CN104466204B - Fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method - Google Patents

Fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method Download PDF

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CN104466204B
CN104466204B CN201410742322.3A CN201410742322A CN104466204B CN 104466204 B CN104466204 B CN 104466204B CN 201410742322 A CN201410742322 A CN 201410742322A CN 104466204 B CN104466204 B CN 104466204B
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graphene
carbon nano
nano tube
catalyst
platinum
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CN104466204A (en
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朱红
魏伶俐
孔令汉
王芳辉
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Beijing University of Chemical Technology
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    • 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

Abstract

The invention provides a kind of fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method thereof, belong to electrochemical field.This catalyst quality percentage ratio consists of: array carbon nano tube/Graphene: 60% 80%, platinum: 20% 40%.Metal component platinum as catalyst carrier, then is carried on carrier by it by array carbon nano tube/Graphene.The present invention first prepares nickel cobalt and carries graphene composite material, then is deposited on, by chemical gaseous phase, the CNT that growing upright on Graphene is orderly, is finally reduced by platinum on carrier graphene array CNT.This kind of carrier has special structure, the most orderly carbon nano tube growth not only has bigger specific surface area can improve platinum utilization on Graphene, also provide unimpeded ion, electron channel for electrocatalytic reaction, be conducive to improving electrocatalytic reaction speed, ultimately facilitate catalytic efficiency and the utilization rate of noble metal improving catalyst.

Description

Fuel cell array carbon nano tube/Graphene platinum catalyst and preparation method
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 In electrochemical field.
Background technology
Fuel cell is a kind of electrochemical appliance directly converting chemical energy into electric energy, and 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 of its catalytic performance with brilliance always.But Owing to platinum metal content in the earth's crust is limited, expensive, and the interest rate that platinum is in the battery is the highest, thus limit fuel The development of battery.Although alloy catalyst can reduce the carrying capacity of Pt, improve catalytic efficiency, but at aspects such as catalyst stabilities also Have much room for improvement.Nucleocapsid catalyst, owing to having the catalytic performance of uniqueness, is the most increasingly paid close attention to by people, thus by extensively It is applied to various chemical process.Owing to the electronics of alloy is different from simple metal with surface texture, therefore bimetallic catalyst Some reaction is shown and is preferably catalyzed activity.This is due to after the another kind of metal of deposition of the surface of metal single crystal, table Two kinds of intermetallic interaction of layer can cause the change of bimetallic electronics and geometry, thus the electricity of the particle that changes Lotus, it is possible to functionalization, can carry out the advantages such as surface reaction.
US20100197490 describes a kind of platinum cladding base metal and prepares a kind of method of nucleocapsid catalyst.The method First the method for the base metal salt electronations such as Fe, Co, Ni, W, Cu is reduced into the granule of 2-10nm, is dried in atmosphere Rear intensification 600 DEG C makes annealing treatment to 800 DEG C, depending on annealing time is because of different metal.After having annealed, by this nano-particle Immerse in platinum salt solution, utilize electrochemical displacement method to deposit a thin layer Pt shell on the surface of ISTon-noble metal particles, thus prepare core- Core-shell type nanometer catalyst.Although the method can make complete core-shell catalyst, but operating process is complicated, need to consume a large amount of energy Source, preparation cost is high.
CN200610019303 describes a kind of chemical replacement method and prepares a kind of method of nucleocapsid catalyst.The method is Base metal salt is configured to solution, adds a certain amount of surfactant, in mixed solution, then add the reduction of excess Agent, makes non-noble metal nano metal solution.In non-noble metal nano metal solution, add precious metal salt solution again enter Row chemical replacement, obtains noble metal and is wrapped in the catalyst with core-casing structure solution on non-noble metal nanoparticles surface, obtain non-load Load type nucleocapsid catalyst.The last carbon carrier that adds in non-supported nucleocapsid catalyst solution adsorbs, and obtains loaded core Shell 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 It is connected with carbon carrier by adsorption, it 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 CNT to be uprightly arranged in the carrier structure that on Graphene, this is special, makes reaction possess Unimpeded ion, electron channel, improve proton transport efficiency, increase the mass transfer rate of reactant and product.Additionally, this In invention, Graphene and CNT also provide bigger specific surface area for platinum, decrease the consumption of noble metal platinum, from And also improve the catalytic efficiency of catalyst.
