CN104226292B - Multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles and preparation method thereof - Google Patents
Multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles and preparation method thereof Download PDFInfo
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Abstract
The invention discloses multilevel structure material of a kind of graphitization Carbon-encapsulated Metal Nanoparticles and preparation method thereof.The nanometer sheet that material is stood by carbon fiber and surface crosswise thereof forms, wherein, carbon fiber is the carbide of the high polymer of diameter 20～1500nm, and nanometer sheet is made up of nano-metal particle outer cladding graphitized carbon, its sheet high 70～300nm, sheet thick 20～100nm, nano-metal particle footpath is 5～30nm；Method is first to high polymeric solution electrostatic spinning, again the high polymer fibre spun is added in soluble metal salt solution and be placed on air-tight state, react at temperature 80～200 DEG C, its surface crosswise of intermediate product is stood the high polymer fibre of nanometer sheet, afterwards, intermediate product is first placed in high polymer mixed solution or high polymer be dried after infiltration in the mixed liquid of soluble metallic salt, then is placed in reducing atmosphere at 600～1300 DEG C reaction, prepare purpose product.Its anti-toxic is good, specific surface area is high, can be widely used in fuel cell, lithium ion battery and ultracapacitor.
Description
Technical field
The present invention relates to a kind of multilevel structure material and preparation method, especially a kind of graphitized carbon cladding is received
Multilevel structure material of rice metallic particles and preparation method thereof.
Background technology
In fuel cell, lithium ion battery and ultracapacitor field, people have higher urging to obtain
Change performance material, be made that various effort, as Chinese invention patent application CN 103545536 A in
Carbon fiber loaded metallic catalyst of one that on January 29th, 2014 announces and its preparation method and application.
Catalyst disclosed in this patent application by carbon fiber, graphitization additive, metallic particles is in mass ratio
100:0.01:0.01～100:50:90 is mixed to get, wherein, and a diameter of 50nm of carbon fiber～5 μm,
Graphitization additive is the material with carbon element that degree of graphitization is high, a diameter of the 0.1 of metallic particles～50nm；Urge
The preparation method of agent is that first mixed liquor to polyacrylonitrile and material with carbon element additive carries out electrostatic spinning, then
By its high temperature cabonization, obtain the carbon nano-fiber containing material with carbon element additive, afterwards, first to carbon Nanowire
After the dispersion liquid of dimension adding metal precursor and stirring, regulate its pH with potassium hydroxide aqueous solution
Value is 9～13, and stirring carries out reduction reaction, then obtains product through filtering, being vacuum dried；Product can
It is applied in fuel cell, lithium ion battery and ultracapacitor hydrogen storage material.But, either it is catalyzed
Agent, or its preparation method, all also exist weak point, and first, product is only and adds containing material with carbon element
It is loaded with nano-metal particle, though it is effectively improved the resistance to of catalyst carrier on the carbon nano-fiber of agent
Corrosivity, but still cannot be avoided the carbon monoxide poison to it for exposed shape because of the nano-metal particle of load
Property infringement；Secondly, the specific surface area of product is still unsatisfactory, particularly as the efficient combustion of small size
When expecting the electrode of battery, lithium ion battery and ultracapacitor；Finally, preparation method can not obtain anti-one
The product that carbonoxide toxicity is good, specific surface area is bigger.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, it is provided that a kind of structure
Rationally, anti-poisoning, it is catalyzed the multilevel structure material of efficient graphitization Carbon-encapsulated Metal Nanoparticles.
Another technical problem that the invention solves the problems that is for providing a kind of above-mentioned graphitized carbon cladding nanometer gold
The preparation method of the multilevel structure material of metal particles.
For solving the technical problem of the present invention, the technical scheme used is: graphitized carbon cladding nanometer gold
The multilevel structure material of metal particles includes carbon fiber, particularly,
The nanometer sheet that described multilevel structure material is stood by carbon fiber and surface crosswise thereof forms；
Described carbon fiber is the carbide of high polymer, and they are a diameter of 20～1500nm years old；
The sheet a height of 70～300nm of described nanometer sheet, sheet thickness are 20～100nm, and it is by nano metal
Grain outer cladding graphitized carbon is constituted；
The particle diameter of described nano-metal particle is 5～30nm.
Further improvement as the multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles:
Preferably, high polymer is polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyphenyl
Ethylene, the polyvinyl alcohol of Cross-linked, polyvinyl butyral, cellulose acetate, poly-para Toluic Acid's ethylene glycol
Ester, polybutylene terephthalate (PBT), Polyetherimide (PEI), polylactic acid, polyamide, polylactic acid-
One or more mixture in co-glycolic acid (PLGA)；Not only make coming of raw material
Source relatively horn of plenty, also makes preparation technology be more easy to implement and flexible.
