catalysts.

In order to achieve the above object, the present invention provides a method for preparing a metal-carbon composite with a core-shell structure, which includes the steps of providing metal precursors vaporized in respective vaporizers and organic precursors for forming carbon skeletons- S1; Step-S2 of supplying vaporized metal precursors and organic precursors in the reactor in a non-contact state by using a carrier gas; Step-S3 of synthesizing metal-carbon composites by heating the reactor and maintaining a constant temperature .

Furthermore, the present invention provides a metal-carbon composite having a core-shell structure, wherein the core is formed of metal and the shell is formed of carbon, characterized in that the shell has a structure in which part or all of the core is surrounded by the shell.

The present invention also provides a method for preparing a metal-carbon composite with a core-shell structure supported on a carrier, which includes: step-S1 of arranging the carrier in the reactor; providing metal precursors vaporized in each vaporizer and using In the step-S2 of forming the organic precursor of the carbon skeleton; the step-S3 of supplying vaporized metal precursors and organic precursors in the reactor in a non-contact state by using the carrier gas; and keeping a constant temperature after heating the above reactor The step-S4 of synthesizing the metal-carbon composite loaded on the support at the temperature.

Finally, the present invention provides a metal-carbon composite with a core-shell structure supported on a carrier, characterized in that the core is formed of metal and the shell is formed of carbon, and the shell wraps part or all of the core.

According to an embodiment of the present invention, the metal-carbon composite with a core-shell structure is prepared by vaporizing metal and carbon precursors at the same time. By adjusting the synthesis temperature and composition, it can have different properties and does not require other post-treatments. Therefore It is process simplification.

Description of drawings

The above and other objects, features and advantages of the present invention will be easier to understand by referring to the description of the embodiments given in the accompanying drawings, wherein:

Figure 1 is a photograph of the platinum-carbon composite with a core-shell structure prepared in Example 1 and the platinum-carbon composite with a core-shell structure prepared on a carrier prepared in Examples 2 to 4 using a scanning electron microscope (SEM). micrograph.

FIG. 2 is a photomicrograph of the platinum-carbon composite with core-shell structure supported on carbon paper prepared in Example 2, taken with a transmission electron microscope (TEM).

detailed description

Hereinafter, the embodiments of the present invention will be further described in detail with reference to the accompanying drawings.

In one aspect of the present invention, a metal-carbon composite with a core-shell structure can be prepared in an independent powder form by using a simultaneous vaporization process. Specifically, the method for preparing a metal-carbon composite with a core-shell structure of the present invention is characterized in that it includes: step-S1 of providing metal precursors vaporized in respective vaporizers and organic precursors for forming carbon skeletons ; The step-S2 of supplying vaporized metal precursors and organic precursors in the reactor in a non-contact state by using the carrier gas; the step-S3 of synthesizing the metal-carbon composite by heating the reactor and maintaining a constant temperature.

First, metal precursors vaporized in respective vaporizers and organic precursors for forming carbon skeletons are provided—step S1.

In this step, the metal precursor is supplied in one vaporizer, and the organic precursor used to form the carbon skeleton is supplied in the other vaporizer, and the temperature of each vaporizer is raised to around the boiling point of each precursor, so that the metal precursor can be vaporized simultaneously. bodies and organic precursors. When a gaseous organic precursor is used, the precursor is directly supplied in the vaporizer without going through an additional vaporization process.

