CN104466204A - Array carbon nano-tube/graphene platinum-supported catalyst for fuel cell and preparation method of array carbon nano-tube/graphene platinum-supported catalyst - Google Patents
Array carbon nano-tube/graphene platinum-supported catalyst for fuel cell and preparation method of array carbon nano-tube/graphene platinum-supported catalyst Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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Abstract
The invention provides an array carbon nano-tube/graphene platinum-supported catalyst for a fuel cell and a preparation method of the array carbon nano-tube/graphene platinum-supported catalyst, belonging to the field of electrochemistry. The catalyst comprises the following components in percentage by mass: 60-80% of array carbon nano-tube/graphene and 20-40% of platinum. The array carbon nano-tubes/graphene is used as a catalyst support, and the platinum serving as a metal component is loaded on the support. The preparation method comprises the steps of firstly, preparing a nickel/cobalt-supported graphene composite; then, growing an upright ordered carbon nano-tube on the graphene through chemical vapor deposition; and finally, reducing platinum on the support, namely the graphene-array carbon nano-tube. The support has a special structure, and the upright ordered carbon nano-tube grows on the graphene, so that the relatively large specific surface area is obtained, the utilization ratio of platinum can be increased, a smooth ion and electron channel is also provided for electro-catalytic reaction, the electro-catalytic reaction rate can be favorably increased, and finally, the catalytic efficiency of the catalyst and the utilization ratio of precious metal can be favorably increased.
Description
Technical field
The present invention relates to a kind of fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method thereof, belong to electrochemical field.
Background technology
Fuel cell is a kind of electrochemical appliance directly converts chemical energy being become electric energy, one of its critical material is electrode catalyst, for a long time, the noble metal such as platinum (Pt), ruthenium (Ru) is widely used because it has remarkable catalytic performance always.But because the content of platinum metal in the earth's crust is limited, expensive, and platinum interest rate is in the battery not high, thus limits the development of fuel cell.Although alloy catalyst can reduce the carrying capacity of Pt, improve catalytic efficiency, need to improve in catalyst stability etc.Nucleocapsid catalyst, owing to having unique catalytic performance, in recent years more and more by the concern of people, is thus widely used in various chemical process.Because the electronics of alloy is different from simple metal with surface texture, therefore bimetallic catalyst shows better catalytic activity to some reaction.This is that the intermetallic interaction in two kinds, top layer can cause the change of bimetallic electronics and geometry, and the electric charge of the particle that thus changes, can be functionalized, can carry out the advantages such as surface reaction due to after the another kind of metal of the surface deposition of metal single crystal.
US20100197490 describes a kind of method that the coated base metal of a kind of platinum prepares nucleocapsid catalyst.The method of the base metal salt electronations such as Fe, Co, Ni, W, Cu is first reduced into the particle of 2-10nm by the method, and dry rear intensification 600 DEG C carries out annealing in process to 800 DEG C in atmosphere, and annealing time is determined because of different metal.After having annealed, this nano particle is immersed in platinum salting liquid, utilizes electrochemical displacement method at the surface deposition skim Pt shell of ISTon-noble metal particles, thus prepare core-shell type nanocatalyst.Although the method can make complete core-shell catalyst, operating process is complicated, and need consume mass energy, preparation cost is high.
CN200610019303 describes a kind of method of a kind of chemical replacement legal system for nucleocapsid catalyst.The method is that base metal salt is mixed with solution, adds a certain amount of surfactant, then in mixed solution, adds excessive reducing agent, make non-noble metal nano metal solution.In non-noble metal nano metal solution, add precious metal salt solution again and carry out chemical replacement, obtain the catalyst with core-casing structure solution that noble metal is wrapped in non-noble metal nanoparticles surface, obtain non-supported nucleocapsid catalyst.Finally in non-supported nucleocapsid catalyst solution, add carbon carrier to adsorb, obtain loaded nucleocapsid catalyst.The advantage of the method is that operating process is simple, and preparation cost is low, but catalyst particle size is bigger than normal, and catalyst is only connected with carbon carrier by suction-operated, is easy to come off in electrochemical reaction process, thus reduces catalytic efficiency.