Preferably, one or more the mixture during metal is nickel, cobalt, copper, ferrum；Not only make
The selection of metal has had the bigger room for maneuver, is additionally favorable for the preparation of purpose product.
For solving another technical problem of the present invention, another technical scheme used is: above-mentioned stone
The preparation method of the multilevel structure material of inkization Carbon-encapsulated Metal Nanoparticles includes method of electrostatic spinning, especially
It is that key step is as follows:
Step 1, is first placed in the high polymeric solution that concentration is 1～35wt% on electrostatic spinning machine and carries out spinning,
Obtain the high polymer fibre of a diameter of 20～1500nm, be 0.1～20:80～99.9 according still further to weight ratio
Ratio high polymer fibre is added soluble nickel salt, soluble cobalt, soluble copper salt, soluble iron
In the solution of one or more mixture in salt, and it is placed in together air-tight state, in temperature
Be react at least 1h at 80～200 DEG C after carry out solid-liquid separation, wherein, soluble nickel salt, solubility cobalt
A kind of solution in salt, soluble copper salt, soluble ferric iron salt by soluble nickel salt, soluble cobalt,
One, carbamide and ethanol in soluble copper salt, soluble ferric iron salt is 0.6～0.8 according to weight ratio:
The proportions of 0.1～0.3:40, soluble nickel salt, soluble cobalt, soluble copper salt, solubility
The solution of the two or more mixture in iron salt by soluble nickel salt, soluble cobalt, soluble copper salt,
Two or more mixture in soluble ferric iron salt, concentration are ethanol water and six methylenes of 40～60vol%
Urotropine, according to the proportions that mol ratio is 1.4～1.6:1.0～1.4:3, obtains intermediate product
Its surface crosswise is stood the high polymer fibre of nanometer sheet；
Step 2, is first placed in intermediate product according to the ratio that weight ratio is 0.01～10:90～99.99
In the mixed liquid of high polymer mixed solution or high polymer and soluble metallic salt after infiltration, take out and be dried, wherein,
High polymer mixed solution is polyvinyl butyral resin ethanol solution, polylactic acid dichloromethane solution, poly-methyl
Acrylic acid methyl ester. N, N dimethylformamide (DMF) solution, poly-para Toluic Acid's glycol ester solution, poly-
One or more mixing in vinyl alcohol aqueous solution, polyamide butanol solution and xylene solution
Solution, the mixed liquid of high polymer and soluble metallic salt by aforementioned high polymer mixed solution and soluble nickel salt,
One or more mixture in soluble cobalt, soluble copper salt, soluble ferric iron salt is according to weight
Amount than being the proportions of 80～99.9:0.1～20, obtain its surface be covered with high polymer or high polymer with
The intermediate product of soluble metal salt mixture, then its surface is covered with high polymer or high polymer and solubility
The intermediate product of metal salt mixture is placed in reducing atmosphere, at 600～1300 DEG C heat 1～
60min, prepares the multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles.
Preparation method further as the multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles
Improve:
Preferably, intermediate product is being placed in high polymer mixed solution or high polymer and soluble metallic salt
In mixed liquid before infiltration, after first using deionized water to clean the powder of intermediate product surface precipitation, it is dried；
Ensure that the quality of purpose product.
Preferably, the high polymer of spinning be polymethyl methacrylate (PMMA), polyacrylonitrile (PAN),
Polystyrene, the polyvinyl alcohol of Cross-linked, polyvinyl butyral, cellulose acetate, poly-para Toluic Acid's second
Diol ester, polybutylene terephthalate (PBT), Polyetherimide (PEI), polylactic acid, polyamide, poly-
One or more mixture in poly lactic coglycolic acid (PLGA).
Preferably, soluble nickel salt is nickel sulfate, Nickel dichloride., nickelous bromide, nickel acetate, nickel sulfamic acid,
One or more mixture in nickel nitrate, nickelous hypophosphite.
Preferably, the one during soluble cobalt is cobaltous sulfate, cobaltous chloride, cobalt nitrate, cobalt acetate or two
Plant above mixture.
Preferably, the one during soluble copper salt is copper sulfate, copper chloride, copper nitrate, copper acetate or two
Plant above mixture.
Preferably, during soluble ferric iron salt is iron sulfate, iron chloride, ferric nitrate one or more
Mixture.