The metal precursor used in this step is a precursor of the metal that finally forms the core of the heterocomposite, and any vaporizable substance can be used. Preferably use one selected from the group consisting of a platinum precursor, a palladium precursor, a ruthenium precursor, a nickel precursor, a cobalt precursor, a molybdenum precursor, and a gold precursor. Cyclopentadiene) platinum (IV), platinum acetylacetonate (II), platinum tetrakis (phosphorus trifluoride) (0), platinum tetrakis (triphenylphosphine) (0), platinum hexafluoroacetylacetonate (II) , trimethyl(methylcyclopentadiene)platinum(IV) and (1,5-cyclooctadiene)dimethylplatinum(II) selected from the group. Palladium(II) acetate, palladium(II) hexafluoroacetylacetonate, or palladium(II) acetylacetonate are preferably used as palladium (Pd) precursors, and ruthenium acetylacetonate, bis(ethyl Cyclopentadiene)ruthenium(II), bis(cyclopentadienyl)ruthenium(II), or tris(2,2,6,6-tetramethyl-3,5-heptanedione)ruthenium(III). Nickel(II) acetoacetonate, nickel bis(cyclopentadiene), or nickel tetrakis(phosphorous trifluoride) is preferentially used as nickel (Ni) precursor, and cobalt acetylacetonate is preferentially used as cobalt (Co) precursor (II), cobalt dicarbonyl cyclopentadiene, cobalt carbonyl, or cyclopentadiene dicarbonyl cobalt (I), and molybdenum hexacarbonyl or molybdenum chloride (V) is preferentially used as a molybdenum (Mo) precursor, as gold The (Au) precursor is preferentially methyl(triphenylphosphine) gold (I), but the gas phase conditions and vaporization temperatures suitable for each precursor are different, so appropriate adjustments are required.

The organic precursor used in this step is a precursor of carbon that finally forms the shell of the heterocomposite, and a hydrocarbon-based precursor containing carbon can be used. Preferably a liquid precursor selected from the group consisting of methanol, ethanol, acetone, benzene, toluene and xylene is used, or a gaseous precursor such as methane or acetylene is used.

The evaporator used in this step can be known or directly manufactured, and generally can use a evaporator made of metal material or glass (such as quartz glass or pyrex glass). In order to confirm the nature and balance of the content while maintaining a constant temperature, the vaporizer should be made of glass that does not react with the precursor.

The specific vaporization conditions of the precursor in this step vary according to the type of precursor selected. According to a specific embodiment of the present invention, if trimethyl (methylcyclopentadiene) platinum is used as the platinum precursor, vaporization is carried out at a temperature of 50-70° C., and if acetone is used as the organic precursor, it is vaporized with 50- Vaporization is carried out at a temperature of 60°C. According to another specific embodiment of the present invention, if (1,5-cyclooctadiene) dimethyl platinum (II) is used as the platinum precursor, in the state of being dissolved in a solvent such as benzene, use a temperature above 100 ° C high temperature vaporization.

Then, the respective metal precursors and organic precursors vaporized in step S1 are supplied in the reactor in a non-contact state using a carrier gas—step S2.

In this step, a carrier gas including each precursor in a gaseous state is supplied to the reactor in a non-contact state, for example, through an independent supply line. The vaporized precursors thus merge at the inflow portion of the reactor where the final reaction takes place. If the various precursors meet during the transmission, unexpected side reactions will occur or may be attached to the path wall.

The carrier gas used in this step is used to prevent the condensation of the precursor phase or side reactions, and nitrogen, argon, helium, oxygen or hydrogen can be used. Inert gases such as nitrogen, argon, and helium are preferably used mainly, but oxygen or hydrogen may also be used depending on the precursor.

In this step, the properties of the final complex can be controlled by adjusting the flow ratio of each precursor supplied to the reactor. For example, when the flow ratio of the metal precursor to the organic precursor is 2:1, compared with the flow ratio of 1:1, the thickness of the carbon shell and the number of graphite layers are reduced. Thus, various metal-composites can be synthesized by changing the flow ratio according to the applicable catalytic reaction.

According to an embodiment of the present invention, each precursor vaporized in an oven maintained at a certain temperature is transported to the reactor through a gas delivery channel, and a heating wire is wound around the gas delivery channel to prevent condensation or condensation of the vaporized precursor. At this time, when supplying each precursor in the reactor, it is preferable to keep the temperature near the boiling point of the precursor.

