CN105186009A - Fuel-cell catalyst with nano-graphite carbon rivet structure and preparation method of fuel-cell catalyst - Google Patents
Fuel-cell catalyst with nano-graphite carbon rivet structure and preparation method of fuel-cell catalyst Download PDFInfo
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- CN105186009A CN105186009A CN201510566754.8A CN201510566754A CN105186009A CN 105186009 A CN105186009 A CN 105186009A CN 201510566754 A CN201510566754 A CN 201510566754A CN 105186009 A CN105186009 A CN 105186009A
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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
- H01M4/88—Processes of manufacture
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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
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M8/00—Fuel cells; Manufacture thereof
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- 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 relates to a fuel-cell catalyst with a nano-graphite carbon rivet structure and a preparation method of the fuel-cell catalyst. Nano-graphite carbon with a graphite or graphite-like structure is introduced into a carbon carrier-loaded metal active component catalyst to form the fuel-cell catalyst with the nano-graphite carbon rivet structure; and the nano-graphite carbon rivet structure is the structure which is formed by covering the surfaces of metal particles with the nano-graphite carbon with the graphite or graphite-like structure and combining with a metal particle-loaded carbon carrier. Migrating agglomeration of catalyst particles on the carrier surface can be effectively suppressed; the service life of the catalyst is prolonged; and meanwhile, small particles which are formed by dissolving and redepositing the catalyst particles directly enter the solution in general in an electrochemical environment. The catalyst has the graphite carbon rivet structure, so that redeposited small particles can be deposited on a graphite carbon layer for further catalytic reaction; the redeposited particles are small in particle size and large in specific surface area; and the fuel-cell catalyst has more excellent catalytic activity than an ordinary carbon-loaded metal catalyst.
Description
Technical field
The present invention relates to a kind of novel high performance fuel cell Catalysts and its preparation method, belong to field of fuel cell technology.
Background technology
Fuel cell, due to the feature such as its high efficiency, no pollution, startup be fast, is considered to very potential a kind of electrical power storage and reforming unit in future.Carbon-supported nano size Pt or Pt alloy catalyst are widely used in fuel cell negative and positive the two poles of the earth.So far, such as carbon black, carbon nano-tube, carbon nanocoils, the material with carbon elements such as Graphene are still widely used as fuel-cell catalyst carrier due to large, the high conductivity of its specific area, excellent pore structure.But catalyst activity and stability hinder the commercialization process of fuel cell greatly.Early stage research display fuel cell, after specified conditions run a period of time, declines because catalyst activity and stability reduce performance thereupon.
In general, Pt catalyst has four kinds of main mechanism of degradations: 1) Pt grain dissolution precipitates again; 2) Pt nano particle is grown up in carrier surface migration; 3) the Pt particle agglomeration that support corrosion causes comes off; 4) pollutant causes the deterioration of Pt catalyst particle surface.It is the principal element affecting its activity that catalyst support corrosion and noble metal catalyst are reunited.Wen Zhenhai seminar of Tsing-Hua University (Adv.Mater., 2008,20,743.) has synthesized a kind of nucleocapsid structure Pt/C:MC catalyst being embedded in mesoporous carbon, due to the nanostructure of its uniqueness, shows excellent catalytic activity and high stability.Takenaka etc. (J.Phys.Chem.C, 2007,111,15133) have synthesized a kind of SiO
2/ Pt/CNT catalyst, has the stability more excellent than Pt/CNT, but due to SiO
2the performance of poorly conductive thus this catalyst is lower.The people such as wood scholar's spring have done a large amount of research work to catalyst carrier, as sulfonate functional carbon nano tube carries Pt catalyst (Carbon, 2011, 49, 82-88), material with carbon element (J.Mater.Chem. is substituted with more stable carriers such as carbide, 2012, 22, 9155), use non-precious metal catalyst or Pt alloy catalyst, with (Carbon such as macromolecule modified Pt particles, 2014, 66, 312-319), porous graphene carries Pt catalyst (ElectrochimicaActa, 2014, 132, 356 – 363), conductive nano pottery wedge and Graphene compound carry Pt catalyst (SCIENTIFICREPORTS, 2014, 4, 3968), these catalyst all show the electrocatalysis characteristic better than common commercial catalyst.