Summary of the invention
An object of the present invention is to provide a kind of array carbon nano tube/Graphene platinum catalyst.
This catalyst utilizes carbon nano-tube to be uprightly arranged in this special carrier structure on Graphene, reaction is possessed unimpeded ion, electron channel, improves proton transport efficiency, increases the mass transfer rate of reactant and product.In addition, in the present invention, Graphene and carbon nano-tube are also for platinum provides larger specific area, decrease the consumption of noble metal platinum, thus also improve the catalytic efficiency of catalyst.
In order to realize above-mentioned purpose of the present invention, adopt following technical scheme:
This catalyst makes carrier by array carbon nano tube/Graphene, and active component is platinum.Its mass percent consists of: array carbon nano tube/Graphene: 60%-80% platinum: 20%-40%.
A kind of preferred technical scheme, is characterized in that:
Described array carbon nano tube/Graphene, is prepared by chemical vapour deposition (CVD) as carbon source by acetylene, and its carbon nano-tube is arranged on graphenic surface, as the carrier of platinum uprightly in order.
A kind of preferred technical scheme, is characterized in that:
Active metal platinum passes through the reducing loaded surface at array carbon nano tube/Graphene carrier of infusion process by chloroplatinic acid.
Another object of the present invention is to the preparation method that a kind of array carbon nano tube/Graphene platinum catalyst is provided.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A preparation method for array carbon nano tube/Graphene platinum catalyst, comprises the steps:
(1) get crystalline flake graphite appropriate, add the concentrated sulfuric acid and SPA, pre-oxidation 24h; Slowly add appropriate potassium permanganate under condition of ice bath, temperature control is below 20 DEG C; At 50 DEG C, add thermal response 12h afterwards, question response thing is down to room temperature, is poured in 400 ~ 500ml ice deionized water, adds 10 ~ 15ml 30% hydrogen peroxide, first uses the HCl centrifuge washing of 5%, then uses deionized water centrifuge washing, obtain the graphite oxide wet;
The volume ratio of the above-mentioned concentrated sulfuric acid and SPA is preferably 9:1;
(2) the wet graphite oxide obtained in step one is put into 400 ~ 500ml deionized water, continual ultrasonic 3 ~ 4h makes it fully dissolve.Add 10 ~ 15ml hydrazine hydrate after ultrasonic, 90 DEG C of back flow reaction 6h, cooling, by products therefrom filtering and washing and freeze drying, products therefrom is Graphene (RGO);
(3) Graphene obtained in step 2 is first carried out sensitization and activation with tin chloride solution and palladium bichloride hydrochloric acid solution respectively, dry through suction filtration, by electroless plating method, catalyst nickel or cobalt are loaded on Graphene again, obtain the Graphene carrying nickel or cobalt.
Above-mentioned electroless plating method can adopt following system: wherein the concentration of nickel nitrate/cobalt nitrate is 7 ~ 13g/L, the concentration of inferior sodium phosphate is 7 ~ 13g/L, the concentration of natrium citricum is 60 ~ 70g/L, the concentration of ammonium chloride is 37 ~ 43g/L, plating conditions is pH=6 ~ 9, temperature 70 C, the reaction time is about 1h.
(4) Graphene carrying nickel or cobalt in step 3 is put into tube furnace, employing acetylene is carbon source, chemical vapour deposition (CVD) is passed through under the effect of high temperature, metallic catalyst, between 550 ~ 750 DEG C on Graphene chemical vapour deposition (CVD) 25 ~ 50min, more all products to be immersed in 0.6mol/L HCl solution 10h to remove nickel/Co catalysts.Finally by filtering and washing, after freeze drying 24h, obtain array carbon nano tube/Graphene.