In order to realize the above-mentioned purpose of the present invention, use following technical scheme:
This catalyst is made carrier by array carbon nano tube/Graphene, and active component is platinum.Its mass percent forms For: array carbon nano tube/Graphene: 60%-80% platinum: 20%-40%.
A kind of preferably technical scheme, it is characterised in that:
Described array carbon nano tube/Graphene, is prepared by chemical gaseous phase deposition, its carbon as carbon source by acetylene Nanotube is the most orderly being arranged on graphenic surface, as the carrier of platinum.
A kind of preferably technical scheme, it is characterised in that:
Active metal platinum is passed 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 provide the preparation method of a kind of array carbon nano tube/Graphene platinum catalyst.
The above-mentioned purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of array carbon nano tube/Graphene platinum catalyst, comprises the steps:
(1) take crystalline flake graphite appropriate, add concentrated sulphuric acid and strong phosphoric acid, pre-oxidize 24h；It is slowly added to appropriate under condition of ice bath Potassium permanganate, temperature control is below 20 DEG C；Reacting by heating 12h at 50 DEG C afterwards, question response thing is down to room temperature, is poured into 400 ～in 500ml ice deionized water, add 10～15ml 30% hydrogen peroxide, first with 5% HCl centrifuge washing, then use deionized water Centrifuge washing, obtains wet graphite oxide；
The volume ratio of above-mentioned concentrated sulphuric acid and strong phosphoric acid is preferably 9:1；
(2) the wet graphite oxide obtained in step one is put in 400～500ml deionized waters, continual ultrasonic 3～4h It is made fully to dissolve.Adding 10～15ml hydrazine hydrates, 90 DEG C of back flow reaction 6h after ultrasonic, cooling, by products therefrom filtering and washing And lyophilization, products therefrom is Graphene (RGO)；
(3) Graphene obtained in step 2 is carried out with tin chloride solution and Palladous chloride. hydrochloric acid solution the most respectively Sensitization and activation, dried through sucking filtration, then catalyst nickel or cobalt be loaded on Graphene by electroless plating method, obtains carrying nickel or cobalt Graphene.
Above-mentioned electroless plating method can use following system: wherein the concentration of nickel nitrate/cobalt nitrate is 7～13g/L, secondary phosphorous The concentration of acid sodium is 7～13g/L, and the concentration of sodium citrate is 60～70g/L, and the concentration of ammonium chloride is 37～43g/L, plating bar Part is pH=6～9, temperature 70 C, and the response time is about 1h.
(4) putting in tube furnace by the Graphene carrying nickel or cobalt in step 3, employing acetylene is carbon source, at high temperature, metal Being deposited by chemical gaseous phase under the effect of catalyst, between 550～750 DEG C, on Graphene, chemical gaseous phase deposits 25～50min, All of product is immersed in 0.6mol/L HCl solution 10h again to remove nickel cobalt catalyst.Finally by filtering and washing, Array carbon nano tube/Graphene is obtained after lyophilization 24h.
(5) array carbon nano tube/graphene composite material obtained in step 4 is mixed with chloroplatinic acid aqueous solution, Heat under magnetic agitation and solvent evaporation is formed slurry liquid, then put it in 60 DEG C of baking ovens and dry.After mortar grinds, by it Putting into and use Acetylene Reduction 1～3h in tube furnace between 150～300 DEG C, last nitrogen cools down, and obtains final catalyst platinum and carries array carbon Nanotube/Graphene.
By end product is carried out structural characterization, it was demonstrated that this product is with array carbon nano tube/Graphene as carrier, live Property metal component platinum is supported on CNT and graphenic surface, and particle diameter is 3～5nm.And the row that CNT is the most orderly It is listed on Graphene.
Beneficial effects of the present invention: the present invention utilizes Graphene-array carbon nano tube for carrier, and metal platinum is carried on stone It is prepared into platinum in ink alkene-carbon nanotube carrier and carries array carbon nano tube/graphen catalyst.Due to Graphene and CNT Conductive capability is strong, and electron mobility is big, and meanwhile, CNT is uprightly arranged in the carrier structure that on Graphene, this is special, makes Reaction has possessed unimpeded ion, electron channel, improves proton transport efficiency, increases the mass transfer speed of reactant and product Rate.Additionally, Graphene and CNT also provide bigger specific surface area for platinum in the present invention, decrease noble metal platinum Consumption.And make the combination having more oxygen-containing functional group to also enhance Pt catalyst granule and carbon carrier on Graphene by oneself, Make catalyst more stable.The present invention can be greatly improved the catalytic efficiency of catalyst and the utilization rate of noble metal, promotion is fired The fast development of material battery.