Reunite to reduce catalyst granules migration and come off, utilize the dissolving of catalyst granules in electrochemical environment PRECIPITATION MECHANISM more dexterously simultaneously, the present inventor successfully introduces nano graphite carbon with chemical gaseous phase depositing process between nano-catalyst particles and carrier granular, thus form a kind of catalyst with nano graphite carbon rivet arrangement, make to combine between catalyst granules and body carriers more firm, improve the electrochemical stability of catalyst; Simultaneously, in electrochemical environment especially Acceleration study time generally can enter in electrolyte because catalyst dissolution precipitates again, and the catalyst with this rivet arrangement can make the catalyst of dissolving redeposited at nano-graphite carbon surface, redeposited catalyst granules particle diameter is less, avtive spot increases, this greatly increases the utilance of catalyst, adds the electro-chemical activity of catalyst.
At present, there is not yet the relevant report with chemical vapour deposition technique synthesis with the high performance fuel cell catalyst of nano graphite carbon rivet arrangement.
Summary of the invention
The present invention aims to provide a kind ofly has fuel-cell catalyst of nano graphite carbon rivet arrangement and preparation method thereof, and the existence of this rivet arrangement can suppress catalyst granules to be reunited in the migration of carrier surface effectively, thus improves the life-span of catalyst; Simultaneously, in electrochemical environment, catalyst granules dissolves the granule deposited again and usually directly enters in solution, and catalyst of the present invention is owing to having graphitic carbon rivet arrangement, thus these granules deposited again and then can be deposited on graphite carbon-coating and continue catalytic electrochemical reaction, and due to the granule deposited again, particle diameter is little, specific area is large, compares general carbon-supported metal catalyst and has more excellent catalytic activity.
For achieving the above object, the technical solution used in the present invention:
There is the fuel-cell catalyst of nano graphite carbon rivet arrangement, it is characterized in that: it is the nano graphite carbon introducing graphite or graphite-like structure in carbon carrier carried metal active constituent catalyst, form the fuel-cell catalyst with nano graphite carbon rivet arrangement, described nano graphite carbon rivet arrangement refers to that the nano graphite carbon with graphite or graphite-like structure covers surface of metal particles and the structure formed that combines with the body carbon carrier of carried metal particle.
By such scheme, described nano graphite carbon comprises Graphene, carbon nano-tube (comprising Single Walled Carbon Nanotube and multi-walled carbon nano-tubes), carbon nano-fiber, nano-graphite ball, nano-graphite rod, one or more in fullerene.The main component of described nano-graphite carbon structure is sp
2hydridization carbon.Its kind determines by vapour deposition temperature during synthesis, and size determines primarily of the kind and quantity passing into gas phase carbon source.
By such scheme, in described nano graphite carbon rivet arrangement, carbon is that part covers or covers completely in surface of metal particles.
By such scheme, described nano graphite carbon is less than or equal to 10nm usually at the thickness of catalyst surface, is usually no more than 5nm.
By such scheme; described nano graphite carbon utilizes chemical vapour deposition technique; at high temperature in carbon carrier carried metal seed activity component catalyst presoma, introduce gas phase carbon source; also be rearranged into the nano graphite carbon of various structure at metal surface catalytic pyrolysis carbon further, prepare the fuel-cell catalyst with nano graphite carbon rivet arrangement.
By such scheme, the metallic catalyst mentioned in technical solution of the present invention comprises fuel cell noble metal catalysts and alloy thereof and non-precious metal catalyst, specifically comprise a kind of simple substance in Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, Mo, or consisting of binary and multicomponent alloy.
By such scheme, the high temperature mentioned in technical solution of the present invention is 600-1000 DEG C, typically no more than 800 DEG C.
By such scheme, the gaseous carbon sources mentioned in technical solution of the present invention comprises acetylene, methane, ethane, propine, propylene, propane, 1,3-butadiene, 1-butylene, ethene, butine.The amount used is 50mg at catalyst precursor usually, and flow velocity is no more than 15ml/min, and when being generally 5-15ml/min, duration of ventilation is 10s-5min, is generally no more than 3min, by that analogy.