Finally, heating the reactor supplied with each precursor in step S2 and maintaining a predetermined temperature, thereby preparing a powdery metal-carbon composite with a core-shell structure—step S3. The reaction temperature used to synthesize the metal-carbon composite with core-shell structure in this step varies according to the types of precursors, metal and organic precursors. Usually, the temperature is about 300 ° C or above, preferably 300-1800 ° C. The synthesis proceeds well at 0°C, but it is understood that the synthesis temperature can be selected with proper design of the furnace and reactor. For example, if a quartz glass reactor is used, the temperature of 300-1100°C is preferred, and if an aluminum tube or graphite (graphite) reactor is used, it can be used up to 1800°C, and by properly designing the furnace and reactor, it can also be used Use a temperature of 1800°C or above. As the synthesis temperature rises, the defects in the shell covering the metal particles decrease, improving crystallinity. The synthesis time is preferably 5 minutes or more, preferably about 1 hour, but the longer the synthesis time is, the more the amount of metal-carbon composites will increase.

The metal-carbon composite with a core-shell structure prepared according to the preparation method of the present invention has a core formed by metal and a shell formed by carbon, and is characterized in that the shell wraps part or all of the core.

When applied to ordinary molecular catalysis, the complex according to the present invention has a core-shell structure, which is characterized in that the above-mentioned shell wraps a part of the core, that is, due to the partial shell defect in the core-shell structure composition, it is formed in the The movement of reactants and products in the catalytic reaction is very smooth. And, when the composite according to the present invention is used as an electrode material such as a fuel cell or a secondary battery, the core-shell structure composite has a core-shell structure in which the movement of ions or electrons is targeted, so It is preferable to have a complete structure in which the core is surrounded by the shell, that is, to form a smooth carbon shell without defects like graphene. According to the compound of the present invention, because the carbon shell wraps a part or all of the surface of the metal core, even if it is used at high temperature, for a long time, in severe reaction projects such as strong acidity and alkalinity, the metal particles will not aggregate or fall off, And there will be no corrosion, so it has high performance and high durability.

In another aspect of the present invention, a metal-carbon composite with a core-shell structure can be prepared in the form of being supported on a carrier by using a simultaneous vaporization process and a carrier. Specifically, the method for preparing a metal-carbon composite with a core-shell structure loaded on a carrier of the present invention includes: step-S1 of arranging a carrier in a reactor; providing metal precursors vaporized in respective vaporizers and using In the step-S2 of forming the organic precursor of the carbon skeleton; the step-S3 of supplying vaporized metal precursors and organic precursors in the reactor in a non-contact state by using the carrier gas; and keeping a constant temperature after heating the above reactor The step-S4 of synthesizing the metal-carbon composite supported on the carrier at a higher temperature.

The carrier used in the present invention is not particularly limited, and carbons such as carbon paper, activated carbon, and carbon black, aluminums such as aluminum powder and aluminum plate, silica fume, titanium oxide powder, zirconium oxide powder, various zeolites, and nickel, Selected from the group consisting of aluminum and other metal foils (foil). Prioritize the use of a carrier with a large surface area, which can maximize the loading effect, so carbon powder, aluminum powder, and zeolite powder can be used to prepare a metal core-carbon shell structure, and the metal core-carbon shell structure is suitable for modification reactions , thermal decomposition reaction, hydrogenation/dehydrogenation reaction and other catalytic reactions.

The composite synthesis method of this specific embodiment of the present invention is to arrange the carrier in advance in the reactor, and synthesize the composite on the carrier, and the final product is a metal-carbon composite with a core-shell structure loaded on the carrier, from This point is different from the above specific embodiment, but steps S2 to S4 are the same as the method of the above specific embodiment.