Provide the benefit that relative to prior art:
One, uses scanning electron microscope, transmission electron microscope, laser Raman spectroscopy respectively to prepared purpose product
Instrument and X-ray diffractometer characterize, and from its result, purpose product is the table of numerous fibrous material
Face is covered with the nanometer sheet that cross stand；Wherein, a diameter of the 20 of fiber～1500nm, the sheet of nanometer sheet
A height of 70～300nm, sheet thickness is 20～100nm, and it is by equally distributed granular substance outer cladding membranoid substance
Constituting, the particle diameter of granular substance is 5～30nm.Fiber is the carbide of high polymer, and granular substance is for receiving
Rice metallic particles, metal is one or more the mixture in nickel, cobalt, copper, ferrum, membranoid substance
For graphitized carbon.This three dimensional structure mesh being assembled into by carbon fiber, nano-metal particle and graphitized carbon
Product, both owing to the carbon fiber of one-dimentional structure is difficult to reunite for the purpose of the high-specific surface area of product establish
Basis, greatly increases purpose product because the surface of carbon fiber is covered with the nanometer sheet of cross stand again
Specific surface area, due also to nanometer sheet on one's feet is by equally distributed nano-metal particle outer cladding stone
Inkization carbon constitutes and not only prevent the reunion between nano-metal particle, and beneficially the turning of electronics in system
Move, more avoid the exposed of nano-metal particle, stopped the carbon monoxide murder by poisoning to it, so that mesh
The overall catalysis efficiency of product and anti-poisoning performance all obtain raising greatly.
Its two, preparation method is simple, science, efficiently, has not only prepared rational in infrastructure, anti-poisoning, urges
Change the multilevel structure material of efficient purpose product graphitization Carbon-encapsulated Metal Nanoparticles；Also because of it
Distinctive pattern and structure and not only greatly increase the usefulness of its catalysis, also drastically increase it and resist
The ability of carbon monoxide poisoning；More have that technique is simple, low cost, it is easy to the feature of industrialized production；
And then make it be expected in the field such as energy storage, catalysis to obtain commercial applications widely.
Accompanying drawing explanation
Fig. 1 is that the purpose product preparing preparation method uses scanning electron microscope (SEM) and transmission electron microscope (TEM)
Carry out one of result of characterizing.Wherein, the SEM image of product for the purpose of Fig. 1 a, Fig. 1 b is Fig. 1 a
The TEM image of the single purpose product in shown purpose product, Fig. 1 c is in purpose product shown in Fig. 1 b
The high power TEM image of nanometer sheet.
Fig. 2 is to one of result that purpose product use laser Raman spectrometer characterizes.By this Raman
Spectrogram understands, and the membranoid substance that nano-metal particle outer cladding is graphitized carbon.
Fig. 3 is to one of result that purpose product use X-ray diffraction (XRD) instrument characterizes.XRD
Spectrogram demonstrates that nano-metal particle is nickel simple substance, itself and the standard x RD spectrogram JCPDS of metallic nickel
210-2279 is identical.
Detailed description of the invention
Below in conjunction with the accompanying drawings the optimal way of the present invention is described in further detail.
First buy from market or prepare by conventional method:
As the polymethyl methacrylate of high polymer, polyacrylonitrile, polystyrene, the poly-second of Cross-linked
Enol, polyvinyl butyral, cellulose acetate, poly-para Toluic Acid's glycol ester, poly terephthalic acid fourth
Diol ester, Polyetherimide, polylactic acid, polyamide and Poly(D,L-lactide-co-glycolide；
As the nickel sulfate of soluble nickel salt, Nickel dichloride., nickelous bromide, nickel acetate, nickel sulfamic acid, nitre
Acid nickel and nickelous hypophosphite；
Cobaltous sulfate, cobaltous chloride, cobalt nitrate and cobalt acetate as soluble cobalt；
Copper sulfate, copper chloride, copper nitrate and copper acetate as soluble copper salt；
Iron sulfate, iron chloride and ferric nitrate as soluble ferric iron salt.
