CN106077701B - A kind of preparation method of metallized metal oxide composite nanoparticle - Google Patents
A kind of preparation method of metallized metal oxide composite nanoparticle Download PDFInfo
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
- B22F9/305—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis of metal carbonyls
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- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of preparation method of metallized metal oxide composite nanoparticle, step is：Metal carbonyl carries out cracking reaction in the Isosorbide-5-Nitrae diethylbenzene solution of amphipathic nature block polymer, forms the relatively active metal simple substance of block copolymer cladding；After reaction solution cooling, add more inactive metal precursor, displacement reaction occurs compared with active metal with part, obtain more inactive metal nanoparticle, it is remaining compared with metal oxide is formed after active metal and air contact, finally give the metallized metal oxide composite nanoparticle of block copolymer cladding.The present invention is used as the presoma compared with active metal using metal carbonyl, the 1 of amphipathic nature block polymer, cracked in 4 diethylbenzene solution, cracking temperature substantially reduces, it can carry out at ambient pressure, products obtained therefrom is quantum size, has application value in fields such as chemical sensor, biological detection and intelligent devices.
Description
Technical field
The present invention relates to a kind of preparation method of metal-metallic oxide composite nanoparticle, belongs to nano material synthesis
Technical field.
Background technology
Block copolymer coats the characteristic that different types of nano-particle can make composite nanoparticle have multiple response,
And the cladding of block copolymer can also prevent nano-particle from reuniting, make nano-particle fully dispersed.For example, gold and four oxidations three
Iron composite nanoparticle had both had the near infrared light fuel factor of golden nanometer particle, had the magnetic of ferriferrous oxide nano-particle again
Property.If block copolymer also has the functions such as Thermo-sensitive, pH responses, optical Response, block copolymer can be utilized stable
The multiple response characteristic of composite nanoparticle prepare carrier, chemical sensor and intelligent device etc. of medicament slow release and targeting
Material.
Conventional block copolymer cladding or the preparation method of stable metal-metallic oxide composite nanoparticle are embedding
Section copolymer and self-assembly method, the metal-metallic oxide nano-particle and block copolymer that will have been synthesized
Mixing carries out self assembly.Block copolymer micelle cladding or the amount and nanoparticle of stable nano-particle prepared by this method
Distribution of the son in micella cannot get good control, so as to cause the performance poor controllability of composite nanoparticle, it is difficult in medicine
Applied on carrier, chemical sensor and the intelligent device that thing is sustained and targetted.Such as Sun Shouheng seminars（H. Yu, M. Chen,
Philip M. Rice, S. Wang, R. L. White, S. Sun, nano letters. 2005, 5(2), 379-
382.）Dumbbell shape gold-ferriferrous oxide nano-particle is prepared in 310 DEG C of Pintsch process iron pentacarbonyls and gold chloride, this method is anti-
Answer temperature high, it is necessary to which high-temperature service and resistance to more than 300 DEG C of solvent, system complexity, condition is relatively harsh, and the nanoparticle synthesized
Sub- size is in 20nm or so, and surface is hydrophobic grouping, and the ligand exchange processes of nanoparticle surface are cumbersome and effect is undesirable,
So as to limit application.
Pyrolysismethod prepares the more of nano-particle（Ron Snovski, Judith Grinblat, Shlomo Margel,
Langmuir. 2011,27,11071-11080；Mahmud Diab, Taleb Mokari, Inorg. Chem. 2014,
53,2304-2309.）, but for preparing the research of the stable metal-metallic oxide composite nanoparticle of block copolymer very
It is few, and be the single nano-particle of cladding mostly, if the species of increase nano-particle, block copolymer and different nano-particles
Interaction is different, can increase cladding difficulty.In addition, low temperature preparation is uniformly dispersed, the composite nanoparticle of quantum size report
Seldom.
The content of the invention
In view of the deficienciess of the prior art, the invention provides a kind of metal-metallic oxide composite nanoparticle
Preparation method, raw material type needed for the preparation method is few, and reaction condition is relatively mild, and without using high-tension apparatus, what is obtained is compound
Nano-particle block copolymer coats, and dispersed in the solution, particle diameter distribution is uniform, and size can reach quantum stage.
