CN104289242B - Preparation method for the high graphitization degree carbon base catalyst of fuel battery negative pole - Google Patents
Preparation method for the high graphitization degree carbon base catalyst of fuel battery negative pole Download PDFInfo
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- CN104289242B CN104289242B CN201310303367.6A CN201310303367A CN104289242B CN 104289242 B CN104289242 B CN 104289242B CN 201310303367 A CN201310303367 A CN 201310303367A CN 104289242 B CN104289242 B CN 104289242B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to the preparation method of a kind of high graphitization degree carbon base catalyst for fuel battery negative pole, it is with Colophonium as carbon precursor, after presoma high-temperature heating is melted, immerses template;After stirring, it is added thereto to nitrogenous precursor, adds slaine simultaneously;Then drying, high-temperature process and secondary nitridation;Wash the most in an acidic solution, remove template;Eventually pass filter, wash and be dried the N doping carbon base catalyst material finally giving high graphitization degree;This catalyst has high graphitization degree, high-specific surface area and orderly pore structure.When it is used as fuel battery cathode with proton exchange film catalyst, show good oxygen reduction activity, and this catalyst environmental friendliness, low cost, microcosmic are controlled, aboundresources, promise to be the eelctro-catalyst of Proton Exchange Membrane Fuel Cells.
Description
Technical field
The present invention relates to fuel-cell catalyst preparation field, particularly to the system of a kind of cathod catalyst
Preparation Method.
Background technology
As the one of fuel cell, Proton Exchange Membrane Fuel Cells (proton exchange membrane
Fuel cell, PEMFC) with pure hydrogen or purification reformation gas as fuel, with perfluoro sulfonic acid membrane as electrolyte,
Can stable operation between room temperature to 100 DEG C, thus have can room temperature quickly start, electroless liquid stream lose,
Contamination-free discharge, specific power and specific energy high.Following with hydrogen for main energetic carrier
Hydrogen energy era, Proton Exchange Membrane Fuel Cells as electric powered motor source, portable power supply and
The aspects such as dispersion power station have broad application prospects.
Eelctro-catalyst is one of critical material of Proton Exchange Membrane Fuel Cells (PEMFC), current fuel
Cell cathode oxygen reduction catalyst is mainly Pt/C catalyst;Anode mainly uses the PtRu/C of anti-CO
Catalyst.The cost that this kind of catalyst is too high, is that restriction Proton Exchange Membrane Fuel Cells is business-like heavy
Want one of factor.The cathode reaction of PEMFC is oxygen reduction reaction, and its electrode reaction speed is far below sun
The hydroxide reaction of pole, more than the 80% of PEMFC loss in efficiency is from negative electrode.ORR is complicated
Four electron reactions, occur multiple intermediate state species in the reaction mechanism mechanism of reaction, such as hydrogen peroxide, ADSORPTION STATE hydroxyl
Base etc..Additionally, along with environment deteriorates increasingly, air quality degradation, in air, impurity causes
Catalyst poisoning problem becomes one of key factor affecting its durability, thus in recent years by height
Pay close attention to.Therefore, the ORR catalyst business to PEMFC of high activity, low cost, high mithridatism is developed
Industry melts a tool and is of great significance.
Carbon nano-material has bigger serface, homogeneous nanostructured, strong corrosion resistant performance, height are led
The feature such as electrically, thus it is widely used in electronics, catalysis, hydrogen storage and electrochemical field.But
Nano carbon itself has catalysis activity hardly to fuel cell oxygen reduction reaction.Research table in recent years
Bright, the nano-carbon material of some doping N or B, during oxygen reduction reaction, shows higher oxygen
Reduction reaction catalysis activity, this result has promoted rapidly the research and development of carbon-supported catalysts.
Chinese patent (application number 200310108845.4) provides a kind of with Colophonium as presoma, SiO2
For the preparation method of template high graphitization material with carbon element, prepared material with carbon element has high graphitization degree.But
The Carbon Materials prepared due to the method, does not the most have hydrogen reduction catalytic performance without N doping;
Chinese patent (application number 200910248475.1) provides one and utilizes phenolic resin to prepare nitrogen
The preparation method of doped catalyst, due to resorcinol price, limits the big life of its industrialization
Produce.Additionally, use Carbon Materials prepared by this presoma, need higher than more than 2000 DEG C, ability
Realize high graphitization.But the high-temperature process of this more than 2000 DEG C, the hole of material can be caused to subside,
Specific surface area and pore volume is caused drastically to decline.