(5) array carbon nano tube/graphene composite material obtained in step 4 is mixed with chloroplatinic acid aqueous solution, heat under magnetic stirring and solvent evaporation is formed slurry liquid, then put it in 60 DEG C of baking ovens and dry.After mortar grinds, put it in tube furnace and use Acetylene Reduction 1 ~ 3h between 150 ~ 300 DEG C, last nitrogen cooling, obtains final catalyst platinum and carries array carbon nano tube/Graphene.
By carrying out structural characterization to end product, prove that this product is with array carbon nano tube/Graphene for carrier, the load of active metal component platinum is in carbon nano-tube and graphenic surface, and particle diameter is 3 ~ 5nm.And carbon nano-tube is uprightly orderly is arranged on Graphene.
Beneficial effect of the present invention: the present invention utilizes Graphene-array carbon nano tube for carrier, is carried on metal platinum and graphene-carbon nano tube carrier is prepared into platinum carries array carbon nano tube/graphen catalyst.Because the conductive capability of Graphene and carbon nano-tube is strong, electron mobility is large, simultaneously, carbon nano-tube is uprightly arranged in this special carrier structure on Graphene, reaction is possessed unimpeded ion, electron channel, improve proton transport efficiency, increase the mass transfer rate of reactant and product.In addition, in the present invention, Graphene and carbon nano-tube are also for platinum provides larger specific area, decrease the consumption of noble metal platinum.And self-control Graphene has more oxygen-containing functional group also enhance the combination of Pt catalyst granule and carbon carrier, make catalyst more stable.The present invention can improve the catalytic efficiency of catalyst and the utilance of noble metal greatly, will promote the fast development of fuel cell.
Accompanying drawing explanation
Fig. 1 is SEM spectrogram and the HRTEM figure of the array carbon nano tube/Graphene of preparation;
Fig. 2 is the XRD spectra that platinum carries array carbon nano tube/graphen catalyst, nickel carries array carbon nano tube/Graphene of preparation;
Fig. 3 is the polarization curves of oxygen reduction figure that 20% platinum prepared carries array carbon nano tube/graphen catalyst and commercialization JM-20%Pt/C catalyst.
Embodiment
Below by specific embodiment, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Embodiment 1
(1) get crystalline flake graphite 3g, add the concentrated sulfuric acid and SPA respectively, pre-oxidation 24h; Slowly add appropriate potassium permanganate 18g under condition of ice bath, temperature control is below 20 DEG C; At 50 DEG C, add thermal response 12h afterwards, question response thing is down to room temperature, is poured in 400ml ice deionized water, adds 10ml 30% hydrogen peroxide, first uses the HCl centrifuge washing of 5%, then uses deionized water centrifuge washing, obtain the graphite oxide wet;
(2) get the wet graphite oxide 100ml obtained in step one, put into 500ml deionized water, continual ultrasonic 3h makes it fully dissolve.Add 10ml hydrazine hydrate after ultrasonic, 90 DEG C of back flow reaction 6h, cooling, by products therefrom filtering and washing and freeze drying, products therefrom is Graphene (RGO);
(3) get the Graphene 0.1g obtained in step 2 and first carry out sensitization and activation with tin chloride solution and palladium bichloride hydrochloric acid solution respectively, wherein stannous chloride solution is 100ml concentration is the solution (10% diluted hydrochloric acid dissolution) that 10g/L newly configures, and palladium chloride solution is 100ml concentration is 10g/L solution (10% diluted hydrochloric acid dissolution).Dry through suction filtration, then by electroless plating method, catalyst nickel or cobalt are loaded on Graphene, obtain the Graphene carrying nickel or cobalt.Wherein the concentration of nickel nitrate/cobalt nitrate is 10g/L, and the concentration of inferior sodium phosphate is 10g/L, and the concentration of natrium citricum is 65g/L, and the concentration of ammonium chloride is 40g/L, and plating conditions is pH=8, temperature 70 C, and the reaction time is about 1h.