The present invention carries out the obtained block of cracking reaction using carbonyl metal compound as raw material in block copolymer weak solution
The relatively active metal simple substance of copolymer cladding, then less active metal presoma passes through block copolymer clad, with relatively living
Sprinkle metal simple-substance and displacement reaction occurs, form less active metal simple substance；Become ion, remainder compared with active metal simple substance part
Divide and formed when running into air compared with active metal oxide, ultimately form block copolymer cladding（Or alternatively referred to as block is total to
Polymers is stable）Quantum size metal-metallic oxide composite nanoparticle.
Concrete technical scheme of the present invention is as follows：
A kind of preparation method of metal-metallic oxide composite nanoparticle, this method comprise the following steps：Metal-carbonyl
Compound carries out cracking reaction in Isosorbide-5-Nitrae-diethylbenzene solution of amphipathic nature block polymer, forms block copolymer cladding
Compared with active metal simple substance；After reaction solution cooling, more inactive metal precursor is added, is replaced with part compared with active metal
Reaction, more inactive metal nanoparticle is obtained, it is remaining compared with metal oxide is formed behind active metal and air contact, most
The metal-metallic oxide composite nanoparticle of block copolymer cladding, abbreviation metal-metallic oxide composite Nano are obtained eventually
Particle.
In above-mentioned preparation method, the metal carbonyl includes carbonyl iron, carbonyl cobalt or carbonyl nickel.
In above-mentioned preparation method, more inactive metal is including Au Ag Pt Pd etc., more inactive metal front
Body is the inorganic salts or acid of these metals, such as can be gold chloride, lithium chloraurate, acetic acid gold, silver nitrate, platinum nitrate, tetrachloro
Close the one or more in palladium acid and palladium nitrate, but not limited to this.
In above-mentioned preparation method, the effect of the amphipathic nature block polymer is that the active metal that stable cracking is formed is single
Matter, preferable amphipathic nature block polymer are to contain polyacrylic acid, polyethylene glycol oxide, polyvinylpyridine, polyvinylpyrrolidine
The block copolymer of the block such as alkanone or N- vinyl imidazoles, i.e. one in amphipathic nature block polymer section are polyacrylic acid, gathered
Ethylene oxide, polyvinylpyridine, PVP or N- vinyl imidazoles, for example, amphipathic nature block polymer can
Be polystyrene-b- polyacrylic acid, polystyrene-b- polyethylene glycol oxide and polyvinylpyridine-bIn-polyethylene glycol oxide
One or more, but not limited to this.
In above-mentioned preparation method, the mol ratio of metal carbonyl and carboxyl in amphipathic nature block polymer is 5:1 -
30:1, preferably 10:1-20:1.If amphipathic nature block polymer dosage is excessive, the yield of the nano-particle finally given compared with
Low, if amphipathic nature block polymer dosage is too low, block polymer can not uniformly coat nano-particle, the size of nano-particle
Can be larger.
In above-mentioned preparation method, more inactive metal precursor dosage is less than metal carbonyl, is so occurring
A part just can be also left after displacement reaction compared with active metal simple substance.In general, less active metal presoma and metal-carbonyl
The mol ratio of compound is 1:5-1:20, preferably 1:10-1:20.
In above-mentioned preparation method, using Isosorbide-5-Nitrae-diethylbenzene as solvent in reaction system, ethyl therein is donor residues
Group, the cloud density of phenyl ring is added, make the metallic element active force of solvent molecule and electron deficient in metal carbonyl
Increase（Coordination）, i.e., metallic element is more readily pulled from the coordination of carbonyl and decomposed, therefore metal carbonyl is existed
Cracking obtains nano-particle under relatively low temperature conditionss.In the present invention, metal carbonyl is carried out at 150 DEG C -185 DEG C
Cracking reaction, preferably reacted at 170 DEG C -180 DEG C.The time of cracking reaction is 1-5h.
