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
- Publication number
- CN104466204A CN104466204A CN201410742322.3A CN201410742322A CN104466204A CN 104466204 A CN104466204 A CN 104466204A CN 201410742322 A CN201410742322 A CN 201410742322A CN 104466204 A CN104466204 A CN 104466204A
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon nano
- platinum
- catalyst
- array carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 101
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 75
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 119
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 55
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 230000004044 response Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000007772 electroless plating Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- 206010070834 Sensitisation Diseases 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000003426 co-catalyst Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000003863 metallic catalyst Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 230000008313 sensitization Effects 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000000935 solvent evaporation Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000010970 precious metal Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/8817—Treatment of supports before application of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410742322.3A CN104466204B (en) | 2014-12-08 | 2014-12-08 | Fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410742322.3A CN104466204B (en) | 2014-12-08 | 2014-12-08 | Fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104466204A true CN104466204A (en) | 2015-03-25 |
CN104466204B CN104466204B (en) | 2016-10-05 |
Family
ID=52911885
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410742322.3A Expired - Fee Related CN104466204B (en) | 2014-12-08 | 2014-12-08 | Fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104466204B (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN106219531A (en) * | 2016-07-29 | 2016-12-14 | 碳元科技股份有限公司 | A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film |
CN107256973A (en) * | 2017-06-30 | 2017-10-17 | 天津工业大学 | A kind of preparation method of three-dimensional structure graphene carbon nanotube composite carrier load PtSn catalyst |
CN107829107A (en) * | 2017-09-25 | 2018-03-23 | 中国科学院山西煤炭化学研究所 | A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application |
CN109873175A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of low-temperature fuel cell supports the preparation method of platinum cobalt iridium alloy structure catalyst with nitridation three-dimensional carrier |
CN111530462A (en) * | 2020-04-20 | 2020-08-14 | 无锡东恒新能源科技有限公司 | Synthetic array type carbon nanotube catalyst and preparation method and application thereof |
CN112007636A (en) * | 2020-08-26 | 2020-12-01 | 郑州大学 | Method for preparing graphene quantum dot doped noble metal nanotube array by constant current codeposition |
CN112169845A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Preparation method of composite carbon catalytic material |
CN113113622A (en) * | 2021-03-16 | 2021-07-13 | 国家电投集团氢能科技发展有限公司 | Fuel cell catalyst layer slurry and preparation method and application thereof |
CN113140742A (en) * | 2021-04-01 | 2021-07-20 | 邵阳学院 | PtM/CNT/C catalyst and preparation method and application thereof |
CN113769774A (en) * | 2021-10-12 | 2021-12-10 | 深圳稳石氢能科技有限公司 | Nitrogen-doped graphene-carbon nanotube composite catalyst and preparation method thereof |
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102179244A (en) * | 2011-04-13 | 2011-09-14 | 山西大学 | Preparation method of catalyst of proton exchange membrane fuel cell |
CN103286318A (en) * | 2013-04-03 | 2013-09-11 | 华中科技大学 | Preparation method of nano precious metal-carbon nano tube-graphene composite and nano precious metal-carbon nano tube-graphene composite product |
CN103384007A (en) * | 2013-07-23 | 2013-11-06 | 深圳清华大学研究院 | Carbon nano tube/graphene composite negative pole material, preparation method thereof and lithium battery |
-
2014
- 2014-12-08 CN CN201410742322.3A patent/CN104466204B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102179244A (en) * | 2011-04-13 | 2011-09-14 | 山西大学 | Preparation method of catalyst of proton exchange membrane fuel cell |
CN103286318A (en) * | 2013-04-03 | 2013-09-11 | 华中科技大学 | Preparation method of nano precious metal-carbon nano tube-graphene composite and nano precious metal-carbon nano tube-graphene composite product |
CN103384007A (en) * | 2013-07-23 | 2013-11-06 | 深圳清华大学研究院 | Carbon nano tube/graphene composite negative pole material, preparation method thereof and lithium battery |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
FR3035800A1 (en) * | 2015-05-06 | 2016-11-11 | Commissariat Energie Atomique | CATALYST SUPPORTED BY CARBON NANOTUBES AND GRAPHENE, AND PROCESS FOR PREPARING THE SAME |
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 |
CN106219531A (en) * | 2016-07-29 | 2016-12-14 | 碳元科技股份有限公司 | A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film |
CN106219531B (en) * | 2016-07-29 | 2018-12-25 | 碳元科技股份有限公司 | A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film |