The present invention is directed to disadvantages mentioned above, it is provided that a kind of high graphitization degree, the doping charcoal base catalysis of high-ratio surface
The preparation method of agent.I.e. using cheap hard mould agent, with Colophonium as carbon source, nitrogenous precursor is nitrogen
Source, and simultaneously add metallic element, is then passed through high temperature pyrolysis, nitridation, after through pickling, ball milling
The carbon nano-material of high graphitization degree, high-specific surface area is obtained etc. process.
Summary of the invention
It is an object of the invention to provide high graphitization degree, the system of high-specific surface area doping carbon base catalyst
Preparation Method.
For the preparation method of the high graphitization degree carbon base catalyst of fuel battery negative pole, it with Colophonium is
Carbon precursor, after presoma high-temperature heating is melted, immerses template;After stirring, wherein
Add nitrogenous precursor, add slaine simultaneously;Then drying, high-temperature process and secondary nitridation;
Wash the most in an acidic solution, remove template;Eventually pass filter, wash and be dried and finally give height
The N doping carbon base catalyst material of degree of graphitization;Its preparation process is:
1). Colophonium is heated to softening temperature 40-400 DEG C so that it is form melted precursor A;
2) template is joined in A, and continuously stirred, it is allowed to mix homogeneously, obtains mixture B;
Wherein hard template is 10:1-1:10 with the mass ratio of Colophonium, is preferably in a proportion of 4:1-1:5;
3) in mixture B, nitrogen-containing precursor is added, continuously stirred more than 1h, mix homogeneously,
Obtain mixture C;Wherein nitrogen-containing precursor and asphalt quality are than for 1:10-1:1000, the most preferably
Ratio is 1:10-1:100;
4) in C add metal salt solution, continue stirring, obtain mixture D, wherein slaine with
The mol ratio of Colophonium is 1:10-1:100, is preferably in a proportion of: 1:10-1:40;
5) by mixture D high-temperature process 1~6 hours under 500~1800 DEG C of nitriding atmosphere protective conditions,
Obtaining pressed powder E, preferable temperature is 800-1200 DEG C;
6). pressed powder E is soaked 24~50 hours in the acid solution of 0.5~5M, cleans, do
Dry, ball milling, obtains pressed powder F;
7). by pressed powder F under 500 DEG C~1800 DEG C of nitriding atmosphere protective conditions high temperature reprocessing 1~
6 hours, obtaining the carbon base catalyst H of the present invention, preferable temperature is 800 DEG C~1200 DEG C;
Described template is SiO2Colloidal sol, zeolite, Al2O3, mesoporous SiO2, magnesium oxide, magnesium acetate,
Magnesium gluconate, copper oxide, zinc oxide, ferrous oxide, iron sesquioxide, calcium carbonate, magnesium carbonate,
Ferroso-ferric oxide, tin ash, silicon dioxide, aluminium oxide, zirconium oxide, molybdenum trioxide, three oxidations
Two vanadium, nano titanium oxide powder, metallic nickel hydroxide, metallic iron hydroxide, the hydrogen of magnesium metal
One or two or more kinds in oxide, polystyrene microsphere, poly (methyl methacrylate) micro-sphere.
Described nitrogenous precursor is ethylenediamine, n-hexylamine, trimethylamine, tripolycyanamide, polyurethane, gathers
In pyridine, polypyrrole, polyacrylonitrile, polyaniline, two/melamine resin, Lauxite
One or two or more kinds.
Described slaine is the one in IVB, VB, VIB, VIIB, VIII, IB and Group IIB or two
Plant the soluble-salt of above metallic element;Soluble-salt be the nitrate of metal, carbonate, sulfate,
Acetate, halogenide, dinitroso diamine salts, acetylacetonate or macro ring complex porphyrin,
One or two or more kinds in one or more (multiple can cosolvency salt) in the phthalein mountain valley with clumps of trees and bamboo and polymer thereof;
Described metallic element is in Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W, Mo
One or two or more kinds.