In above-mentioned preparation method, cracking reaction is carried out at ambient pressure, is not required to reaction under high pressure.
In above-mentioned preparation method, cracking reaction is carried out under gas shield, more active to prevent being generated in crack arrest solution preocess
Metal simple-substance is oxidized.Protective gas can be the inert gases such as nitrogen, argon gas.
In above-mentioned preparation method, amphipathic nature block polymer is dissolved in Isosorbide-5-Nitrae-diethylbenzene, the work of Isosorbide-5-Nitrae-diethylbenzene
With being dissolving block copolymer, and it is allowed to form micella, while make solvent molecule with metallic element in metal carbonyl match somebody with somebody
Position, i.e., metallic element is more readily pulled from the coordination of carbonyl and decomposed, so as to reduce metal carbonyl cracking temperature.1,
The amount of 4- diethylbenzenes can be selected according to actual conditions, as long as making amphipathic nature block polymer form micella.
In above-mentioned preparation method, after the completion of cracking, reaction solution is cooled to room temperature, then will less active metal presoma
Introduce reaction system at room temperature to be reacted, the reaction is carried out in atmosphere.Reaction time is generally 10-48h.
In above-mentioned preparation method, after reaction terminates, will react liquid precipitate can obtain the metal -- Au of block copolymer cladding
Belong to oxide composite nanoparticle, metal-metallic oxide composite nanoparticle can also be disperseed to preserve in organic solvent.
In above-mentioned preparation method, the size of the metal-metallic oxide composite nanoparticle of gained block copolymer cladding
For below 10nm, generally in 3-8nm.Containing metal simple-substance and metal oxide in the composite nanoparticle, particle diameter distribution is uniform,
And be not easy to reunite in the case where block copolymer is stable, it is easily scattered, there is good application prospect.
The inventive method first adds metal carbonyl amphipathic using amphiphilic block copolymer micelle as reactor
In block copolymer weak solution, the relatively active metal that cracking reaction prepares block copolymer cladding is carried out at 150 DEG C -185 DEG C
Nano-particle, system cooling after, using compared with active metal simple substance nano-particle for sacrifice template, will be compared with torpescence by replacing reaction
Metal precursor is reduced to less active metal simple substance, remaining to form oxide in atmosphere compared with active metal exposure, final to obtain
To the metal-metallic oxide nano-particle of block copolymer cladding.The present invention is used as relatively active gold using metal carbonyl
The presoma of category, cracked in Isosorbide-5-Nitrae-diethylbenzene solution of amphipathic nature block polymer, cracking temperature substantially reduces, in normal pressure
Under can carry out, it is not necessary to high-tension apparatus, gained block copolymer cladding metal-metallic oxide composite nanoparticle for amount
Sub- size, in the solution dispersed soilless sticking.The size reduction of nano particle is to after quantum size, electron energy level intensity of variation
More than heat energy, luminous energy etc. change and after occupying an leading position, compared to blocky particle, the magnetic of quantum size nano particle, light, electricity etc.
Great changes will take place for performance, has application value in fields such as chemical sensor, biological detection and intelligent devices.
Brief description of the drawings
The low multiplication factor of gold-iron oxide composite nanoparticle of block copolymer stabilization prepared by Fig. 1 embodiments 1
TEM photos.
The high-amplification-factor of gold-iron oxide composite nanoparticle of block copolymer stabilization prepared by Fig. 2 embodiments 1
TEM photos.
The UV-vis collection of illustrative plates of gold-iron oxide composite nanoparticle of block copolymer stabilization prepared by Fig. 3 embodiments 1.
The energy spectrum diagram and element of gold-iron oxide composite nanoparticle of block copolymer stabilization prepared by Fig. 4 embodiments 1
Content.
The iron of gold-iron oxide composite nanoparticle of block copolymer stabilization prepared by Fig. 5 embodiments 1, gold element point
Butut.
Embodiment
The present invention is described in further detail with reference to specific embodiment.In following embodiments, amphiphilic used
Block copolymer, metal carbonyl, torpescence metal precursor are the commodity from market purchasing.