According to the method of this specific example, a metal-carbon composite in which a core is formed of metal and a shell is formed of carbon can be prepared in the form of being supported on a carrier, and the shell wraps a part or all of the core. When applied to catalytic reactions of ordinary molecules in the gas phase state, the composition of the present invention has a core-shell structure, wherein the shell wraps a part of the core, that is, the shell of the core-shell structure has defects. According to this embodiment of the present invention, the composite is loaded on, therefore, after the catalytic reaction is completed, it is convenient to recycle the catalyst, and the composite is used in the state loaded on the carrier, so when using the previous monolithic catalyst, honeycomb catalyst ( Honeycomb) or microreactors, membrane reactors, fixed bed (packed bed) reactors, etc., are particularly useful for catalytic reactions, and when the complex according to the present invention is loaded on an existing adsorbent, it is easy to apply to various Adsorption/desorption engineering.

Below, in order to facilitate the understanding of the present invention to propose preferred embodiments, but the following embodiments are only illustrations of the present invention, various changes and amendments can be made within the scope of the present invention and the scope of technical ideas, therefore, the protection scope of the present invention is limited only by limited by the appended claims and their equivalents.

Embodiment 1: Prepare the platinum-carbon composite of core-shell structure

Methylcyclopentadiene platinum (MeCpPtMe ₃ ) was used as platinum precursor and acetone (99.8%, Merck) was used as carbon precursor. In order to capture metal-carbon complexes, a quartz filter was installed in a quartz tube (1/2 inch), and nitrogen gas was flowed in at 120°C and maintained for 2 hours to remove moisture and impurities inside the reagent. At this time, the two evaporators installed in the oven, while maintaining a nitrogen environment inside, closed all inflow and outflow cocks, and flowed nitrogen gas for 30 minutes through a bypass line that does not pass through the evaporator to remove the reaction. Impurities inside the device.

Then, at a heating rate of 10°C per minute, the temperature of the reactor part is raised to 400°C to form the conditions for the synthesis of complexes. When the temperature of the reactor part reaches the final reaction temperature, the vaporizer containing the platinum precursor is installed The temperature of the inner oven 1 was raised to 60°C, and the temperature of the inner oven 2 was raised to 55°C with a vaporizer containing acetone installed. When the temperature of each precursor and the reactor reaches the final target temperature, open the valve of each vaporizer so that the carrier gas and the vaporized precursor can reach the reactor part. Now use nitrogen as the carrier gas, for the pipeline through the oven 1 filled with platinum precursor, the flow rate is 20 sccm, and for the pipeline through the oven 2 filled with acetone, the flow rate is 10 sccm, nitrogen is also supplied with the flow rate of 20 sccm in addition Pipelines connected to the reactor independently. The instant the reaction starts is when the cock of the vaporizer is opened, and the reaction time is maintained for 1 hour from this moment to synthesize a platinum-carbon composite with a core-shell structure.

Examples 2 to 4: Preparation of platinum-carbon composites with a core-shell structure loaded on a carrier

Methylcyclopentadiene platinum (MeCpPtMe ₃ ) was used as platinum precursor and acetone (99.8%, Merck) was used as carbon precursor. In order to trap metal-carbon composites, a quartz filter is set in a quartz tube (1/2inch), and a carbon paper of a size of 10mm X10mm (Example 2), an aluminum plate of a size of 10mmX10mm (Example 3), A nickel foil (Ni foil) with a size of 10mm×10mm (Example 4) was then flowed into nitrogen gas at 120° C. and maintained for 2 hours to remove moisture and impurities inside the reagent. At this time, the two vaporizers installed in the oven, while maintaining a nitrogen environment inside, close all the inflow and outflow valves, and flow nitrogen through a bypass line that does not pass through the vaporizer for 30 minutes to remove the reaction. Impurities inside the device.