Described acid is the one in sulphuric acid, nitric acid, phosphoric acid or hydrochloric acid;Concentration is 0.2M~5M, excellent
Selecting concentration is 0.5M~2M.
Described high-temperature process temperature is preferably 800~1200 DEG C;Described secondary nitriding temperature is preferable temperature
800~1200 DEG C.
Described nitriding atmosphere is nitrogen, argon, helium, NH3、CH3In CN or HCN gas one
Kind or two kinds mixed above.
The present invention uses the Colophonium of high graphite degree as presoma, utilizes cheap hard mould agent, to contain
Nitrogen presoma is nitrogen source, adds metallic element simultaneously, is then passed through high temperature pyrolysis, nitridation, after warp
The process such as pickling, ball milling obtains the carbon nano-material of high graphitization degree, high-specific surface area.With Colophonium it is
Presoma, not only avoids high temperature graphitization processing procedure, draws during it also avoid high temperature graphitization
The hole risen subsides problem;In building-up process, add nitrogenous precursor in situ, can be in situ in catalysis
The defect lattice of agent introduces nitrogen element and the interpolation of scarce slaine, changes the microstructure of Carbon Materials,
But also improve N doping degree, add the avtive spot of electrochemical reaction;Use hard mould agent,
Price is cheap, and the material of preparation has high-specific surface area and high pore volume.Prepared material is carried out two
Secondary nitridation, utilizes the corrasion of ammonia, is got rid of by micropore disadvantageous to electrochemical reaction, and
The oxygen-containing functional group introduced after pickling can also be made to remove, and graphite mould, pyrimidine Type atom N can be changed
Content, enhance the oxygen reduction catalytic activity of catalyst.
The present invention compared with prior art has the advantage that
(1). employing cheap, the reaction monomers of high graphitization, product cost is low, graphitization journey
Degree height, good conductivity;
(2). in building-up process, add nitrogenous precursor in situ, can be in situ in the defect of catalyst
Lattice introduces nitrogen element and the interpolation of scarce slaine, changes the microstructure of Carbon Materials, but also
Improve N doping degree, add the avtive spot of electrochemical reaction;
(3) material using hard mould agent to prepare has high-specific surface area and high pore volume, adds catalysis
The avtive spot of agent.
(4) prepared material is carried out heat treatment and secondary nitridation, utilizes the corrasion of ammonia, will
Micropore disadvantageous to electrochemical reaction is got rid of, and the oxygen-containing functional group introduced after pickling can also be made
Removing, and can change graphite mould, the content of pyrimidine Type atom N, the hydrogen reduction enhancing catalyst is urged
Change activity
(5). provide the preparation method of a kind of new metal-loaded catalysis, i.e. mix in carbonization process
Enter metallic element, metal can not only be made to be uniformly dispersed in carbon surface, and the structure of charcoal can also be changed,
Thus improve the performance of catalyst.
(6) catalyst has high stability and high activity in acidic fuel cell, and has the highest
Methanol tolerance, CO and SO in Pt/C2Performance.
(7). it is used in PEMFC field, it is also possible to for carrying metal, such as platinum etc., and is provided that more
Strong catalytic capability;And less transition metal can be used, such as cobalt, ferrum etc., show higher
The active and long stability of oxygen reduction reaction;
(8). preparation method is simple, conventional production device, is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1. the oxygen reduction activity curve comparison of catalyst prepared by the embodiment of the present invention 1 and comparative example.
Detailed description of the invention
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
1.0g Colophonium is heated to softening temperature 200 DEG C so that it is form melted precursor A;By 50nm
The CaCO of nano-scale3Hard template joins in A, and continuously stirred, is allowed to mix homogeneously, obtains
Mixture B, wherein hard template is 1:2 with the mass ratio of Colophonium;Nitrogenous forerunner is added in mixture B
Thing, continuously stirred more than 1h, mix homogeneously, obtain mixture C, wherein the own diammonium of nitrogen-containing precursor
With Colophonium molal weight than for 1:100;With ferric nitrate and the Colophonium mol ratio ratio as 1:30 to C
Middle addition metal salt solution, continues stirring, obtains mixture D;By mixture D in 900 DEG C at NH3
Under the conditions of atmosphere protection, carbonization processes 2 hours, obtains pressed powder E;By pressed powder E at 1M
Dilute acid soln in soak 24 hours, clean, be dried, ball milling, the charcoal base obtaining the present invention is catalyzed
Agent H.