The preparation method with the fuel-cell catalyst of nano graphite carbon rivet arrangement mentioned in technical solution of the present invention specifically comprises the following steps:
1) take a certain amount of carbon-supported metal active constituent catalyst precursor samples, be placed in little porcelain boat, vibration makes catalyst precursor be laid in equably in porcelain boat;
2) porcelain boat that carbon-supported metal active constituent catalyst precursor is housed is put into the centre of quartz ampoule on tube furnace, pass into a period of time inert gas and get rid of quartzy air in tube, or be evacuated to below 0.1Pa in vacuum tube furnace;
3) under an inert atmosphere, be warming up to 80 DEG C-120 DEG C, be usually no more than 100 DEG C, insulation, temperature retention time is generally no more than 3h, the moisture in removing catalyst;
4) continue to be warming up to 600-1000 DEG C, when temperature reaches set point, pass into carbon-source gas carry out chemical vapour deposition reaction, afterwards, close carbon-source gas, pass into inert gas, be incubated 15min-2h at this temperature, be generally not less than 30min;
5) continue to pass into inert gas, after tube furnace temperature is down to room temperature, take out sample, use.
By such scheme, described inert gas is high pure nitrogen or high-purity argon gas.
By such scheme, through electrochemical activation process when the described fuel-cell catalyst with nano graphite carbon rivet arrangement uses, use after the part graphite carbon-coating of catalyst surface is removed.By this catalyst through electrochemical activation process, the part graphite carbon-coating of catalyst surface is removed, more avtive spot in catalyst can be made to come out, catalyst after process has than the better electro catalytic activity of process procatalyst and stability, can be used for alternative existing commercial catalysts.
Graphitic carbon rivet catalyst application of the present invention, in fuel-cell catalyst, has very strong reference to the design of other technologies field durability catalyst simultaneously.
Compared with background technology, the present invention has following outstanding advantage:
(1) catalyst related in the present invention has unique nano graphite carbon rivet arrangement, not only can increase site when catalyst granules deposits again, and catalyst granules can be greatly reduced in carrier surface migration reunion, and the degree of graphitization of carrier is higher compared to commercial catalysts, thus catalyst has good stability.
(2) the nano graphite carbon rivet fuel-cell catalyst related in the present invention has higher electro-chemical activity and more excellent electrochemical stability, and its preparation method is simple, and cost is low, can synthesize in batches.
(3) CVD (Chemical Vapor Deposition) method of the present invention uses gaseous carbon sources range of choice wide, comprises acetylene, methane, ethane, propine, propylene, propane, 1,3-butadiene, 1-butylene, ethene, butine.
Accompanying drawing illustrates:
Fig. 1 is the TEM figure with nano graphite carbon rivet fuel-cell catalyst: the catalyst of (a) non-activation processing; B () accelerates the catalyst after 2500 circles (electrochemical activation process) through electrochemistry.
Fig. 2 is the Raman spectrogram with nano graphite carbon rivet fuel-cell catalyst.
Fig. 3 is the electrochemical surface area variation diagram of the business Pt/C catalyst with nano graphite carbon rivet fuel-cell catalyst and identical carrying capacity.
Embodiment
Below by embodiment in detail summary of the invention of the present invention is described in detail.
Embodiment 1
Take 50mg, 37%Pt/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 80 DEG C with 5 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 700 DEG C with 10 DEG C/min, after temperature constant, close high-purity argon gas, pass into C with the flow velocity of 15ml/min
2h
2gas, time 10s;
After having reacted, then slowly closing acetylene air valve passes into high-purity argon gas, and insulation 30min, until temperature is down to room temperature.
Catalyst electro-chemical activity and stability test method:
1) ink medium is configured: accurately take testing sample 0.003 ± 0.0005g with electronic balance and be placed in the little centrifuge tube of 3ml, add 100ul deionized water, 1000ul isopropyl alcohol, 20ul, 5%nafion solution, more than ultrasonic disperse 30min, to form uniform " ink " solution;
2) with deerskin, intact glassy carbon electrode is polished flat, there to be reflective just looking to be advisable less than any minute scratch marks/pit etc. under low-light, then to use alcohol more than ultrasonic cleaning 10min, and be placed in less than 40 DEG C natural dryings;
3) get 5ul " ink " solution with 10ul trace transfering device, slowly drip equably on glassy carbon electrode surface, be placed in constant humidity environment slowly dry at 40 DEG C, treat its bone dry, then repeat to drip once, to form solid homogenous membrane electrode.