Then, at a rate of 10°C per minute, the temperature of the reactor part was raised to 400°C to form conditions for the synthesis of metal-carbon composites. When the temperature of the reactor part reached the final reaction temperature (carbon paper: 400°C, Aluminum plate: 400°C, nickel foil: 400°C), the temperature of Oven 1 equipped with a vaporizer containing a platinum precursor is raised to 60°C, and the temperature of Oven 2 equipped with a vaporizer containing acetone is increased is 55°C. When the temperature of each precursor and the reactor reaches the final target temperature, open the valve of each vaporizer so that the carrier gas and the vaporized precursor can reach the reactor part. At this time, nitrogen is used as the carrier gas. For the pipeline passing through the oven 1 containing the platinum precursor, the flow rate is 20 sccm, and for the pipeline passing through the oven 2 containing acetone, the flow rate is 10 sccm. Nitrogen gas was flowed at 20 sccm. The moment the reaction starts is when the stopcock of the vaporizer is opened, and a certain period of time (carbon paper: 1 hour, aluminum plate: 1 hour, nickel foil: 1 hour) is maintained from then on to synthesize platinum-carbon with a core-shell structure. Complex.

Experimental Example 1: Scanning Electron Microscopy (SEM) Analysis

The platinum-carbon composite (A) with a core-shell structure prepared in Example 1 and the platinum-carbon Carbon composites (referred to as B, C, D in turn), the results are shown in Figure 1. The conclusion is that platinum-carbon composites can be synthesized on the surface of carbon paper, aluminum, and nickel foil, and the largest amount of platinum-carbon composites is formed on carbon paper. The platinum particle size synthesized on nickel foil was larger than in the other two cases.

Experimental Example 2: Transmission Electron Microscopy (TEM) Analysis

The platinum-carbon composite with a core-shell structure prepared in Example 1 was analyzed using a transmission electron microscope, and the results are shown in FIG. 2 . FIG. 2A is a TEM micrograph in which the overall distribution of composite particles can be confirmed, and FIG. 2B is a further enlarged micrograph in which a fine structure can be observed. In FIG. 2, it can be confirmed that a platinum-carbon composite having a core-shell structure was synthesized by the present invention, wherein platinum is located in the center of the structure to form a core, and carbon, that is, graphite layers are wrapped around the core to form a shell. The carbon shell located outside the core is generally composed of 1-5 graphite layers, and the defect degree of the carbon shell can be adjusted by changing the synthesis temperature. Also, the size of the particles is about in the range of 2-5nm. That is, the higher the core-shell structure synthesized at high temperature, the fewer defects of the carbon shell and the smoother the surface. Moreover, as the ratio of organic precursor flow rate to metal precursor flow rate decreases, the thickness of the carbon shell becomes smaller. However, the shape of the carbon shell varies not only due to the flow of carbon but also due to the type of organic precursor. That is, when a precursor with a low carbon number such as methane is used, the number of carbon shells formed is smaller than when a precursor such as acetylene or alcohol is used. This metal-carbon core-shell structure provides reaction conditions that facilitate the movement of gas molecules, ions, and electrons, and the platinum particles do not corrode.

As mentioned above, according to the present invention, in the metal-carbon composite of core-shell structure, the carbon shell wraps a part or all of the metal surface, so it is suitable for severe reaction projects such as high temperature, long time, strong acidity and alkalinity. At the same time, there will be no aggregation or shedding of metal particles and no corrosion, so it has high performance and high durability. The metal-carbon composite with a core-shell structure of the present invention can be applied to a variety of application fields, specifically, it can be applied to catalytic materials in various reactions, catalytic materials such as monolithic catalysts, honeycomb (Honeycomb) catalysts, etc. Channel-type catalytic reactor, various separation membrane materials, absorption and adsorbents, etc.

Although some specific examples are provided to illustrate the present invention, it should be understood that these examples are given by way of example only, and that various modifications, changes and substitutions can be made without departing from the spirit and scope of the invention. The scope of the invention should be limited only by the appended claims and their equivalents.