(4) Graphene carrying nickel or cobalt in step 3 is put into tube furnace, employing acetylene is carbon source, chemical vapour deposition (CVD) is passed through under the effect of high temperature, metallic catalyst, between 600 DEG C on Graphene chemical vapour deposition (CVD) 35min, more all products to be immersed in 0.6mol/L HCl solution 10h to remove nickel/Co catalysts.Finally by filtering and washing, after freeze drying 24h, obtain array carbon nano tube/Graphene.
(5) get the array carbon nano tube/graphene composite material 80mg obtained in step 4 to mix with 2655 μ l chloroplatinic acids ethylene glycol solution (1g/50ml), heat under magnetic stirring and solvent evaporation is formed slurry liquid, then put it in 60 DEG C of baking ovens and dry.Mortar puts it in tube furnace and uses Acetylene Reduction 2h between 150 DEG C after grinding, and last nitrogen cooling, obtains final catalyst platinum and carry array carbon nano tube/Graphene.
Embodiment 2
(1) get crystalline flake graphite 3g, add the concentrated sulfuric acid and SPA 360ml and 40ml respectively, pre-oxidation 24h; Slowly add appropriate potassium permanganate 18g under condition of ice bath, temperature control is below 20 DEG C; At 50 DEG C, add thermal response 12h afterwards, question response thing is down to room temperature, is poured in 400ml ice deionized water, adds 10ml 30% hydrogen peroxide, first uses the HCl centrifuge washing of 5%, then uses deionized water centrifuge washing, obtain the graphite oxide wet;
(2) get the wet graphite oxide 100ml obtained in step one, put into 500ml deionized water, continual ultrasonic 3h makes it fully dissolve.Add 10ml hydrazine hydrate after ultrasonic, 90 DEG C of back flow reaction 6h, cooling, by products therefrom filtering and washing and freeze drying, products therefrom is Graphene (RGO);
(3) get the Graphene 0.1g obtained in step 2 and first carry out sensitization and activation with tin chloride solution and palladium bichloride hydrochloric acid solution respectively, wherein stannous chloride solution is 100ml concentration is the solution (10% diluted hydrochloric acid dissolution) that 10g/L newly configures, and palladium chloride solution is 100ml concentration is 10g/L solution (10% diluted hydrochloric acid dissolution).Dry through suction filtration, then by electroless plating method, catalyst nickel or cobalt are loaded on Graphene, obtain the Graphene carrying nickel or cobalt.Wherein the concentration of nickel nitrate/cobalt nitrate is 10g/L, and the concentration of inferior sodium phosphate is 10g/L, and the concentration of natrium citricum is 65g/L, and the concentration of ammonium chloride is 40g/L, and plating conditions is pH=8, temperature 70 C, and the reaction time is about 1h.
(4) Graphene carrying nickel or cobalt in step 3 is put into tube furnace, employing acetylene is carbon source, chemical vapour deposition (CVD) is passed through under the effect of high temperature, metallic catalyst, between 600 DEG C on Graphene chemical vapour deposition (CVD) 35min, more all products to be immersed in 0.6mol/L HCl solution 10h to remove nickel/Co catalysts.Finally by filtering and washing, after freeze drying 24h, obtain array carbon nano tube/Graphene.
(5) get the array carbon nano tube/graphene composite material 60mg obtained in step 4 to mix with 5310 μ l chloroplatinic acids ethylene glycol solution (1g/50ml), heat under magnetic stirring and solvent evaporation is formed slurry liquid, then put it in 60 DEG C of baking ovens and dry.Mortar puts it in tube furnace and uses Acetylene Reduction 2h between 150 DEG C after grinding, and last nitrogen cooling, obtains final catalyst platinum and carry array carbon nano tube/Graphene.