Cyclic voltammetric (CV) and accelerated test step as follows:
1) be fixed on rotating disk electrode (r.d.e) testboard by dried glassy carbon electrode, and be deep into below electrolytic cell liquid level 1/3rd place, electrolyte is the HClO of 0.1mol/L
4solution, connects electrochemical workstation;
2) at logical high-purity argon gas in electrolyte after 30min, starting in sweep speed is 100mV/s, and activation scanning 40 is enclosed with clearing electrode surface impurity and adsorbate;
3) be 50mV/s in sweep speed, test voltage scope is-0.3V-0.9V, and test 3 circle, obtains CV curve;
4) test voltage scope is adjusted to 0.3V-0.9V, sweep speed is adjusted to 100mV/s, and accelerated scan 100 is enclosed, and then repeats step 3 and obtains a CV curve;
5) step 4 is repeated, accelerated scan 100 is enclosed again, obtain the CV curve after acceleration 200 circle, and logical high-purity argon gas 30min disturbs to get rid of dissolved oxygen after often accelerating 1000 circles, often accelerate 500 circles after 1000 circles and survey a CV curve, accelerate 1000 circle surveys CV curve after 3000 circles, so both can obtain the CV curve after acceleration 100/200/400/600/800/1000/1500/2000/2500/3000/4000.
Data processing:
Choose the second circle CV curve, integration is carried out to hydrogen desorption peak, then use formulae discovery electrochemical surface area below: ECA=100 × S/ (C × v × M)
ECA in formula---electrochemical surface area, unit is m
2/ g;
S---the integral area at hydrogen desorption peak, unit is A*V;
C---smooth; Pt adsorption hydroxide absorption electricity constant, 0.21mC/cm
2;
V---sweep speed, unit is mV/s;
M---the quality of Pt on electrode, unit is g.
Take electrochemical surface area as ordinate, the accelerated scan number of turns is ordinate, and electrochemical stability is evaluated in mapping.
Fig. 1 (a) is the high power TEM figure of the catalyst prepared by the present invention, wherein metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.35nm, roughly the same with graphite material spacing of lattice, thickness is about 3nm, and metal catalyst particles particle diameter is no more than 5nm;
Fig. 2 is the Raman spectrogram of this catalyst, from about 2720cm
-1the 2D peak at place, can find out that this is the characteristic peak of typical graphite, can think nano-graphite, and ID/IG value be 1.05, illustrates that the nano-graphite generated is containing more defect.
Fig. 3 is this catalyst and Pt/C catalyst activity and stability comparison diagram.Relative to standard hydrogen electrode, this catalyst has the highest electrochemical surface area, accelerates 2500 circles, is worth for 151m
2/ g, catalyst after the present invention encloses acceleration 2500 has carried out TEM sign, see Fig. 1 (b), itself and Fig. 1 (a) contrast and can find out: catalyst of the present invention is after electrochemical activation process, the part graphite carbon-coating of catalyst surface is removed, the thickness of surface graphite carbon-coating is close to 0nm, and this makes more avtive spot in catalyst expose out, and the catalyst therefore after process has and has better electro catalytic activity and stability than before process.Accelerating 4000 circle its value rear is 100m
2/ g, remains 66%; The electrochemical surface area of Pt/C catalyst is 108m
2/ g is 58m after accelerating 1500 circles
2/ g only remains 54%.Illustrate thus: catalyst of the present invention has excellent electro-chemical activity and stability.
Embodiment 2
Take 50mg, 37%Ru/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 100 DEG C with 5 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 750 DEG C with 10 DEG C/min, after temperature constant, close high pure nitrogen and pass into methane gas with 8ml/min, time 30s;
After having reacted, then slowly closing methane air valve passes into high pure nitrogen, and insulation 45min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1 method of testing.
Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.34nm, and roughly the same with grapheme material spacing of lattice, thickness is about 1.7nm, and the Graphene number of plies the chances are 4-5 layer, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 112m of acceleration 2000 when enclosing
2/ g is 90m after accelerating 4000 circles
2/ g, still remains 79% of peak; The electrochemical surface area of Ru/C catalyst is 91m
2/ g is 56m after accelerating 2000 circles
2/ g only remains 62%.
Embodiment 3
Take 50mg, 37%Pd/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 120 DEG C with 8 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 600 DEG C with 10 DEG C/min, after temperature constant, close high-purity argon gas and pass into ethane gas with 10ml/min flow velocity, time 20s;
After having reacted, then slowly closing ethane air valve passes into high-purity argon gas, and insulation 1h, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1 method of testing, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.342nm, and thickness is about 1.7nm, and carbon-coating is nano-graphite rod, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 105m of acceleration 2000 when enclosing
2/ g is 88m after accelerating 4000 circles
2/ g, still remains 83% of peak, and by comparison, the electrochemical surface area of Pd/C catalyst is 96m
2/ g is 58m after accelerating 2000 circles
2/ g only remains 60%.