Claims (16)

1. the preparation method of the metal-carbon composite of a nucleocapsid structure, it is characterised in that including:

There is provided metal precursor and for forming the organic matter precursor of carbon skeleton, wherein, described metal precursor It is the presoma of a kind of metal, for forming the core in nucleocapsid structure, before described metal precursor and Organic substance Drive body through respective carburator, to be fed into the step (S1) of reactor under vapor state；

Introduce vaporization presoma to before reactor, be utilized respectively delivery gas with contactless state, separately and with Time in reactor, supply each metal precursor of vaporization and the step (S2) of organic matter precursor；

A steady temperature is kept to synthesize the step (S3) of metal-carbon composite after heating above-mentioned reactor；

Before above-mentioned metal precursor is choosing free platinum presoma, palladium presoma, ruthenium presoma, nickel presoma, cobalt Drive one of group of body, molybdenum presoma and gold presoma composition.

The preparation method of the metal-carbon composite of nucleocapsid structure the most according to claim 1, it is characterised in that

Above-mentioned platinum (Pt) presoma choosing free trimethyl (methyl cyclopentadiene) platinum (IV), acetylacetone,2,4-pentanedione platinum (II), Four (phosphorus trifluoride) platinum (0), four (triphenylphosphine) platinum (0), hexafluoroacetylacetone platinum (II), trimethyl (first Butylcyclopentadiene) group that forms of platinum (IV) and (1,5-cyclo-octadiene) dimethyl platinum (II),

Above-mentioned palladium (Pd) presoma is palladium (II), hexafluoroacetylacetone palladium (II) or acetylacetone,2,4-pentanedione Palladium (II),

Above-mentioned ruthenium (Ru) presoma is acetyl ethyl ketone ruthenium, double (ethyl cyclopentadiene) ruthenium (II), double (ring Pentadiene) ruthenium (II) or three (2,2,6,6-tetramethyl-3,5-heptadione) ruthenium (III),

Above-mentioned nickel (Ni) presoma is acetyl ethyl ketone nickel (II), double (cyclopentadiene) nickel or four (trifluoros Change phosphorus) nickel,

Above-mentioned cobalt (Co) presoma be acetyl ethyl ketone cobalt (II), dicarbapentaborane cyclopentadiene cobalt, carbonyl cobalt, Or cyclopentadiene dicarbapentaborane cobalt (I),

Above-mentioned molybdenum (Mo) presoma is hexacarbonylmolybdenum or molybdenum chloride (V),

Above-mentioned gold (Au) presoma is methyl (triphenylphosphine) gold (I).

The preparation method of the metal-carbon composite of nucleocapsid structure the most according to claim 1, it is characterised in that

It is choosing free methanol, ethanol, acetone, benzene, toluene for forming the organic matter precursor of above-mentioned carbon skeleton And the liquid precursor of the group of dimethylbenzene composition.

The preparation method of the metal-carbon composite of nucleocapsid structure the most according to claim 1, it is characterised in that

It is the gaseous precursor selected from methane or acetylene for forming the organic matter precursor of above-mentioned carbon skeleton.

The preparation method of the metal-carbon composite of nucleocapsid structure the most according to claim 1, it is characterised in that

Above-mentioned delivery gas is oxygen, hydrogen, argon, helium or nitrogen.

The preparation method of the metal-carbon composite of nucleocapsid structure the most according to claim 1, it is characterised in that

In above-mentioned S3 step, the temperature of reactor is heated to more than 300 DEG C.

The preparation method of the metal-carbon composite of nucleocapsid structure the most according to claim 1, it is characterised in that

In above-mentioned S3 step, the temperature of reactor is heated to the temperature in the range of 300-1800 DEG C.

8. a metal-carbon composite for the nucleocapsid structure that preparation method as claimed in claim 1 obtains, it uses metal Form core and form shell with carbon, it is characterised in that

There is the some or all of structure of above-mentioned shell parcel core.