Comparative example 1
1.0g Colophonium is heated to softening temperature 200 DEG C so that it is form melted precursor A;By 50nm
The CaCO of nano-scale3Hard template joins in A, and continuously stirred, is allowed to mix homogeneously, obtains
Mixture B, wherein hard template is 1:2 with the mass ratio of Colophonium;Nitrogenous forerunner is added in mixture B
Thing, continuously stirred more than 1h, mix homogeneously, obtain mixture C, with ferric nitrate and Colophonium mol ratio
Ratio for 1:30 adds metal salt solution in C, continues stirring, obtains mixture D;Will
Mixture D carbonization under 900 DEG C of nitriding atmosphere protective conditions processes 2 hours, obtains pressed powder E;
Pressed powder E is soaked 24 hours in the dilute acid soln of 1M, cleans, be dried, ball milling, i.e.
Obtain the carbon base catalyst H of the present invention.
Comparative example 2
1.0g Colophonium is heated to softening temperature 200 DEG C so that it is form melted precursor A;By 50nm
The CaCO of nano-scale3Hard template joins in A, and continuously stirred, is allowed to mix homogeneously, obtains
Mixture B, wherein hard template is 1:2 with the mass ratio of Colophonium;Nitrogenous forerunner is added in mixture B
Thing, continuously stirred more than 1h, mix homogeneously, obtain mixture C, wherein the own diammonium of nitrogen-containing precursor
With Colophonium molal weight than for 1:100;By mixture C in 900 DEG C at NH3Under the conditions of atmosphere protection
Carbonization processes 2 hours, obtains pressed powder E;Pressed powder E is soaked in the dilute acid soln of 1M
Steep 24 hours, clean, be dried, ball milling, obtain the carbon base catalyst H of the present invention.
In oxygen reduction reaction, the catalysis activity of catalyst uses rotating disk electrode (r.d.e) (RDE) technology to survey
Examination, experiment is with EG&G636 rotating disk electrode (r.d.e) controller (Princeton Applied Research)
Potentiostat carry out.Test condition is as follows: test forward direction 0.5mol L-1H2SO4Electrolyte is passed through
30min nitrogen or oxygen, make electrolyte reach oxygen saturation, respectively the hydrogen reduction under two kinds of atmosphere of test
Polarization curve.Sweep limits is 1.14~0.04V, and scanning speed is 5mV s-1, electrode rotating speed is 1600
rpm。
Poison ability to investigate the antioxidation sulfur of catalyst, test system and other test condition with
In the case of aforementioned RDE test is identical, changing electrolyte solution is 0.5mol L-1H2SO4With 0.1
mol L-1Na2SO3Mixed liquor, after poisoning two minutes, then at 0.5mol L-1H2SO4Middle test its
Polarization curves of oxygen reduction, poisons before and after's polarization curves of oxygen reduction by contrast, evaluates its anti-SO2Anti-
Poison performance.
Fig. 1. according to the catalysis expression activitiy of the catalyst of embodiment 1 preparation, rpm=1600;By
Fig. 1 it can be seen that compared with comparative example 1, the oxygen reduction activity ratio of Carbon Materials prepared by Colophonium is relatively low,
After N doping, the performance of catalyst significantly improves.Compared with comparative example 2, after adding metal,
The performance of catalyst is apparently higher than the catalyst being not added with metal.The catalyst of embodiment 1 preparation has
The highest oxygen reduction catalytic activity, its hydrogen reduction starting point is about 0.85V.
Embodiment 2
0.5g Colophonium is heated to softening temperature 280 DEG C so that it is form melted precursor A;By 30nm
The MgO hard template of nano-scale joins in A, and continuously stirred, is allowed to mix homogeneously, is mixed
Compound B, wherein MgO is 1:2 with the mass ratio of Colophonium;Nitrogen-containing precursor is added in mixture B
Tripolycyanamide, continuously stirred 2h, mix homogeneously, obtain mixture C, wherein nitrogen-containing precursor and drip
Blue or green molal weight ratio is for 1:100;Add in C with cobalt nitrate and the Colophonium mol ratio ratio as 1:50
Metal salt solution, continues stirring, obtains mixture D;Mixture D is protected in 800 DEG C of ammonia atmospheres
Under the conditions of carbonization process 2 hours, obtain pressed powder E;Pressed powder E is molten at the diluted acid of 0.5M
Liquid soaks 24 hours, cleans, be dried, ball milling 3h, obtain the carbon base catalyst H of the present invention.