Embodiment 4
Take 50mg, 37%Rh/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 90 DEG C with 10 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 800 DEG C with 10 DEG C/min, after temperature constant, close high pure nitrogen and pass into propane gas with 5ml/min flow velocity, time 2min;
After having reacted, then slowly closing propane air valve passes into high pure nitrogen, and insulation 1h, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.338nm, and thickness is about 2.4nm, and carbon-coating is nano graphite carbon ball, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 118m of acceleration 1500 when enclosing
2/ g is 94m after accelerating 4000 circles
2/ g, still remains 79% of peak, and by comparison, the electrochemical surface area of Rh/C catalyst is 93m
2/ g is 55m after accelerating 2500 circles
2/ g only remains 59%.
Embodiment 5
Take 50mg, 37%PtIr/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 90 DEG C with 8 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 850 DEG C with 10 DEG C/min, after temperature constant, close high-purity argon gas and pass into propylene gas with 7ml//min flow velocity, time 2min;
After having reacted, then slowly closing propylene air valve passes into high-purity argon gas, and insulation 50min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.339nm, and roughly the same with grapheme material spacing of lattice, thickness is about 2nm, and the Graphene number of plies the chances are 5-6 layer, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 121m of acceleration 2000 when enclosing
2/ g is 96m after accelerating 4000 circles
2/ g, still remains 79% of peak, and by comparison, the electrochemical surface area of PtIr/C catalyst is 95m
2/ g is 58m after accelerating 2000 circles
2/ g only remains 61%.
Embodiment 6
Take 50mg, 37%PtOs/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 100 DEG C with 15 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 900 DEG C with 10 DEG C/min, after temperature constant, close high pure nitrogen and pass into 1-butene gas with 12ml/min flow velocity, time 60s;
After having reacted, then slowly closing 1-butylene air valve passes into high pure nitrogen, and insulation 1h, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.343nm, and thickness is about 2nm, and from pattern, carbon-coating is carbon nano-fiber, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 135m of acceleration 2500 when enclosing
2/ g is 106m after accelerating 4000 circles
2/ g, still remain 78% of peak, and by comparison, the electrochemical surface area of PtOs/C catalyst is 96m
2/ g is 52m after accelerating 1500 circles
2/ g only remains 54%.
Embodiment 7
Take 50mg, 37%PtFe/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 120 DEG C with 12 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 950 DEG C with 15 DEG C/min, after temperature constant, close high-purity argon gas and pass into propyne gas with 6ml/min flow velocity, time 20s;
After having reacted, then slowly closing propine air valve passes into high-purity argon gas, and insulation 40min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.336nm, and thickness is about 5nm, and carbon-coating is nano graphite carbon ball and Graphene compound, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 143m of acceleration 1500 when enclosing
2/ g is 113m after accelerating 4000 circles
2/ g, still remain 79% of peak, and by comparison, the electrochemical surface area of PtFe/C catalyst is 105m
2/ g is 51m after accelerating 2500 circles
2/ g only remains 48%.
Embodiment 8
Take 50mg, 37%Cr/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 100 DEG C with 10 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 1000 DEG C with 15 DEG C/min, after temperature constant, close high pure nitrogen and pass into butine gas with 15ml/min flow velocity, time 10s;
After having reacted, then slowly closing butine air valve passes into high pure nitrogen, and insulation 30min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.34nm, and thickness is about 1.2nm, and carbon-coating is Single Walled Carbon Nanotube, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 95m of acceleration 2500 when enclosing
2/ g is 78m after accelerating 4000 circles
2/ g, still remain 83% of peak, and by comparison, the electrochemical surface area of Cr/C catalyst is 85m
2/ g is 47m after accelerating 1500 circles
2/ g only remains 55%.