9. the preparation method of the metal-carbon composite of the nucleocapsid structure being supported on carrier, it is characterised in that bag Include:

The step (S1) of carrier is arranged in reactor；

There is provided metal precursor and for forming the organic matter precursor of carbon skeleton, wherein, described metal precursor It is the presoma of a kind of metal, for forming the core in nucleocapsid structure, before described metal precursor and Organic substance Drive body through respective carburator, to be fed into the step (S2) of reactor under vapor state；

Introduce vaporization presoma to before reactor, be utilized respectively delivery gas with contactless state, separately and with Time in the reactor containing carrier, supply each metal precursor and the step of organic matter precursor of vaporization (S3)；And

A steady temperature is kept to synthesize the step of the metal-carbon composite being supported on carrier after heating above-mentioned reactor Suddenly (S4)；

Before above-mentioned metal precursor is choosing free platinum presoma, palladium presoma, ruthenium presoma, nickel presoma, cobalt Drive one of group of body, molybdenum presoma and gold presoma composition.

The preparation method of the metal-carbon composite of the nucleocapsid structure being supported on carrier the most according to claim 9, It is characterized in that,

Above-mentioned carrier choosing free carbon paper, activated carbon, carbon black, aluminium powder, aluminium sheet, silicon ash, titanium oxide powder, oxidation The group of the metal forming composition of zirconium powder, zeolite and nickel or aluminum.

The preparation method of the metal-carbon composite of 11. nucleocapsid structures being supported on carrier according to claim 9, It is characterized in that,

Above-mentioned platinum (Pt) presoma choosing free trimethyl (methyl cyclopentadiene) platinum (IV), acetylacetone,2,4-pentanedione platinum (II), Four (phosphorus trifluoride) platinum (0), four (triphenylphosphine) platinum (0), hexafluoroacetylacetone platinum (II), trimethyl (first Butylcyclopentadiene) group that forms of platinum (IV) and (1,5-cyclo-octadiene) dimethyl platinum (II),

Above-mentioned palladium (Pd) presoma is palladium (II), hexafluoroacetylacetone palladium (II) or palladium acetylacetonate (II),

Above-mentioned ruthenium (Ru) presoma is acetyl ethyl ketone ruthenium, double (ethyl cyclopentadiene) ruthenium (II), double (ring Pentadiene) ruthenium (II) or three (2,2,6,6-tetramethyl-3,5-heptadione) ruthenium (III),

Above-mentioned nickel (Ni) presoma is acetyl ethyl ketone nickel (II), double (cyclopentadiene) nickel or four (trifluoros Change phosphorus) nickel,

Above-mentioned cobalt (Co) presoma be acetyl ethyl ketone cobalt (II), dicarbapentaborane cyclopentadiene cobalt, carbonyl cobalt, Or cyclopentadiene dicarbapentaborane cobalt (I),

Above-mentioned molybdenum (Mo) presoma is hexacarbonylmolybdenum or molybdenum chloride (V),

Above-mentioned gold (Au) presoma is methyl (triphenylphosphine) gold (I).

The preparation method of the metal-carbon composite of 12. nucleocapsid structures being supported on carrier according to claim 9, It is characterized in that,

It is choosing free methanol, ethanol, acetone, benzene, toluene for forming the organic matter precursor of above-mentioned carbon skeleton And the liquid precursor of the group of dimethylbenzene composition.

The preparation method of the metal-carbon composite of 13. nucleocapsid structures being supported on carrier according to claim 9, It is characterized in that,

It is the gaseous precursor selected from methane or acetylene for forming the organic matter precursor of above-mentioned carbon skeleton.

The preparation method of the metal-carbon composite of 14. nucleocapsid structures being supported on carrier according to claim 9, It is characterized in that,

Above-mentioned delivery gas is oxygen, hydrogen, argon, helium or nitrogen.

The preparation method of the metal-carbon composite of 15. nucleocapsid structures being supported on carrier according to claim 9, It is characterized in that,

In above-mentioned S3 step, the temperature of reactor is heated to more than 300 DEG C.

The preparation method of the metal-carbon composite of 16. nucleocapsid structures being supported on carrier according to claim 9, It is characterized in that,

In above-mentioned S3 step, the temperature of reactor is heated to the temperature in the range of 300-1800 DEG C.