Embodiment 3
Colophonium 0.5g is heated to softening temperature 180 DEG C so that it is form melted precursor A;By 0.5g
SiO2(SBA-15) during hard template joins A and continuously stirred, it is allowed to mix homogeneously, is mixed
Compound B;Adding nitrogen-containing precursor tripolycyanamide, continuously stirred 2h in mixture B, mixing is all
Even, obtain mixture C, wherein nitrogen-containing precursor and Colophonium molal weight are than for 1:300;With cobalt nitrate
In C, add metal salt solution with the ratio that Colophonium mol ratio is 1:20, continue stirring, obtain
Mixture D;Mixture D carbonization under 1000 DEG C of nitriding atmosphere protective conditions is processed 2 hours,
To pressed powder E;Pressed powder E is soaked 24 hours in the dilute acid soln of 0.5M, clean,
Dry, ball milling 3h, obtains the carbon base catalyst H of the present invention.
Embodiment 4
1.5g Colophonium is heated to softening temperature 260 DEG C so that it is form melted precursor A;By 50nm
The CaCO of nano-scale3Hard template 2g joins in A, and continuously stirred, is allowed to mix homogeneously,
Obtain mixture B;Nitrogen-containing precursor, continuously stirred more than 1h, mixing is added in mixture B
Uniformly, obtaining mixture C, wherein nitrogen-containing precursor second diammonium and Colophonium molal weight are than for 1:100;
In C, add metal salt solution with ferrous nitrate amine and the Colophonium mol ratio ratio as 1:30, continue
Continuous stirring, obtains mixture D;Mixture D carbonization under the conditions of 900 DEG C of nitrogen atmosphere protections is processed
2 hours, obtain pressed powder E;Pressed powder E is soaked in the dilute acid soln of 1M 24 little
Time, clean, be dried, ball milling, obtain the carbon base catalyst H of the present invention.
Embodiment 5
1.0 Colophoniumes are heated to softening temperature 320 DEG C so that it is form melted precursor A;By 80nm
The Al of nano-scale2O3 hard template 3.0 joins in A, and continuously stirred, is allowed to mix homogeneously,
Obtain mixture B;Adding in mixture B containing polypyrrole, continuously stirred more than 1h, mixing is all
Even, obtain mixture C, wherein nitrogen-containing precursor second diammonium and Colophonium molal weight are than for 1:100;With
Ferrous nitrate amine and Colophonium mol ratio are that the ratio of 1:30 adds metal salt solution in C, continue to stir
Mix, obtain mixture D;Mixture D carbonization under the conditions of 800 DEG C of protection of ammonia is processed 2 hours,
Obtain pressed powder E;Pressed powder E is soaked 24 hours in the dilute acid soln of 1M, clean,
Dry, ball milling, obtains H.By pressed powder H 800 DEG C of carbonization treatment 1h in nitrogen atmosphere,
Pressed powder G is the catalyst that the present invention is protected.
Embodiment 6
1.0 Colophoniumes are heated to softening temperature 220 DEG C so that it is form melted precursor A;By CaO
Hard template 3.0g joins in A, and continuously stirred, is allowed to mix homogeneously, obtains mixture B;To
Mixture B adds containing polyaniline, continuously stirred more than 1h, mix homogeneously, obtains mixture C, its
Middle nitrogen-containing precursor second diammonium and Colophonium molal weight are than for 1:100;With ferrocene with Colophonium mol ratio it is
The ratio of 1:50 adds metal salt solution in C, continues stirring, obtains mixture D;By mixture
D carbonization under the conditions of 1000 DEG C of protection of ammonia processes 2 hours, obtains pressed powder E;By solid powder
End E soaks 24 hours in the dilute acid soln of 1M, cleans, is dried, ball milling, obtains H.Will be solid
Body powder H 900 DEG C of carbonization treatment 1h in ammonia atmosphere, obtain pressed powder G and are the present invention and are protected
The catalyst protected.