Accompanying drawing explanation
Fig. 1 is SEM spectrogram and the HRTEM figure of the array carbon nano tube/Graphene prepared；
Fig. 2 is that the platinum prepared carries array carbon nano tube/graphen catalyst, the XRD of nickel load array carbon nano tube/Graphene Spectrogram；
Fig. 3 is that 20% platinum prepared carries array carbon nano tube/graphen catalyst and commercialization JM-20%Pt/C catalyst Polarization curves of oxygen reduction figure.
Detailed description of the invention
Below by specific embodiment, the present invention will be further described, but is not meant to scope Limit.
Embodiment 1
(1) take crystalline flake graphite 3g, be separately added into concentrated sulphuric acid and strong phosphoric acid, pre-oxidize 24h；It is slowly added to fit under condition of ice bath Amount potassium permanganate 18g, temperature control is below 20 DEG C；Reacting by heating 12h at 50 DEG C afterwards, question response thing is down to room temperature, is fallen Enter in 400ml ice deionized water, add 10ml 30% hydrogen peroxide, first with 5% HCl centrifuge washing, then be centrifuged with deionized water Washing, obtains wet graphite oxide；
(2) taking the wet graphite oxide 100ml obtained in step one, put in 500ml deionized water, continual ultrasonic 3h makes It fully dissolves.Adding 10ml hydrazine hydrate, 90 DEG C of back flow reaction 6h after ultrasonic, cooling, by products therefrom filtering and washing freezing Being dried, products therefrom is Graphene (RGO)；
(3) the Graphene 0.1g obtained in step 2 is taken the most respectively with tin chloride solution and Palladous chloride. hydrochloric acid solution Carry out sensitization and activation, wherein stannous chloride solution be 100ml concentration be that (10% dilute hydrochloric acid is molten for solution newly configured for 10g/L Solve), palladium chloride solution be 100ml concentration be 10g/L solution (10% diluted hydrochloric acid dissolution).Dry through sucking filtration, then by chemistry Catalyst nickel or cobalt are loaded on Graphene by plating method, obtain carrying nickel or the Graphene of cobalt.Wherein the concentration of nickel nitrate/cobalt nitrate is 10g/L, the concentration of sodium hypophosphite is 10g/L, and the concentration of sodium citrate is 65g/L, and the concentration of ammonium chloride is 40g/L, plating Condition is pH=8, temperature 70 C, and the response time is about 1h.
(4) putting in tube furnace by the Graphene carrying nickel or cobalt in step 3, employing acetylene is carbon source, at high temperature, metal Being deposited by chemical gaseous phase under the effect of catalyst, between 600 DEG C, on Graphene, chemical gaseous phase deposits 35min, then will be all Product be immersed in 0.6mol/L HCl solution 10h to remove nickel cobalt catalyst.Finally by filtering and washing, lyophilization Array carbon nano tube/Graphene is obtained after 24h.
(5) array carbon nano tube/graphene composite material 80mg obtained by step 4 and 2655 μ l chloroplatinic acid second are taken Glycol solution (1g/50ml) mixes, and heats under magnetic stirring and solvent evaporation is formed slurry liquid, then put it into 60 DEG C of bakings Case is dried.After mortar grinds, putting it into and use Acetylene Reduction 2h in tube furnace between 150 DEG C, last nitrogen cools down, and obtains target Catalyst platinum carries array carbon nano tube/Graphene.