Embodiment 1
Stable gold-iron oxide composite nanoparticle the preparation process of block copolymer：Claim 5mg block copolymers（Polyphenyl second
Alkene-b- polyacrylic acid, polyacrylic acid content 19.4%, wherein molecular weight 15000-3600g/mol, polystyrene chain segment molecular weight
For 15000g/mol, polyacrylic acid chain segment molecular weight is 3600g/mol）In three-necked flask, and 10mL solvents are added thereto（1,
4- diethylbenzenes）Lead to nitrogen under magnetic stirring, be warming up to 120 DEG C and obtain the solution of clear.Then 36.5 μ L five are added
Carbonyl iron（Iron pentacarbonyl:Carboxyl mol ratio 20 in block copolymer:1）, it is continuously heating to 180 DEG C and is incubated 3h, is cooled to room
Temperature, the solution of the gold chloride containing 4.6mg is added into system（Mol ratio is HAuCl4/Fe=1:20), continue stirring reaction 24h, obtain
Gold-iron oxide composite Nano of the stable gold-iron oxide composite nanoparticle of block copolymer, also referred to as block copolymer cladding
Particle, it is standby after product filtering is taken out.
Fig. 1 and 2 is product transmission electron microscope（TEM）Picture, it can be seen that gold-oxidation that block copolymer is stable
Iron（Fe2O3）The size of composite nanoparticle is uniform in 6nm or so, particle diameter distribution；Nano-particle lattice fringe is obvious, shows to tie
Crystalline substance is good.Fig. 3 is the UV-vis collection of illustrative plates of product, it can be seen that the ultraviolet absorption peak of golden nanometer particle is in 556nm,
Generation red shift more obvious than the ultraviolet absorption peak of the golden nanometer particle of same particle size, show that gold and iron oxide have stronger phase interaction
With.
Fig. 4 is the energy spectrum diagram of gold-iron oxide composite nanoparticle, and following table is each element content situation, it can be seen that
There are ferro element and gold element simultaneously in composite nanoparticle, illustrate block copolymer micelle while coated two kinds of nano-particles.
Fig. 5 is iron, the gold element distribution map of the stable gold-iron oxide composite nano-granule subsample of block copolymer, can from figure
Go out, most golden nanometer particle is all combined together with iron.
Note：O K represent the K linear systems of oxygen element, and Fe K represent the K linear systems of ferro element, and Au L represent the L linear systems of gold element.
Embodiment 2
By block copolymer（Polystyrene-b- polyacrylic acid, molecular weight 15000-3600g/mol, polyacrylic acid content
19.4%）In three-necked flask, and solvent is added thereto（1,4- diethylbenzenes）Lead to nitrogen under magnetic stirring, be warming up to 120 DEG C
Obtain the micellar solution of clear.According to the mol ratio 10 of the carboxyl in iron pentacarbonyl and block copolymer:1 ratio, will
Block copolymer solution and the mixing of 18.2 μ L iron pentacarbonyls, are continuously heating to 180 DEG C and are incubated 3h, be cooled to room temperature, according to
HAuCl4/Fe=1:20 mol ratio adds chlorauric acid solution into system, continues stirring reaction 24h, and it is stable to obtain block copolymer
Gold-iron oxide composite nanoparticle, also referred to as block copolymer cladding gold-iron oxide composite nanoparticle, by product mistake
Leaching goes out rear standby.
Products therefrom is shown to be quantum size gold-metal oxide composite nanoparticle, the chi of nano-particle through TEM tests
Very little is 5nm.
Embodiment 3
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：The mol ratio 30 of carboxyl in iron pentacarbonyl and block copolymer:1.Products therefrom is shown to be quantum size through TEM tests
Gold-metal oxide composite nanoparticle, the size of nano-particle is 10nm.
Embodiment 4
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：The mol ratio 5 of carboxyl in iron pentacarbonyl and block copolymer:1.Products therefrom through TEM test be shown to be quantum size gold-
Metal oxide composite nanoparticle, the size of nano-particle is 3nm.