Embodiment 3
(1) get crystalline flake graphite 3g, add the concentrated sulfuric acid and SPA 360ml and 40ml respectively, pre-oxidation 24h; Slowly add appropriate potassium permanganate 18g under condition of ice bath, temperature control is below 20 DEG C; At 50 DEG C, add thermal response 12h afterwards, question response thing is down to room temperature, is poured in 400ml ice deionized water, adds 10ml 30% hydrogen peroxide, first uses the HCl centrifuge washing of 5%, then uses deionized water centrifuge washing, obtain the graphite oxide wet;
(2) get the wet graphite oxide 100ml obtained in step one, put into 500ml deionized water, continual ultrasonic 3h makes it fully dissolve.Add 10ml hydrazine hydrate after ultrasonic, 90 DEG C of back flow reaction 6h, cooling, by products therefrom filtering and washing and freeze drying, products therefrom is Graphene (RGO);
(3) get the Graphene 0.1g obtained in step 2 and first carry out sensitization and activation with tin chloride solution and palladium bichloride hydrochloric acid solution respectively, wherein stannous chloride solution is 100ml concentration is the solution (10% diluted hydrochloric acid dissolution) that 10g/L newly configures, and palladium chloride solution is 100ml concentration is 10g/L solution (10% diluted hydrochloric acid dissolution).Dry through suction filtration, then by electroless plating method, catalyst nickel or cobalt are loaded on Graphene, obtain the Graphene carrying nickel or cobalt.(4) Graphene carrying nickel or cobalt in step 3 is put into tube furnace, employing acetylene is carbon source, chemical vapour deposition (CVD) is passed through under the effect of high temperature, metallic catalyst, between 600 DEG C on Graphene chemical vapour deposition (CVD) 35min, more all products to be immersed in 0.6mol/L HCl solution 10h to remove nickel/Co catalysts.Finally by filtering and washing, after freeze drying 24h, obtain array carbon nano tube/Graphene.
(5) get the array carbon nano tube/graphene composite material 70mg obtained in step 4 to mix with 3983 μ l chloroplatinic acids ethylene glycol solution (1g/50ml), heat under magnetic stirring and solvent evaporation is formed slurry liquid, then put it in 60 DEG C of baking ovens and dry.Mortar puts it in tube furnace and uses Acetylene Reduction 2h between 150 DEG C after grinding, and last nitrogen cooling, obtains final catalyst platinum and carry array carbon nano tube/Graphene.
Embodiment 4
Fig. 1 is SEM spectrogram and the HRTEM figure of the array carbon nano tube/Graphene of preparation.Can find out that from SEM figure the almost orderly aligned growth of carbon nano-tube prepared by chemical vapour deposition (CVD) is on the graphene-based end, pattern comparison rule is consistent, and arrange on Graphene tight, caliber is 15 ~ 20nm, and pipe range is 200 ~ 250nm.The a lot of granule of carbon nano-tube outer wall load can be seen from HRTEM figure, through the measurement of spacing of lattice, about 0.228nm, conform to the interplanar distance of platinum (111), illustrate that load is the metal platinum be reduced at the granule of carbon pipe outer wall.
Fig. 2 is the XRD spectra that platinum carries array carbon nano tube/graphen catalyst, nickel carries array carbon nano tube/Graphene of preparation.Peak wherein in 2 θ=26.22 ° is the characteristic diffraction peak of Graphene.Nickel carries in 2 θ=44.47 ° in the XRD figure of Graphene, 51.8 °, and the diffraction maximum of 76.37 ° is the characteristic peak of nickel.The platinum obtained after HCl process Supported Pt Nanoparticles carries in the XRD figure of array carbon nano tube/graphen catalyst, in 2 θ=44.47 °, 51.8 °, the peak of 76.37 ° disappears, and in 2 θ=39.8 °, there is diffraction maximum in 46.2 ° and 67.5 ° of places, this is the crystallographic plane diffraction peak of platinum (111), (200), (220), illustrate that chloroplatinic acid has been reduced and obtain platinum grain, prepared target product platinum and carried array carbon nano tube/graphen catalyst.
Fig. 3 is the polarization curves of oxygen reduction figure that 20% platinum prepared carries array carbon nano tube/graphen catalyst and commercialization JM-20%Pt/C catalyst.This is at O
2saturated 0.1mol/L HClO
4oRR polarization curve in electrolyte, rotating disk electrode (r.d.e) rotating speed 1600rpm
-1.As can be seen from the figure 20% platinum carries array carbon nano tube/graphen catalyst has higher initial reduction current potential than the business Pt/C catalyst of identical platinum carrying capacity, illustrate that it has higher oxygen reduction catalytic activity, this is because the structure of array carbon nano tube/Graphene uniqueness decreases ohmic polarization and the concentration polarization of reaction, for reaction carry out smoothly provide unimpeded ion channel and proton channel, thus improve platinum utilization.