Then,
Embodiment 1
Concretely comprising the following steps of preparation:
Step 1, is first placed in the high polymeric solution that concentration is 1wt% on electrostatic spinning machine and carries out spinning；Its
In, high polymeric solution is polymethyl methacrylate N, and N dimethyl formamide solution obtains a diameter of
The high polymer fibre of 20nm.Being added by high polymer fibre according still further to the ratio that weight ratio is 0.1:99.9 can
One or more mixing in insoluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
In the solution of thing, now take in soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
A kind of solution, i.e. Nickelous nitrate hexahydrate solution, and it is placed in together air-tight state, it is 80 DEG C in temperature
Solid-liquid separation is carried out after lower reaction 2h；Wherein, Nickelous nitrate hexahydrate solution is by Nickelous nitrate hexahydrate, carbamide
With ethanol according to the proportions that weight ratio is 0.6:0.3:40 (if choosing soluble nickel salt, solubility
The solution of the two or more mixture in cobalt salt, soluble copper salt, soluble ferric iron salt, then by soluble nickel
Two or more mixture in salt, soluble cobalt, soluble copper salt, soluble ferric iron salt, concentration be 40～
The ethanol water of 60vol% and hexamethylenetetramine are 1.4～1.6:1.0～1.4:3 according to mol ratio
Proportions), obtain its surface crosswise of intermediate product and stand the high polymer fibre of nanometer sheet.
Step 2, first uses deionized water to clean the powder of intermediate product surface precipitation the most after drying, according to
Weight ratio be the ratio of 0.01:99.99 intermediate product is placed in high polymer mixed solution (or high polymer with
The mixed liquid of soluble metallic salt) in infiltration after, take out be dried；Wherein, high polymer mixed solution is poly-first
Base acrylic acid methyl ester. N, N dimethyl formamide solution (or polyvinyl butyral resin ethanol solution, poly-breast
Acid dichloride dichloromethane, poly-para Toluic Acid's glycol ester solution, polyvinyl alcohol water solution, the positive fourth of polyamide
One or more mixed solution in alcoholic solution and xylene solution, high polymer and soluble metal
The mixed liquid of salt by aforementioned high polymer mixed solution and soluble nickel salt, soluble cobalt, soluble copper salt,
One or more mixture in soluble ferric iron salt is 80～99.9:0.1～20 according to weight ratio
Proportions), obtain its surface and be covered with high polymer (or high polymer with soluble metal salt mixture)
Intermediate product.Again its surface is covered with in high polymer (or high polymer with soluble metal salt mixture)
Between product be placed in reducing atmosphere, at 600 DEG C heat 60min, prepare be similar to shown in Fig. 1, with
And the multilevel structure material of the graphitization Carbon-encapsulated Metal Nanoparticles as shown in the curve in Fig. 2 and Fig. 3.
Embodiment 2
Concretely comprising the following steps of preparation:
Step 1, is first placed in the high polymeric solution that concentration is 9wt% on electrostatic spinning machine and carries out spinning；Its
In, high polymeric solution is polymethyl methacrylate N, and N dimethyl formamide solution obtains a diameter of
The high polymer fibre of 370nm.According still further to the ratio that weight ratio is 1:99, high polymer fibre is added solvable
One or more mixture in property nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
Solution in, now take in soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
Plant solution, i.e. Nickelous nitrate hexahydrate solution, and it is placed in together air-tight state, be 110 DEG C in temperature
Solid-liquid separation is carried out after lower reaction 1.8h；Wherein, Nickelous nitrate hexahydrate solution is by Nickelous nitrate hexahydrate, urine
Element and ethanol according to proportions that weight ratio is 0.65:0.25:40 (if choose soluble nickel salt, can
The solution of the two or more mixture in dissolubility cobalt salt, soluble copper salt, soluble ferric iron salt, then by solvable
Two or more mixture in property nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt, concentration
Be 40～60vol% ethanol water and hexamethylenetetramine according to mol ratio be 1.4～1.6:1.0～
The proportions of 1.4:3), obtain its surface crosswise of intermediate product and stand the high polymer of nanometer sheet
Fiber.
Step 2, first uses deionized water to clean the powder of intermediate product surface precipitation the most after drying, according to
Weight ratio be the ratio of 0.05:99.95 intermediate product is placed in high polymer mixed solution (or high polymer with
The mixed liquid of soluble metallic salt) in infiltration after, take out be dried；Wherein, high polymer mixed solution is poly-first
Base acrylic acid methyl ester. N, N dimethyl formamide solution (or polyvinyl butyral resin ethanol solution, poly-breast
Acid dichloride dichloromethane, poly-para Toluic Acid's glycol ester solution, polyvinyl alcohol water solution, the positive fourth of polyamide
One or more mixed solution in alcoholic solution and xylene solution, high polymer and soluble metal
The mixed liquid of salt by aforementioned high polymer mixed solution and soluble nickel salt, soluble cobalt, soluble copper salt,
One or more mixture in soluble ferric iron salt is 80～99.9:0.1～20 according to weight ratio
Proportions), obtain its surface and be covered with high polymer (or high polymer with soluble metal salt mixture)
Intermediate product.Again its surface is covered with in high polymer (or high polymer with soluble metal salt mixture)
Between product be placed in reducing atmosphere, at 775 DEG C heat 45min, prepare be similar to shown in Fig. 1, with
And the multilevel structure material of the graphitization Carbon-encapsulated Metal Nanoparticles as shown in the curve in Fig. 2 and Fig. 3.