Embodiment 5
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：HAuCl4Mol ratio with Fe is 1:15.To be shown to be quantum size gold-metal oxide compound through TEM tests for products therefrom
Nano-particle, the size of nano-particle is 6nm.
Embodiment 6
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：HAuCl4Mol ratio with Fe is 1:10.To be shown to be quantum size gold-metal oxide compound through TEM tests for products therefrom
Nano-particle, the size of nano-particle is 8nm.
Embodiment 7
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：HAuCl4Mol ratio with Fe is 1:5.Products therefrom is shown to be quantum size gold-metal oxide is compound through TEM tests and received
Rice corpuscles, the size of nano-particle is 9nm.
Embodiment 8
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Block copolymer be polystyrene-b- polyethylene glycol oxide, iron pentacarbonyl and block copolymer mol ratio are 20:1.Gained produces
Thing is shown to be quantum size gold-metal oxide composite nanoparticle through TEM tests, and the size of nano-particle is 7nm.
Embodiment 9
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Block copolymer be polyvinylpyridine-b- polyethylene glycol oxide, iron pentacarbonyl and block copolymer mol ratio are 20:1.Institute
Obtain product and be shown to be quantum size gold-metal oxide composite nanoparticle through TEM tests, the size of nano-particle is 5nm.
Embodiment 10
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Reaction temperature is 160 DEG C.Products therefrom is shown to be quantum size gold-metal oxide composite nanoparticle through TEM tests,
The size of nano-particle is 8nm.
Embodiment 11
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Reaction temperature is 170 DEG C.Products therefrom is shown to be quantum size gold-metal oxide composite nanoparticle through TEM tests,
The size of nano-particle is 5nm.
Embodiment 12
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：The Pintsch process reaction time is 1h.Products therefrom is shown to be quantum size gold-metal oxide composite Nano through TEM tests
Particle, the size of nano-particle is 5nm.
Embodiment 13
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：The Pintsch process reaction time is 5h.Products therefrom is shown to be quantum size gold-metal oxide composite Nano through TEM tests
Particle, the size of nano-particle is 6nm.
Embodiment 14
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：The room temperature displacement reaction time is 10h.Products therefrom is shown to be quantum size gold-metal oxide composite Nano through TEM tests
Particle, the size of nano-particle is 5nm.
Embodiment 15
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：The room temperature displacement reaction time is 48h.Products therefrom is shown to be quantum size gold-metal oxide composite Nano through TEM tests
Particle, the size of nano-particle is 6nm.
Embodiment 16
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Torpescence metal precursor is silver nitrate.To be shown to be quantum size silver-metallic oxide compound through TEM tests for products therefrom
Nano-particle, the size of nano-particle is 5nm.
Embodiment 17
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Torpescence metal precursor is platinum nitrate.To be shown to be quantum size platinum-metal oxides compound through TEM tests for products therefrom
Nano-particle, the size of nano-particle is 6nm.
Embodiment 18
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Torpescence metal precursor is palladium nitrate.To be shown to be quantum size palladium-metal oxide compound through TEM tests for products therefrom
Nano-particle, the size of nano-particle is 4nm.
Embodiment 19
Method according to embodiment 2 prepares the stable metal-oxide iron composite nanoparticle of block copolymer, different
It is：Torpescence metal precursor is that tetrachloro closes palladium acid.Products therefrom is shown to be quantum size palladium-metal oxide through TEM tests
Composite nanoparticle, the size of nano-particle is 4nm.
Comparative example 1
According to the method for embodiment 1, the difference is that, after adding iron pentacarbonyl, it is continuously heating to 150 DEG C and is incubated 3h,
Iron pentacarbonyl can not crack in the case of this, be generated without nano-particle.
Comparative example 2
According to the method for embodiment 1, unlike, carboxyl and metal carbonyl rubs in amphipathic nature block polymer
You are than being 1:50, heated up after adding iron pentacarbonyl, then find a large amount of atraments be present on three-necked flask wall, after testing nanoparticle
The size of son is larger, not in quantum size scope.