Embodiment 9
Take 50mg, 37%PtAuNi/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 80 DEG C with 5 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 800 DEG C with 10 DEG C/min, after temperature constant, close high pure nitrogen and pass into ethane gas with 10ml/min flow velocity, time 30s;
After having reacted, then slowly closing ethane air valve passes into high pure nitrogen, and insulation 30min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.34nm, and roughly the same with grapheme material spacing of lattice, thickness is about 1.4nm, and the Graphene number of plies the chances are 3-4 layer, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 133m of acceleration 2000 when enclosing
2/ g is 112m after accelerating 4000 circles
2/ g, still remain 84% of peak, and by comparison, the electrochemical surface area of PtAuNi/C catalyst is 100m
2/ g is 53m after accelerating 2000 circles
2/ g only remains 53%.
Embodiment 10
Take 50mg, 37%PtCo/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 120 DEG C with 8 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 700 DEG C with 10 DEG C/min, after temperature constant, close high-purity argon gas and pass into butane gas with 8ml/min flow velocity, time 50s;
After having reacted, then slowly closing butane air valve passes into high-purity argon gas, and insulation 50min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.334nm, and thickness is about 10nm, and carbon-coating is nano graphite carbon ball and carbon nano-fiber compound, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 114m of acceleration 2000 when enclosing
2/ g is 93m after accelerating 4000 circles
2/ g, still remain 82% of peak, and by comparison, the electrochemical surface area of PtCo/C catalyst is 94m
2/ g is 55m after accelerating 2000 circles
2/ g only remains 58%.。
Embodiment 11
Take 50mg, 37%PtMn/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 90 DEG C with 7 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 900 DEG C with 15 DEG C/min, after temperature constant, close high-purity argon gas and pass into propylene gas with 7ml/min flow velocity, time 3min;
After having reacted, then slowly closing propylene air valve passes into high-purity argon gas, and insulation 1h, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.341nm, and thickness is about 1.5nm, and carbon-coating is Single Walled Carbon Nanotube, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 115m of acceleration 2500 when enclosing
2/ g is 91m after accelerating 4000 circles
2/ g, still remain 79.44% of peak, and by comparison, the electrochemical surface area of PtMn/C catalyst is 96m
2/ g is 51m after accelerating 1500 circles
2/ g only remains 53%.
Embodiment 12
Take 50mg, 37%PtCu/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 90 DEG C with 5 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 700 DEG C with 10 DEG C/min, after temperature constant, close high pure nitrogen and pass into 1-butene gas with 10ml/min flow velocity, time 2min;
After having reacted, then slowly closing 1-butylene air valve passes into high pure nitrogen, and insulation 50min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.332nm, and thickness is about 2.6nm, and carbon-coating is nano graphite carbon ball, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 102.7m of acceleration 2500 when enclosing
2/ g is 94m after accelerating 4000 circles
2/ g, still remain 92% of peak, and by comparison, the electrochemical surface area of PtCu/C catalyst is 88m
2/ g is 49m after accelerating 1500 circles
2/ g only remains 55%.
Embodiment 13
Take 50mg, 37%PtTi/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 90 DEG C with 5 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 800 DEG C with 10 DEG C/min, after temperature constant, close high-purity argon gas and pass into 1,3-butadiene gas with 11ml/min flow velocity, time 3min;
After having reacted, then slowly closing 1,3-butadiene air valve passes into high-purity argon gas, and insulation 1h, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.342nm, and thickness is about 2.7nm, and from pattern, carbon-coating is nano-graphite rod, and metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 118m of acceleration 2000 when enclosing
2/ g is 93m after accelerating 4000 circles
2/ g, still remain 79% of peak, and by comparison, the electrochemical surface area of PtTi/C catalyst is 96m
2/ g is 60m after accelerating 2000 circles
2/ g only remains 62%.
Embodiment 14
Take 50mg, 37%PtSn/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 100 DEG C with 5 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 900 DEG C with 10 DEG C/min, after temperature constant, close high-purity argon gas and pass into propyne gas with 15ml/min flow velocity, time 50s;
After having reacted, then slowly closing propine air valve passes into high-purity argon gas, and insulation 45min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.335nm, and roughly the same with graphite material spacing of lattice, thickness is about 3.4nm, and be graphite nano plate, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 110m of acceleration 1500 when enclosing
2/ g is 95m after accelerating 4000 circles
2/ g, still remain 86% of peak, and by comparison, the electrochemical surface area of PtSn/C catalyst is 97m
2/ g is 49m after accelerating 2500 circles
2/ g only remains 50%.