Embodiment 2
(1) take crystalline flake graphite 3g, be separately added into concentrated sulphuric acid and strong phosphoric acid 360ml and 40ml, pre-oxidize 24h；Condition of ice bath Under be slowly added to appropriate potassium permanganate 18g, temperature control is below 20 DEG C；Reacting by heating 12h at 50 DEG C afterwards, question response thing is down to Room temperature, is poured in 400ml ice deionized water, adds 10ml 30% hydrogen peroxide, first with 5% HCl centrifuge washing, then use Deionized water centrifuge washing, obtains wet graphite oxide；
(2) taking the wet graphite oxide 100ml obtained in step one, put in 500ml deionized water, continual ultrasonic 3h makes It fully dissolves.Adding 10ml hydrazine hydrate, 90 DEG C of back flow reaction 6h after ultrasonic, cooling, by products therefrom filtering and washing freezing Being dried, products therefrom is Graphene (RGO)；
(3) the Graphene 0.1g obtained in step 2 is taken the most respectively with tin chloride solution and Palladous chloride. hydrochloric acid solution Carry out sensitization and activation, wherein stannous chloride solution be 100ml concentration be that (10% dilute hydrochloric acid is molten for solution newly configured for 10g/L Solve), palladium chloride solution be 100ml concentration be 10g/L solution (10% diluted hydrochloric acid dissolution).Dry through sucking filtration, then by chemistry Catalyst nickel or cobalt are loaded on Graphene by plating method, obtain carrying nickel or the Graphene of cobalt.Wherein the concentration of nickel nitrate/cobalt nitrate is 10g/L, the concentration of sodium hypophosphite is 10g/L, and the concentration of sodium citrate is 65g/L, and the concentration of ammonium chloride is 40g/L, plating Condition is pH=8, temperature 70 C, and the response time is about 1h.
(4) putting in tube furnace by the Graphene carrying nickel or cobalt in step 3, employing acetylene is carbon source, at high temperature, metal Being deposited by chemical gaseous phase under the effect of catalyst, between 600 DEG C, on Graphene, chemical gaseous phase deposits 35min, then will be all Product be immersed in 0.6mol/L HCl solution 10h to remove nickel cobalt catalyst.Finally by filtering and washing, lyophilization Array carbon nano tube/Graphene is obtained after 24h.
(5) array carbon nano tube/graphene composite material 60mg obtained by step 4 and 5310 μ l chloroplatinic acid second are taken Glycol solution (1g/50ml) mixes, and heats under magnetic stirring and solvent evaporation is formed slurry liquid, then put it into 60 DEG C of bakings Case is dried.After mortar grinds, putting it into and use Acetylene Reduction 2h in tube furnace between 150 DEG C, last nitrogen cools down, and obtains target Catalyst platinum carries array carbon nano tube/Graphene.
Embodiment 3
(1) take crystalline flake graphite 3g, be separately added into concentrated sulphuric acid and strong phosphoric acid 360ml and 40ml, pre-oxidize 24h；Condition of ice bath Under be slowly added to appropriate potassium permanganate 18g, temperature control is below 20 DEG C；Reacting by heating 12h at 50 DEG C afterwards, question response thing is down to Room temperature, is poured in 400ml ice deionized water, adds 10ml 30% hydrogen peroxide, first with 5% HCl centrifuge washing, then use Deionized water centrifuge washing, obtains wet graphite oxide；
(2) taking the wet graphite oxide 100ml obtained in step one, put in 500ml deionized water, continual ultrasonic 3h makes It fully dissolves.Adding 10ml hydrazine hydrate, 90 DEG C of back flow reaction 6h after ultrasonic, cooling, by products therefrom filtering and washing freezing Being dried, products therefrom is Graphene (RGO)；
(3) the Graphene 0.1g obtained in step 2 is taken the most respectively with tin chloride solution and Palladous chloride. hydrochloric acid solution Carry out sensitization and activation, wherein stannous chloride solution be 100ml concentration be that (10% dilute hydrochloric acid is molten for solution newly configured for 10g/L Solve), palladium chloride solution be 100ml concentration be 10g/L solution (10% diluted hydrochloric acid dissolution).Dry through sucking filtration, then by chemistry Catalyst nickel or cobalt are loaded on Graphene by plating method, obtain carrying nickel or the Graphene of cobalt.(4) step 3 will carry nickel or the stone of cobalt Ink alkene put in tube furnace, employing acetylene is carbon source, high temperature, metallic catalyst effect under deposited by chemical gaseous phase, Between 600 DEG C, on Graphene, chemical gaseous phase deposits 35min, more all of product is immersed in 10h in 0.6mol/L HCl solution Remove nickel cobalt catalyst.Finally by filtering and washing, after lyophilization 24h, obtain array carbon nano tube/Graphene.
(5) array carbon nano tube/graphene composite material 70mg obtained by step 4 and 3983 μ l chloroplatinic acid second are taken Glycol solution (1g/50ml) mixes, and heats under magnetic stirring and solvent evaporation is formed slurry liquid, then put it into 60 DEG C of bakings Case is dried.After mortar grinds, putting it into and use Acetylene Reduction 2h in tube furnace between 150 DEG C, last nitrogen cools down, and obtains target Catalyst platinum carries array carbon nano tube/Graphene.