Claims (8)
1. fuel cell array carbon nano tube/Graphene platinum catalyst, it is characterized in that, described catalyst makes carrier by array carbon nano tube/Graphene, and active component is platinum, its mass percent consists of: array carbon nano tube/Graphene 60%-80%, platinum 20%-40%.
2. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as claimed in claim 1, it is characterized in that, described array carbon nano tube/Graphene, is prepared by chemical vapour deposition (CVD) as carbon source by acetylene, as the carrier of platinum.
3. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as claimed in claim 1 or 2, is characterized in that, described carbon nano-tube is uprightly orderly being arranged on graphenic surface.
4. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as described in claim 1 or 3, is characterized in that, described platinum passes through the reducing loaded surface at array carbon nano tube/Graphene carrier of infusion process by chloroplatinic acid.
5. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as claimed in claim 1, it is characterized in that, the preparation method of described catalyst comprises the steps:
(1) get crystalline flake graphite appropriate, add the concentrated sulfuric acid and SPA, pre-oxidation 24h; Slowly add appropriate potassium permanganate under condition of ice bath, temperature control is below 20 DEG C; At 50 DEG C, add thermal response 12h afterwards, question response thing is down to room temperature, is poured in 400 ~ 500ml ice deionized water, adds 10 ~ 15ml 30% hydrogen peroxide, first uses the HCl centrifuge washing of 5%, then uses deionized water centrifuge washing, obtain the graphite oxide wet;
(2) the wet graphite oxide obtained in step one is put into 400 ~ 500ml deionized water, continual ultrasonic 3 ~ 4h makes it fully dissolve; Add 10 ~ 15ml hydrazine hydrate after ultrasonic, 90 DEG C of back flow reaction 6h, cooling, by products therefrom filtering and washing and freeze drying, products therefrom is Graphene;
(3) Graphene obtained in step 2 is first carried out sensitization and activation with tin chloride solution and palladium bichloride hydrochloric acid solution respectively, dry through suction filtration, by electroless plating method, catalyst nickel or cobalt are loaded on Graphene again, obtain the Graphene carrying nickel or cobalt;
(4) Graphene carrying nickel or cobalt in step 3 is put into tube furnace, employing acetylene is carbon source, chemical vapour deposition (CVD) is passed through under the effect of high temperature, metallic catalyst, between 550 ~ 750 DEG C on Graphene chemical vapour deposition (CVD) 25 ~ 50min, more all products to be immersed in 0.6mol/L HCl solution 10h to remove nickel/Co catalysts; Finally by filtering and washing, after freeze drying 24h, obtain array carbon nano tube/Graphene;
(5) array carbon nano tube/graphene composite material obtained in step 4 is mixed with chloroplatinic acid aqueous solution, heat under magnetic stirring and solvent evaporation is formed slurry liquid, then put it in 60 DEG C of baking ovens and dry.After mortar grinds, put it in tube furnace and use Acetylene Reduction 1 ~ 3h between 150 ~ 300 DEG C, last nitrogen cooling, obtains final catalyst platinum and carries array carbon nano tube/Graphene.
6. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as claimed in claim 5, it is characterized in that, described in step (1), the volume ratio of the concentrated sulfuric acid and SPA is 9:1.
7. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as claimed in claim 5, it is characterized in that, described in step (3), the condition of electroless plating method is as follows: the concentration of nickel nitrate/cobalt nitrate is 7 ~ 13g/L, the concentration of inferior sodium phosphate is 7 ~ 13g/L, the concentration of natrium citricum is 60 ~ 70g/L, and the concentration of ammonium chloride is 37 ~ 43g/L, and plating conditions is pH=6 ~ 9, temperature 70 C, the reaction time is about 1h.