Embodiment 3
Concretely comprising the following steps of preparation:
Step 1, is first placed in the high polymeric solution that concentration is 18wt% on electrostatic spinning machine and carries out spinning；
Wherein, high polymeric solution is polymethyl methacrylate N, and N dimethyl formamide solution obtains diameter
High polymer fibre for 750nm.Being added by high polymer fibre according still further to the ratio that weight ratio is 2:98 can
One or more mixing in insoluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
In the solution of thing, now take in soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
A kind of solution, i.e. Nickelous nitrate hexahydrate solution, and it is placed in together air-tight state, it is 140 in temperature
Solid-liquid separation is carried out after reacting 1.5h at DEG C；Wherein, Nickelous nitrate hexahydrate solution by Nickelous nitrate hexahydrate,
Carbamide and ethanol according to proportions that weight ratio is 0.7:0.2:40 (if choose soluble nickel salt, can
The solution of the two or more mixture in dissolubility cobalt salt, soluble copper salt, soluble ferric iron salt, then by solvable
Two or more mixture in property nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt, concentration
Be 40～60vol% ethanol water and hexamethylenetetramine according to mol ratio be 1.4～1.6:1.0～
The proportions of 1.4:3), obtain its surface crosswise of intermediate product and stand the high polymer of nanometer sheet
Fiber.
Step 2, first uses deionized water to clean the powder of intermediate product surface precipitation the most after drying, according to
Weight ratio be the ratio of 0.1:99.9 intermediate product is placed in high polymer mixed solution (or high polymer with can
The mixed liquid of soluble metal salts) in infiltration after, take out be dried；Wherein, high polymer mixed solution is poly-methyl
Acrylic acid methyl ester. N, N dimethyl formamide solution (or polyvinyl butyral resin ethanol solution, polylactic acid
Dichloromethane solution, poly-para Toluic Acid's glycol ester solution, polyvinyl alcohol water solution, polyamide n-butyl alcohol
One or more mixed solution in solution and xylene solution, high polymer and soluble metallic salt
Mixed liquid by aforementioned high polymer mixed solution and soluble nickel salt, soluble cobalt, soluble copper salt, can
One or more mixture in dissolubility iron salt is 80～99.9:0.1～20 according to weight ratio
Proportions), obtain its surface and be covered with in high polymer (or high polymer with soluble metal salt mixture)
Between product.Its surface is covered with the centre of high polymer (or high polymer with soluble metal salt mixture) again
Product is placed in reducing atmosphere, heats 30min at 950 DEG C, prepares as it is shown in figure 1, and such as scheme
The multilevel structure material of the graphitization Carbon-encapsulated Metal Nanoparticles shown in the curve in 2 and Fig. 3.
Embodiment 4
Concretely comprising the following steps of preparation:
Step 1, is first placed in the high polymeric solution that concentration is 27wt% on electrostatic spinning machine and carries out spinning；
Wherein, high polymeric solution is polymethyl methacrylate N, and N dimethyl formamide solution obtains diameter
High polymer fibre for 1100nm.According still further to the ratio that weight ratio is 10:90, high polymer fibre is added
One or more in soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt mix
In the solution of compound, now take in soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
A kind of solution, i.e. Nickelous nitrate hexahydrate solution, and it is placed in air-tight state together, is 170 in temperature
Solid-liquid separation is carried out after reacting 1.3h at DEG C；Wherein, Nickelous nitrate hexahydrate solution by Nickelous nitrate hexahydrate,
Carbamide and ethanol according to proportions that weight ratio is 0.75:0.15:40 (if choose soluble nickel salt,
The solution of the two or more mixture in soluble cobalt, soluble copper salt, soluble ferric iron salt, then by can
Two or more mixture in insoluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt, dense
Degree be 40～60vol% ethanol water and hexamethylenetetramine be 1.4～1.6 according to mol ratio:
The proportions of 1.0～1.4:3), obtain its surface crosswise of intermediate product and stand the height of nanometer sheet
Polymer fibre.