Comparative example 3
According to the method for embodiment 1, in three-necked flask, and 10mL solvents are added thereto（1,4- diethylbenzenes）In magnetic force
Logical nitrogen under stirring, it is warming up to 120 DEG C and obtains the solution of clear.Unlike, first add 4.6mg chlorauric acid solutions, chlorine
120 DEG C of auric acid, which is decomposed, generates golden nanometer particle, then adds 36.5 μ L iron pentacarbonyls, is continuously heating to 180 DEG C and is incubated
3h.Detection finds that the ultraviolet absorption peak of golden nanometer particle is individually separated in 520nm, gold and ferric oxide nano particles, it is impossible to is formed
Gold-iron oxide composite nanoparticle.
Comparative example 4
According to the method for embodiment 1, the difference is that, the solvent for dissolving amphiphilic block copolymer is toluene.Add pentacarbonyl
After iron, it is warming up to 180 DEG C and is incubated 3h, iron pentacarbonyl can not cracks in the case, be generated without nano-particle.
The size of each embodiment product of table 1. and ultraviolet peak position
Claims (13)
1. a kind of preparation method of metal-metallic oxide composite nanoparticle, it is characterized in that：Metal carbonyl is in amphiphilic
Property block copolymer Isosorbide-5-Nitrae-diethylbenzene solution in carry out cracking reaction, the relatively active metal for forming block copolymer cladding is single
Matter；After reaction solution cooling, add more inactive metal precursor, displacement reaction occur compared with active metal with part, obtain compared with
Inactive metal nanoparticle, it is remaining compared with metal oxide is formed after active metal and air contact, finally give metal-
Metal oxide composite nanoparticle；
The metal carbonyl includes carbonyl iron, carbonyl cobalt or carbonyl nickel；More inactive metal include gold, silver,
Platinum or palladium, more inactive metal precursor are metal inorganic salt or acid.
2. preparation method according to claim 1, it is characterized in that：More inactive metal precursor includes gold chloride, chlorine
Auric acid lithium, acetic acid gold, silver nitrate, platinum nitrate, tetrachloro close the one or more in palladium acid and palladium nitrate.
3. preparation method according to claim 1, it is characterized in that：The amphipathic nature block polymer is to contain polypropylene
Acid, polyethylene glycol oxide, polyvinylpyridine, the block copolymer of PVP or N- vinyl imidazole blocks.
4. preparation method according to claim 3, it is characterized in that：The amphipathic nature block polymer be polystyrene-b-
Polyacrylic acid, polystyrene-b- polyethylene glycol oxide and polyvinylpyridine-bOne or more in-polyethylene glycol oxide.
5. preparation method according to claim 1, it is characterized in that：Metal carbonyl is carried out at 150 DEG C -185 DEG C
Cracking reaction.
6. preparation method according to claim 5, it is characterized in that：Metal carbonyl is carried out at 170 DEG C -180 DEG C
Cracking reaction.
7. preparation method according to claim 1, it is characterized in that：In metal carbonyl and amphipathic nature block polymer
Carboxyl mol ratio be 5:1 -30:1.
8. preparation method according to claim 7, it is characterized in that：In metal carbonyl and amphipathic nature block polymer
Carboxyl mol ratio be 10:1-20:1.
9. preparation method according to claim 1, it is characterized in that：Less active metal presoma and metal carbonyl
Mol ratio be 1:5-1:20.
10. preparation method according to claim 9, it is characterized in that：Less active metal presoma and metal-carbonyl chemical combination
The mol ratio of thing is 1:10-1:20.
11. preparation method according to claim 1, it is characterized in that：Cracking reaction is carried out under normal pressure, gas shield.
12. preparation method according to claim 1, it is characterized in that：The metal-metal oxide of gained block copolymer cladding
The size of thing composite nanoparticle is below 10nm.
13. preparation method according to claim 1, it is characterized in that：The metal-metal oxide of gained block copolymer cladding
The size of thing composite nanoparticle is 3-8nm.
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