Claims (8)
1. being used for the preparation method of the high graphitization degree carbon base catalyst of fuel battery negative pole, it is with Colophonium as carbon precursor, after presoma high-temperature heating is melted, immerses template;After stirring, it is added thereto to nitrogenous precursor, adds slaine simultaneously;Then wash in an acidic solution after drying, high-temperature process, remove template, through filtering, wash and be dried and secondary nitrogenizing and finally gives the N doping carbon base catalyst material of high graphitization degree;Its preparation process is:
1) Colophonium is heated to softening temperature 40-400 DEG C so that it is form melted precursor A;
2) template is joined in A, and continuously stirred, it is allowed to mix homogeneously, obtains mixture B;Wherein hard template is 10:1-1:10 with the mass ratio of Colophonium;
3) in mixture B, add nitrogen-containing precursor, continuously stirred at least 1h, mix homogeneously, obtain mixture C;Wherein nitrogen-containing precursor and asphalt quality are than for 1:10-1:1000;
4) adding metal salt solution in C, continue stirring, obtain mixture D, wherein slaine is 1:10-1:100 with the mol ratio of Colophonium;
5) by mixture D high-temperature process 1~6 hours under 500~1800 DEG C of nitriding atmosphere protective conditions, pressed powder E is obtained;
6) pressed powder E is soaked 24~50 hours in the acid solution of 0.5~5M, clean, be dried, ball milling, obtain pressed powder F;
7) pressed powder F high temperature under 500 DEG C~1800 DEG C of nitriding atmosphere protective conditions is reprocessed 1~6 hour, obtain carbon base catalyst H.
2. according to the preparation method described in claim 1, it is characterized in that: described template is zeolite, magnesium oxide, magnesium acetate, magnesium gluconate, copper oxide, zinc oxide, ferrous oxide, iron sesquioxide, calcium carbonate, magnesium carbonate, ferroso-ferric oxide, tin ash, silicon dioxide, aluminium oxide, zirconium oxide, molybdenum trioxide, Vanadium sesquioxide, nano titanium oxide powder, metallic nickel hydroxide, metallic iron hydroxide, the hydroxide of magnesium metal, polystyrene microsphere, one or two or more kinds in poly (methyl methacrylate) micro-sphere, wherein template grain size scope is 5~500nm.
3. according to the preparation method described in claim 1, it is characterised in that: described nitrogenous precursor is one or two or more kinds in ethylenediamine, n-hexylamine, trimethylamine, tripolycyanamide, polyurethane, polypyridine, polypyrrole, polyacrylonitrile, polyaniline, two/melamine resin, Lauxite.
4. according to the preparation method described in claim 1, it is characterised in that: described slaine is the soluble-salt of one or two or more kinds metallic element in IVB, VB, VIB, VIIB, VIII, IB and Group IIB;Soluble-salt is that one or more in the nitrate of metal, carbonate, sulfate, acetate, halogenide, dinitroso diamine salts, acetylacetonate or macro ring complex porphyrin, the phthalein mountain valley with clumps of trees and bamboo and polymer thereof can one or two or more kinds in cosolvency salt;Described metallic element is one or two or more kinds in Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W, Mo.
5. according to the preparation method described in claim 1, it is characterised in that: described acid is the one in sulphuric acid, nitric acid, phosphoric acid or hydrochloric acid;Concentration is 0.2M~5M.
6. according to the preparation method described in claim 5, it is characterised in that: the concentration of described acid is 0.5 M~2M.
7. according to the preparation method described in claim 1, it is characterised in that: described high-temperature process temperature is 900~1100 DEG C;Described secondary nitriding temperature is 900~1100 DEG C.
8. according to the preparation method described in claim 1, it is characterised in that: described nitriding atmosphere is nitrogen, NH3、CH3One or two or more kinds mixing in CN or HCN gas.
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CN1544321A (en) * | 2003-11-25 | 2004-11-10 | 复旦大学 | Preparation method of carbon material with highly ordered nanometer hole of graphite hole wall structure |
CN1970442A (en) * | 2005-11-22 | 2007-05-30 | 三星Sdi株式会社 | Mesoporous carbon, method of preparing the same, and fuel cell using the carbon |
CN102476058A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Carbon gel catalyst, its preparation and its application |
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