Embodiment 15
Take 50mg, 37%V/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 100 DEG C with 10 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 1000 DEG C with 20 DEG C/min, after temperature constant, close high pure nitrogen and pass into propyne gas with 15ml/min flow velocity, time 1min;
After having reacted, then slowly closing propine air valve passes into high pure nitrogen, and insulation 50min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.337nm, and roughly the same with graphite material spacing of lattice, thickness is about 2.8nm, and be graphite nano plate, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 119m of acceleration 2000 when enclosing
2/ g is 94m after accelerating 4000 circles
2/ g, still remain 79% of peak, and by comparison, the electrochemical surface area of V/C catalyst is 91m
2/ g is 56m after accelerating 2000 circles
2/ g only remains 62%.
Embodiment 16
Take 50mg, 37%Ga/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 80 DEG C with 5 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 750 DEG C with 10 DEG C/min, after temperature constant, close high-purity argon gas and pass into ethylene gas with 12ml/min flow velocity, time 1min;
After having reacted, then slowly closing ethene air valve passes into high-purity argon gas, and insulation 45min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.334nm, and roughly the same with graphite material spacing of lattice, thickness is about 2.3nm, and be graphite nano plate, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 120m of acceleration 2000 when enclosing
2/ g is 92m after accelerating 4000 circles
2/ g, still remain 76% of peak, and by comparison, the electrochemical surface area of Ga/C catalyst is 93m
2/ g is 55m after accelerating 2000 circles
2/ g only remains 590%.
Embodiment 17
Take 50mg, 37%Mo/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 90 DEG C with 10 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 900 DEG C with 15 DEG C/min, after temperature constant, close high-purity argon gas and pass into butine gas with 15ml/min flow velocity, time 40s;
After having reacted, then slowly closing butine air valve passes into high-purity argon gas, and insulation 40min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.34nm, and roughly the same with grapheme material spacing of lattice, thickness is about 34nm, and the Graphene number of plies the chances are 7-8 layer, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 106m of acceleration 2500 when enclosing
2/ g is 93m after accelerating 4000 circles
2/ g, still remain 87% of peak, and by comparison, the electrochemical surface area of Mo/C catalyst is 90m
2/ g is 52m after accelerating 1500 circles
2/ g only remains 58%.
Embodiment 18
Take 50mg, 37%PtMn/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High pure nitrogen 1h is passed into, with the air in remover under room temperature;
In High Purity Nitrogen atmosphere, be warming up to 90 DEG C with 9 DEG C/min, insulation 1h, the moisture in removing sample;
Be warming up to 950 DEG C with 20 DEG C/min, after temperature constant, close high pure nitrogen and pass into propane gas with 13ml/min flow velocity, time 30s;
After having reacted, then slowly closing propane air valve passes into high pure nitrogen, and insulation 1h, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.34nm, and roughly the same with grapheme material spacing of lattice, thickness is about 2nm, and the Graphene number of plies the chances are 6-7 layer, metal catalyst particles particle diameter is no more than 5nm.
The most high electrochemical activity area of this catalyst is the 119m of acceleration 1500 when enclosing
2/ g is 91m after accelerating 4000 circles
2/ g, still remain 76% of peak, and by comparison, the electrochemical surface area of PtMn/C catalyst is 92m
2/ g is 52m after accelerating 2500 circles
2/ g only remains 56%.
Embodiment 19
Take 50mg, 37%Fe/C catalyst, in little porcelain boat, shakes little porcelain boat, makes sample be laid in little porcelain boat uniformly, the little porcelain boat that sample is housed is put into quartz tube type resistance furnace center position lentamente;
Use silica gel sealing experimental provision, check that air-tightness is guaranteed well;
High-purity argon gas 1h is passed into, with the air in remover under room temperature;
In high-purity argon atmosphere, be warming up to 90 DEG C with 5 DEG C/min, insulation 2h, the moisture in removing sample;
Be warming up to 900 DEG C with 15 DEG C/min, after temperature constant, close high-purity argon gas and pass into 1,3-butadiene gas with 15ml/min flow velocity, time 1min;
After having reacted, then slowly closing acetylene air valve passes into high-purity argon gas, and insulation 50min, until temperature is down to room temperature.