Step 2, first uses deionized water to clean the powder of intermediate product surface precipitation the most after drying, according to
Weight ratio is that intermediate product is placed in high polymer mixed solution (or high polymer and solubility by the ratio of 1:99
The mixed liquid of slaine) in infiltration after, take out be dried；Wherein, high polymer mixed solution is polymethyl
Acid methyl ester N, N dimethyl formamide solution (or polyvinyl butyral resin ethanol solution, polylactic acid dichloro
Dichloromethane, poly-para Toluic Acid's glycol ester solution, polyvinyl alcohol water solution, polyamide butanol solution
With one or more the mixed solution in xylene solution, high polymer is mixed with soluble metallic salt
Liquid is by aforementioned high polymer mixed solution and soluble nickel salt, soluble cobalt, soluble copper salt, solubility
One or more mixture in iron salt is according to the ratio that weight ratio is 80～99.9:0.1～20
Preparation), obtain its surface be covered with high polymer (or high polymer with soluble metal salt mixture) in the middle of product
Thing.Its surface is covered with the intermediate product of high polymer (or high polymer with soluble metal salt mixture) again
It is placed in reducing atmosphere, at 1125 DEG C, heats 15min, prepare and be similar to shown in Fig. 1, Yi Jiru
The multilevel structure material of the graphitization Carbon-encapsulated Metal Nanoparticles shown in the curve in Fig. 2 and Fig. 3.
Embodiment 5
Concretely comprising the following steps of preparation:
Step 1, is first placed in the high polymeric solution that concentration is 35wt% on electrostatic spinning machine and carries out spinning；
Wherein, high polymeric solution is polymethyl methacrylate N, and N dimethyl formamide solution obtains diameter
High polymer fibre for 1500nm.According still further to the ratio that weight ratio is 20:80, high polymer fibre is added
One or more in soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt mix
In the solution of compound, now take in soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
A kind of solution, i.e. Nickelous nitrate hexahydrate solution, and it is placed in air-tight state together, is 200 in temperature
Solid-liquid separation is carried out after reacting 1h at DEG C；Wherein, Nickelous nitrate hexahydrate solution is by Nickelous nitrate hexahydrate, urine
Element and ethanol according to proportions that weight ratio is 0.8:0.1:40 (if choosing soluble nickel salt, solvable
The solution of the two or more mixture in property cobalt salt, soluble copper salt, soluble ferric iron salt, then by solubility
Two or more mixture, concentration in nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt are
The ethanol water of 40～60vol% and hexamethylenetetramine according to mol ratio be 1.4～1.6:1.0～
The proportions of 1.4:3), obtain its surface crosswise of intermediate product and stand the high polymer of nanometer sheet
Fiber.
Step 2, first uses deionized water to clean the powder of intermediate product surface precipitation the most after drying, according to
Weight ratio is that intermediate product is placed in high polymer mixed solution (or high polymer and solubility by the ratio of 10:90
The mixed liquid of slaine) in infiltration after, take out be dried；Wherein, high polymer mixed solution is polymethyl
Acid methyl ester N, N dimethyl formamide solution (or polyvinyl butyral resin ethanol solution, polylactic acid dichloro
Dichloromethane, poly-para Toluic Acid's glycol ester solution, polyvinyl alcohol water solution, polyamide butanol solution
With one or more the mixed solution in xylene solution, high polymer is mixed with soluble metallic salt
Liquid is by aforementioned high polymer mixed solution and soluble nickel salt, soluble cobalt, soluble copper salt, solubility
One or more mixture in iron salt is according to the ratio that weight ratio is 80～99.9:0.1～20
Preparation), obtain its surface be covered with high polymer (or high polymer with soluble metal salt mixture) in the middle of product
Thing.Its surface is covered with the intermediate product of high polymer (or high polymer with soluble metal salt mixture) again
It is placed in reducing atmosphere, at 1300 DEG C, heats 1min, prepare and be similar to shown in Fig. 1, and such as figure
The multilevel structure material of the graphitization Carbon-encapsulated Metal Nanoparticles shown in the curve in 2 and Fig. 3.