CN107256973A (en) * | 2017-06-30 | 2017-10-17 | 天津工业大学 | A kind of preparation method of three-dimensional structure graphene carbon nanotube composite carrier load PtSn catalyst |
CN107829107A (en) * | 2017-09-25 | 2018-03-23 | 中国科学院山西煤炭化学研究所 | A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application |
CN109873175A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of low-temperature fuel cell supports the preparation method of platinum cobalt iridium alloy structure catalyst with nitridation three-dimensional carrier |
CN109873175B (en) * | 2017-12-04 | 2021-05-11 | 中国科学院大连化学物理研究所 | Preparation method of nitrided three-dimensional carrier supported platinum-cobalt-iridium alloy structure catalyst for low-temperature fuel cell |
CN111530462A (en) * | 2020-04-20 | 2020-08-14 | 无锡东恒新能源科技有限公司 | Synthetic array type carbon nanotube catalyst and preparation method and application thereof |
CN112007636B (en) * | 2020-08-26 | 2023-01-24 | 郑州大学 | Method for preparing graphene quantum dot doped noble metal nanotube array by constant current codeposition |
CN112007636A (en) * | 2020-08-26 | 2020-12-01 | 郑州大学 | Method for preparing graphene quantum dot doped noble metal nanotube array by constant current codeposition |
CN112169845A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Preparation method of composite carbon catalytic material |
CN112169845B (en) * | 2020-11-08 | 2023-12-26 | 赵伟 | Preparation method of catalytic material |
CN113113622B (en) * | 2021-03-16 | 2022-01-28 | 国家电投集团氢能科技发展有限公司 | Fuel cell catalyst layer slurry and preparation method and application thereof |
CN113113622A (en) * | 2021-03-16 | 2021-07-13 | 国家电投集团氢能科技发展有限公司 | Fuel cell catalyst layer slurry and preparation method and application thereof |
CN113140742A (en) * | 2021-04-01 | 2021-07-20 | 邵阳学院 | PtM/CNT/C catalyst and preparation method and application thereof |
CN113140742B (en) * | 2021-04-01 | 2022-08-30 | 邵阳学院 | PtM/CNT/C catalyst and preparation method and application thereof |
CN113769774A (en) * | 2021-10-12 | 2021-12-10 | 深圳稳石氢能科技有限公司 | Nitrogen-doped graphene-carbon nanotube composite catalyst and preparation method thereof |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN104466204B (en) | 2016-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104466204B (en) | Fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method | |
CN108493461B (en) | N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof | |
Zhang et al. | Single Fe atom on hierarchically porous S, N‐codoped nanocarbon derived from porphyra enable boosted oxygen catalysis for rechargeable Zn‐air batteries | |
CN108906106B (en) | FeNi/N-C high-dispersion core-shell structure catalyst and preparation method thereof | |
Zhan et al. | Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media | |
Zhang et al. | Fe, Co, N-functionalized carbon nanotubes in situ grown on 3D porous N-doped carbon foams as a noble metal-free catalyst for oxygen reduction | |
Gao et al. | Honeysuckles-derived porous nitrogen, sulfur, dual-doped carbon as high-performance metal-free oxygen electroreduction catalyst | |
CN103227334B (en) | Carbon-containing metal catalyst, preparation method and application thereof | |
CN105293483B (en) | A kind of method that original position prepares transient metal doped porous graphene | |
CN101820066B (en) | Single metal/multi-wall carbon nano tube type composite material, preparation method and application thereof | |
CN110142058B (en) | F127-induced three-dimensional porous FeNi-NC dual-functional electrocatalyst and preparation method thereof | |
CN102294255B (en) | Carbon gel catalyst and application thereof | |
CN102104157B (en) | Preparation method for carbon dry gel | |
CN110890558A (en) | Supported platinum-based core-shell catalyst and preparation method thereof | |
CN104923204A (en) | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst | |
CN105244513A (en) | Graphite-phase carbon nitride-modified carbon black-loaded platinum-palladium alloy nano electrocatalyst and preparation method | |
CN108654659B (en) | A kind of phosphating sludge/graphene composite nano material and preparation method thereof | |
CN103537299A (en) | Carbon-loaded Co core-Pt shell nanoparticle catalyst as well as preparation method thereof | |
CN108023074A (en) | A kind of silicon based composite material with nanometer hierarchical structure and its preparation method and application | |
CN102315462B (en) | Electrode used for vanadium redox flow battery and preparation method for electrode | |
Zhang et al. | Three-dimensional hybrid aerogels built from graphene and polypyrrole-derived nitrogen-doped carbon nanotubes as a high-efficiency Pt-based catalyst support | |
CN113809341B (en) | Cu-N-C oxygen reduction catalyst and preparation method thereof | |
CN103007926A (en) | Preparation method of platinum/vertical graphene composite material electrocatalyst | |
CN103915633A (en) | Composite carbon fiber-loaded metal catalyst as well as preparation method and application thereof | |
Wang et al. | WxCoyS core-shell grown on hollow-porous carbon fiber (HCF) as synergetic electrocatalysts for efficient water splitting |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161005 |