In the present embodiment catalyst electro-chemical activity and stability test identical with embodiment 1, unlike the catalyst that used catalyst is prepared for the present embodiment.Metal catalyst particles is covered by carbon-coating, and spacing of lattice is 0.343nm, and thickness is about 3.2nm.Carbon-coating is multi-walled carbon nano-tubes, and metal catalyst particles particle diameter is no more than 5nm.The most high electrochemical activity area of this catalyst is the 101m of acceleration 2000 when enclosing
2/ g is 91m after accelerating 4000 circles
2/ g, still remain 89% of peak, and by comparison, the electrochemical surface area of Fe/C catalyst is 93m
2/ g is 54m after accelerating 2000 circles
2/ g only remains 58%.
Claims (10)
1. there is the fuel-cell catalyst of nano graphite carbon rivet arrangement, it is characterized in that: it is the nano graphite carbon introducing graphite or graphite-like structure in carbon carrier carried metal active constituent catalyst, form the fuel-cell catalyst with nano graphite carbon rivet arrangement, described nano graphite carbon rivet arrangement refers to that the nano graphite carbon with graphite or graphite-like structure covers surface of metal particles and the structure formed that combines with the body carbon carrier of carried metal particle.
2. the fuel-cell catalyst with nano graphite carbon rivet arrangement according to claim 1, is characterized in that: described nano graphite carbon comprises Graphene, carbon nano-tube, carbon nano-fiber, nano-graphite ball, nano-graphite rod, one or more in fullerene.
3. the fuel-cell catalyst with nano graphite carbon rivet arrangement according to claim 1, is characterized in that: in described nano graphite carbon rivet arrangement, carbon is that part covers or covers completely in surface of metal particles.
4. the fuel-cell catalyst with nano graphite carbon rivet arrangement according to claim 1, is characterized in that: described nano graphite carbon is less than or equal to 10nm usually at the thickness of catalyst surface.
5. the fuel-cell catalyst with nano graphite carbon rivet arrangement according to claim 1; it is characterized in that: described nano graphite carbon utilizes chemical vapour deposition technique; at high temperature in carbon carrier carried metal seed activity component catalyst presoma, introduce gas phase carbon source; also be rearranged into the nano graphite carbon of various structure at metal surface catalytic pyrolysis carbon further, prepare the fuel-cell catalyst with nano graphite carbon rivet arrangement.
6. the fuel-cell catalyst with nano graphite carbon rivet arrangement according to claim 1, it is characterized in that: metal active constituent catalyst comprises fuel cell noble metal catalysts and alloy thereof and non-precious metal catalyst, specifically comprise a kind of simple substance in Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, Mo, or consisting of binary and multicomponent alloy.
7. the fuel-cell catalyst with nano graphite carbon rivet arrangement according to claim 1, it is characterized in that: high temperature is 600-1000 DEG C, typically no more than 800 DEG C: gaseous carbon sources comprises acetylene, methane, ethane, propine, propylene, propane, 1,3-butadiene, 1-butylene, ethene, butine.
8. the fuel-cell catalyst with nano graphite carbon rivet arrangement according to claim 1, it is characterized in that: the amount of the gas phase carbon source used is 50mg at catalyst precursor, when gas-phase carbon source and course speed is 5-15ml/min, duration of ventilation is 10s-5min.
9. the preparation method with the fuel-cell catalyst of nano graphite carbon rivet arrangement according to claim 1, is characterized in that: specifically comprise the following steps:
1) take a certain amount of carbon-supported metal active constituent catalyst precursor samples, be placed in little porcelain boat, vibration makes catalyst precursor be laid in equably in porcelain boat;
2) porcelain boat that carbon-supported metal active constituent catalyst precursor is housed is put into the centre of quartz ampoule on tube furnace, pass into a period of time inert gas and get rid of quartzy air in tube, or be evacuated to below 0.1Pa in vacuum tube furnace;
3) under an inert atmosphere, be warming up to 80 DEG C-120 DEG C, insulation, temperature retention time is generally no more than 3h, the moisture in removing catalyst;
4) continue to be warming up to 600-1000 DEG C, when temperature reaches set point, pass into carbon-source gas carry out chemical vapour deposition reaction, afterwards, close carbon-source gas, pass into inert gas, be incubated 15min-2h at this temperature;
5) continue to pass into inert gas, after tube furnace temperature is down to room temperature, take out sample, use.
10. the using method with the fuel-cell catalyst of nano graphite carbon rivet arrangement according to claim 1, it is characterized in that: by there is the fuel-cell catalyst of nano graphite carbon rivet arrangement first through electrochemical activation process during use, use again after the part graphite carbon-coating of catalyst surface is removed.
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