8. a preparation method for fuel cell array carbon nano tube/Graphene platinum catalyst, comprises the steps:
(1) get crystalline flake graphite appropriate, add the concentrated sulfuric acid and SPA, the volume ratio of the concentrated sulfuric acid and SPA is 9:1, pre-oxidation 24h; Slowly add appropriate potassium permanganate under condition of ice bath, temperature control is below 20 DEG C; At 50 DEG C, add thermal response 12h afterwards, question response thing is down to room temperature, is poured in 400 ~ 500ml ice deionized water, adds 10 ~ 15ml 30% hydrogen peroxide, first uses the HCl centrifuge washing of 5%, then uses deionized water centrifuge washing, obtain the graphite oxide wet;
(2) the wet graphite oxide obtained in step one is put into 400 ~ 500ml deionized water, continual ultrasonic 3 ~ 4h makes it fully dissolve; Add 10 ~ 15ml hydrazine hydrate after ultrasonic, 90 DEG C of back flow reaction 6h, cooling, by products therefrom filtering and washing and freeze drying, products therefrom is Graphene;
(3) Graphene obtained in step 2 is first carried out sensitization and activation with tin chloride solution and palladium bichloride hydrochloric acid solution respectively, dry through suction filtration, by electroless plating method, catalyst nickel or cobalt are loaded on Graphene again, obtain the Graphene carrying nickel or cobalt; Wherein the concentration of nickel nitrate/cobalt nitrate is 7 ~ 13g/L, and the concentration of inferior sodium phosphate is 7 ~ 13g/L, and the concentration of natrium citricum is 60 ~ 70g/L, and the concentration of ammonium chloride is 37 ~ 43g/L, and plating conditions is pH=6 ~ 9, temperature 70 C, and the reaction time is about 1h;
(4) Graphene carrying nickel or cobalt in step 3 is put into tube furnace, employing acetylene is carbon source, chemical vapour deposition (CVD) is passed through under the effect of high temperature, metallic catalyst, between 550 ~ 750 DEG C on Graphene chemical vapour deposition (CVD) 25 ~ 50min, more all products to be immersed in 0.6mol/L HCl solution 10h to remove nickel/Co catalysts; Finally by filtering and washing, after freeze drying 24h, obtain array carbon nano tube/Graphene;
(5) array carbon nano tube/graphene composite material obtained in step 4 is mixed with chloroplatinic acid aqueous solution, heat under magnetic stirring and solvent evaporation is formed slurry liquid, then put it in 60 DEG C of baking ovens and dry; After mortar grinds, put it in tube furnace and use Acetylene Reduction 1 ~ 3h between 150 ~ 300 DEG C, last nitrogen cooling, obtains final catalyst platinum and carries array carbon nano tube/Graphene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105186009A (en) * | 2015-09-07 | 2015-12-23 | 武汉理工大学 | Fuel-cell catalyst with nano-graphite carbon rivet structure and preparation method of fuel-cell catalyst |
| WO2016177951A1 (en) * | 2015-05-06 | 2016-11-10 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Catalyst supported by carbon nanotubes and by graphene, and method for preparing same |
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| FR3035800A1 (en) * | 2015-05-06 | 2016-11-11 | Commissariat Energie Atomique | CATALYST SUPPORTED BY CARBON NANOTUBES AND GRAPHENE, AND PROCESS FOR PREPARING THE SAME |
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| CN112169845B (en) * | 2020-11-08 | 2023-12-26 | 赵伟 | Preparation method of catalytic material |
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| CN114360917A (en) * | 2021-12-09 | 2022-04-15 | 中国科学院高能物理研究所 | Three-dimensional composite material of graphdiyne-carbon nano tube and preparation method and application thereof |
| CN114360917B (en) * | 2021-12-09 | 2023-09-29 | 中国科学院高能物理研究所 | Graphite alkyne-carbon nano tube three-dimensional composite material and preparation method and application thereof |
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