Embodiment 4
Fig. 1 is SEM spectrogram and the HRTEM figure of the array carbon nano tube/Graphene prepared.Can be seen that from SEM figure Learning the most orderly aligned growth of the CNT prepared of vapour deposition on the graphene-based end, pattern comparison rule is consistent, and And on Graphene arrangement tight, caliber is 15～20nm, and pipe range is 200～250nm.It can be seen that carbon from HRTEM figure The a lot of little granules of nanotube outer wall load, through the measurement of spacing of lattice, about 0.228nm, with the interplanar distance phase of platinum (111) Symbol, illustrates that the little granule being supported on carbon pipe outer wall is the metal platinum being reduced.
Fig. 2 is that the platinum prepared carries array carbon nano tube/graphen catalyst, the XRD of nickel load array carbon nano tube/Graphene Spectrogram.Wherein at the characteristic diffraction peak that peak is Graphene of 2 θ=26.22 °.Nickel carry Graphene XRD figure in 2 θ= 44.47 °, 51.8 °, the diffraction maximum of 76.37 ° is the characteristic peak of nickel.Platinum obtained by HCl processes after Supported Pt Nanoparticles carries array carbon In the XRD figure of nanotube/graphen catalyst, in 2 θ=44.47 °, 51.8 °, the peak of 76.37 ° disappears, and in 2 θ=39.8 °, Occurring in that diffraction maximum at 46.2 ° and 67.5 °, this is platinum (111), (200), the crystallographic plane diffraction peak of (220), illustrates that chloroplatinic acid is It is reduced and has obtained platinum grain, be prepared for target product platinum and carry array carbon nano tube/graphen catalyst.
Fig. 3 is that 20% platinum prepared carries array carbon nano tube/graphen catalyst and commercialization JM-20%Pt/C catalyst Polarization curves of oxygen reduction figure.This is at O2Saturated 0.1mol/L HClO4ORR polarization curve in electrolyte, rotating circular disk Electrode rotating speed 1600rpm-1.As can be seen from the figure 20% platinum carries array carbon nano tube/graphen catalyst than identical platinum carrying capacity Business Pt/C catalyst have higher initial reduction current potential, illustrate that it has higher oxygen reduction catalytic activity, this be because of Ohmic polarization and the concentration polarization of reaction is decreased, for entering smoothly of reaction for the structure that array carbon nano tube/Graphene is unique Row provides unimpeded ion channel and proton channel, thus improves platinum utilization.

Claims (4)

1. fuel cell array carbon nano tube/Graphene platinum catalyst, it is characterised in that described catalyst is by array Carbon nano tube/graphene makees carrier, and active component is platinum, and its mass percent consists of: array carbon nano tube/Graphene 60%-80%, platinum 20%-40%；
Described array carbon nano tube/Graphene, is prepared, as platinum by chemical gaseous phase deposition as carbon source by acetylene The carrier belonged to；
Described CNT is the most orderly being arranged on graphenic surface；
Described platinum is passed through the reducing loaded surface at array carbon nano tube/Graphene carrier of infusion process by chloroplatinic acid；
The preparation method of described catalyst comprises the steps:
(1) take crystalline flake graphite appropriate, add concentrated sulphuric acid and strong phosphoric acid, pre-oxidize 24 h；Appropriate height it is slowly added under condition of ice bath Potassium manganate, temperature control is below 20 DEG C；Reacting by heating 12 h at 50 DEG C afterwards, question response thing is down to room temperature, is poured into 400 In ~ 500 ml ice deionized waters, add 10 ~ 15 ml 30% hydrogen peroxide, first with 5% HCl centrifuge washing, then with deionized water from The heart washs, and obtains wet graphite oxide；
(2) putting in 400 ~ 500 ml deionized waters by the wet graphite oxide obtained in step one, continual ultrasonic 3 ~ 4 h makes it Fully dissolve；Add 10 ~ 15 ml hydrazine hydrates, 90 DEG C of back flow reaction 6 h after ultrasonic, cool down, by products therefrom filtering and washing also Lyophilization, products therefrom is Graphene；
(3) Graphene obtained in step 2 is carried out sensitization with tin chloride solution and Palladous chloride. hydrochloric acid solution the most respectively And activation, dry through sucking filtration, then by electroless plating method, catalyst nickel or cobalt are loaded on Graphene, obtain carrying nickel or the stone of cobalt Ink alkene；
(4) putting in tube furnace by the Graphene carrying nickel or cobalt in step 3, employing acetylene is carbon source, at high temperature, metal catalytic Being deposited by chemical gaseous phase under the effect of agent, between 550～750 DEG C, on Graphene, chemical gaseous phase deposits 25～50 min, then All of product is immersed in 0.6 mol/L HCl solution 10 h to remove nickel cobalt catalyst；Finally by filtering and washing, Array carbon nano tube/Graphene is obtained after lyophilization 24 h；
(5) array carbon nano tube/graphene composite material obtained in step 4 is mixed with chloroplatinic acid aqueous solution, at magnetic force Solvent evaporation is formed slurry liquid by the lower heating of stirring, then puts it in 60 DEG C of baking ovens and dries；After mortar grinds, put Entering and use Acetylene Reduction 1～3 h in tube furnace between 150～300 DEG C, last nitrogen cools down, and obtains final catalyst platinum and carries array carbon Nanotube/Graphene.
2. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as claimed in claim 1, its feature exists In, described in step (1), the volume ratio of concentrated sulphuric acid and strong phosphoric acid is 9:1.
3. a kind of fuel cell array carbon nano tube/Graphene platinum catalyst as claimed in claim 1, its feature exists In, described in step (3), the condition of electroless plating method is as follows: the concentration of nickel nitrate/cobalt nitrate is 7～13 g/L, sodium hypophosphite Concentration be 7～13 g/L, the concentration of sodium citrate is 60～70 g/L, and the concentration of ammonium chloride is 37～43 g/L, plating bar Part is pH=6～9, temperature 70 DEG C, and the response time is 1 h.
4. a preparation method for fuel cell array carbon nano tube/Graphene platinum catalyst, comprises the steps:
(1) taking crystalline flake graphite appropriate, the volume ratio adding concentrated sulphuric acid and strong phosphoric acid, concentrated sulphuric acid and strong phosphoric acid is 9:1, pre-oxidizes 24 h；Being slowly added to appropriate potassium permanganate under condition of ice bath, temperature control is below 20 DEG C；Reacting by heating 12 h at 50 DEG C, treats afterwards Reactant is down to room temperature, is poured in 400 ~ 500 ml ice deionized waters, adds 10 ~ 15 ml 30% hydrogen peroxide, first with 5% HCl centrifuge washing, then use deionized water centrifuge washing, obtain wet graphite oxide；
(2) putting in 400 ~ 500 ml deionized waters by the wet graphite oxide obtained in step one, continual ultrasonic 3 ~ 4 h makes it Fully dissolve；Add 10 ~ 15 ml hydrazine hydrates, 90 DEG C of back flow reaction 6 h after ultrasonic, cool down, by products therefrom filtering and washing also Lyophilization, products therefrom is Graphene；
(3) Graphene obtained in step 2 is carried out sensitization with tin chloride solution and Palladous chloride. hydrochloric acid solution the most respectively And activation, dry through sucking filtration, then by electroless plating method, catalyst nickel or cobalt are loaded on Graphene, obtain carrying nickel or the stone of cobalt Ink alkene；Wherein the concentration of nickel nitrate/cobalt nitrate is 7～13 g/L, and the concentration of sodium hypophosphite is 7～13 g/L, sodium citrate Concentration be 60～70 g/L, the concentration of ammonium chloride is 37～43 g/L, and plating conditions is pH=6～9, temperature 70 DEG C, reaction Time is 1 h；
(4) putting in tube furnace by the Graphene carrying nickel or cobalt in step 3, employing acetylene is carbon source, at high temperature, metal catalytic Being deposited by chemical gaseous phase under the effect of agent, between 550～750 DEG C, on Graphene, chemical gaseous phase deposits 25～50 min, then All of product is immersed in 0.6 mol/L HCl solution 10 h to remove nickel cobalt catalyst；Finally by filtering and washing, Array carbon nano tube/Graphene is obtained after lyophilization 24 h；
(5) array carbon nano tube/graphene composite material obtained in step 4 is mixed with chloroplatinic acid aqueous solution, at magnetic force Solvent evaporation is formed slurry liquid by the lower heating of stirring, then puts it in 60 DEG C of baking ovens and dries；After mortar grinds, put Entering and use Acetylene Reduction 1～3 h in tube furnace between 150～300 DEG C, last nitrogen cools down, and obtains final catalyst platinum and carries array carbon Nanotube/Graphene.
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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
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