Select the polymethyl methacrylate as high polymer, polyacrylonitrile, polystyrene, friendship the most respectively
The polyvinyl alcohol of connectionization, polyvinyl butyral, cellulose acetate, poly-para Toluic Acid's glycol ester, poly-right
Benzene dicarboxylic acid butanediol ester, Polyetherimide, polylactic acid, polyamide, Poly(D,L-lactide-co-glycolide
In one or more mixture, as the nickel sulfate of soluble nickel salt, Nickel dichloride., nickelous bromide,
Nickel acetate, one or more the mixture in nickel sulfamic acid, nickel nitrate, nickelous hypophosphite, make
Mixed for one or more in the cobaltous sulfate of soluble cobalt, cobaltous chloride, cobalt nitrate, cobalt acetate
Compound, as one or both in the copper sulfate of soluble copper salt, copper chloride, copper nitrate, copper acetate
Above mixture, as one or both in the iron sulfate of soluble ferric iron salt, iron chloride, ferric nitrate
Above mixture, repeats above-described embodiment 1～5, has prepared equally as or be similar to shown in Fig. 1, with
And as Fig. 2 and as or the curve that is similar in Fig. 3 shown in graphitization Carbon-encapsulated Metal Nanoparticles many
Level structure material.
Obviously, those skilled in the art can be to the graphitization Carbon-encapsulated Metal Nanoparticles of the present invention
Multilevel structure material and preparation method thereof carries out various change and modification without deviating from the spirit of the present invention and model
Enclose.So, if these amendments and modification to the present invention belong to the claims in the present invention and equivalent skill thereof
Within the scope of art, then the present invention is also intended to comprise these change and modification.
Claims (9)
1. the multilevel structure material of a graphitization Carbon-encapsulated Metal Nanoparticles, it is characterised in that:
The nanometer sheet that described multilevel structure material is stood by carbon fiber and surface crosswise thereof forms；
Described carbon fiber is the carbide of high polymer, and they are a diameter of 20～1500nm years old；
The sheet a height of 70～300nm of described nanometer sheet, sheet thickness are 20～100nm, and it is by nano-metal particle
Outer cladding graphitized carbon is constituted；
The particle diameter of described nano-metal particle is 5～30nm；
The multilevel structure material of described graphitization Carbon-encapsulated Metal Nanoparticles is obtained by following methods:
Step 1, is first placed in the high polymeric solution that concentration is 1～35wt% on electrostatic spinning machine and carries out spinning,
Obtain the high polymer fibre of a diameter of 20～1500nm, be 0.1～20:80～99.9 according still further to weight ratio
Ratio high polymer fibre is added soluble nickel salt, soluble cobalt, soluble copper salt, soluble iron
In the solution of one or more mixture in salt, and it is placed in together air-tight state, in temperature
Be react at least 1h at 80～200 DEG C after carry out solid-liquid separation, wherein, soluble nickel salt, solubility cobalt
A kind of solution in salt, soluble copper salt, soluble ferric iron salt by soluble nickel salt, soluble cobalt,
One, carbamide and ethanol in soluble copper salt, soluble ferric iron salt according to weight ratio be 0.6～0.8:0.1～
The proportions of 0.3:40, soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
In the solution of two or more mixture by soluble nickel salt, soluble cobalt, soluble copper salt, solvable
Two or more mixture in property iron salt, concentration are ethanol water and the hexa-methylene four of 40～60vol%
Amine according to the proportions that mol ratio is 1.4～1.6:1.0～1.4:3, obtain intermediate product its
Surface crosswise is stood the high polymer fibre of nanometer sheet；
Step 2, is first placed in intermediate product according to the ratio that weight ratio is 0.01～10:90～99.99
In the mixed liquid of high polymer mixed solution or high polymer and soluble metallic salt after infiltration, take out and be dried, wherein,
High polymer mixed solution is polyvinyl butyral resin ethanol solution, polylactic acid dichloromethane solution, poly-methyl
Acrylic acid methyl ester. N, N dimethyl formamide solution, polyvinyl alcohol water solution, polyamide butanol solution
With one or more the mixed solution in xylene solution, high polymer is mixed with soluble metallic salt
Liquid is by aforementioned high polymer mixed solution and soluble nickel salt, soluble cobalt, soluble copper salt, solubility
One or more mixture in iron salt is according to the ratio that weight ratio is 80～99.9:0.1～20
Preparation, obtains its surface and is covered with the intermediate product of high polymer or high polymer and soluble metal salt mixture,
The intermediate product that its surface is covered with high polymer or high polymer and soluble metal salt mixture again is placed in reduction
Property atmosphere in, at 600～1300 DEG C heat 1～60min, prepare graphitized carbon cladding nano metal
The multilevel structure material of grain.
The multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles the most according to claim 1,
It is characterized in that the high polymer in step 1 spinning process is polymethyl methacrylate, polyacrylonitrile, polyphenyl
Ethylene, the polyvinyl alcohol of Cross-linked, polyvinyl butyral, cellulose acetate, poly terephthalic acid fourth two
One in alcohol ester, Polyetherimide, polylactic acid, polyamide, Poly(D,L-lactide-co-glycolide or two
Plant above mixture.
3. the system of the multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles described in a claim 1
Preparation Method, including method of electrostatic spinning, it is characterised in that key step is as follows:
Step 1, is first placed in the high polymeric solution that concentration is 1～35wt% on electrostatic spinning machine and carries out spinning,
Obtain the high polymer fibre of a diameter of 20～1500nm, be 0.1～20:80～99.9 according still further to weight ratio
Ratio high polymer fibre is added soluble nickel salt, soluble cobalt, soluble copper salt, soluble iron
In the solution of one or more mixture in salt, and it is placed in together air-tight state, in temperature
Be react at least 1h at 80～200 DEG C after carry out solid-liquid separation, wherein, soluble nickel salt, solubility cobalt
A kind of solution in salt, soluble copper salt, soluble ferric iron salt by soluble nickel salt, soluble cobalt,
One, carbamide and ethanol in soluble copper salt, soluble ferric iron salt according to weight ratio be 0.6～0.8:0.1～
The proportions of 0.3:40, soluble nickel salt, soluble cobalt, soluble copper salt, soluble ferric iron salt
In the solution of two or more mixture by soluble nickel salt, soluble cobalt, soluble copper salt, solvable
Two or more mixture in property iron salt, concentration are ethanol water and the hexa-methylene four of 40～60vol%
Amine according to the proportions that mol ratio is 1.4～1.6:1.0～1.4:3, obtain intermediate product its
Surface crosswise is stood the high polymer fibre of nanometer sheet；
Step 2, is first placed in intermediate product according to the ratio that weight ratio is 0.01～10:90～99.99
In the mixed liquid of high polymer mixed solution or high polymer and soluble metallic salt after infiltration, take out and be dried, wherein,
High polymer mixed solution is polyvinyl butyral resin ethanol solution, polylactic acid dichloromethane solution, poly-methyl
Acrylic acid methyl ester. N, N dimethyl formamide solution, polyvinyl alcohol water solution, polyamide butanol solution
With one or more the mixed solution in xylene solution, high polymer is mixed with soluble metallic salt
Liquid is by aforementioned high polymer mixed solution and soluble nickel salt, soluble cobalt, soluble copper salt, solubility
One or more mixture in iron salt is according to the ratio that weight ratio is 80～99.9:0.1～20
Preparation, obtains its surface and is covered with the intermediate product of high polymer or high polymer and soluble metal salt mixture,
The intermediate product that its surface is covered with high polymer or high polymer and soluble metal salt mixture again is placed in reduction
Property atmosphere in, at 600～1300 DEG C heat 1～60min, prepare graphitized carbon cladding nano metal
The multilevel structure material of grain.
The multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles the most according to claim 3
Preparation method, is characterized in that intermediate product is being placed in high polymer mixed solution or high polymer and solubility gold
Belong in the mixed liquid of salt before infiltration, after first using deionized water to clean the powder of intermediate product surface precipitation,
It is dried.
The multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles the most according to claim 3
Preparation method, is characterized in that the high polymer of spinning is polymethyl methacrylate, polyacrylonitrile, polyphenyl
Ethylene, the polyvinyl alcohol of Cross-linked, polyvinyl butyral, cellulose acetate, poly terephthalic acid fourth two
One in alcohol ester, Polyetherimide, polylactic acid, polyamide, Poly(D,L-lactide-co-glycolide or two
Plant above mixture.
The multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles the most according to claim 3
Preparation method, is characterized in that soluble nickel salt is nickel sulfate, Nickel dichloride., nickelous bromide, nickel acetate, amino
One or more mixture in nickel sulphonic acid, nickel nitrate, nickelous hypophosphite.
The multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles the most according to claim 3
Preparation method, is characterized in that soluble cobalt is in cobaltous sulfate, cobaltous chloride, cobalt nitrate, cobalt acetate
Kind or two or more mixture.
The multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles the most according to claim 3
Preparation method, is characterized in that soluble copper salt is in copper sulfate, copper chloride, copper nitrate, copper acetate
Kind or two or more mixture.
The multilevel structure material of graphitization Carbon-encapsulated Metal Nanoparticles the most according to claim 3
Preparation method, is characterized in that soluble ferric iron salt is one or both in iron sulfate, iron chloride, ferric nitrate
Above mixture.
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