CN105470532A - Composite carbon material and preparation method and application thereof - Google Patents
Composite carbon material and preparation method and application thereof Download PDFInfo
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- CN105470532A CN105470532A CN201511008255.3A CN201511008255A CN105470532A CN 105470532 A CN105470532 A CN 105470532A CN 201511008255 A CN201511008255 A CN 201511008255A CN 105470532 A CN105470532 A CN 105470532A
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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
- H01M4/88—Processes of manufacture
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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 discloses a composite carbon material and a preparation method and an application thereof. The preparation method of the composite carbon material comprises the following steps: (1) preparing a precursor, wherein the precursor is a mixture of a carbon source, a ferric salt and chlorate; (2) carrying out thermal treatment after mixing the precursor with a nitrogen source to obtain a thermal treatment product containing the chlorate; and (3) removing the chlorate in the thermal treatment product, so as to obtain the composite carbon material. The composite carbon material disclosed by the invention can be used as an oxygen reduction catalyst; and the catalytic performance for oxygen reduction achieves or exceeds that of a commercial platinum-carbon catalyst. The preparation method disclosed by the invention is simple, low in cost and applicable to large-scale production of a non-noble metal catalyst for fuel cell oxygen reduction; and the composite material demonstrates the catalytic performance for oxygen reduction achieving or exceeding that of commercial platinum carbon, and has the potential of being used as a replacement of a noble metal catalyst for fuel cell oxygen reduction.
Description
Technical field
The present invention relates to a kind of complex carbon material and preparation method thereof and application, belong to complex carbon material field.
Background technology
Since entering the new century, energy security and environmental problem are more and more subject to the attention in countries in the world and area.Fuel cell is high because having energy density, fuel rich, and the features such as no pollution become one of important selection of current this two problems of solution.Noble metal is usually used as fuel battery cathod catalyst with catalytic oxygen reduction reaction, but its reserves are rare, price is high, the scale application of poor stability and shortcoming hinders the widely fuel cell such as selectivity is low.In recent years, researcher utilizes this type of noble metal and transition metal to construct the catalyst with the special construction such as nucleocapsid or alloy, and to improve the utilance of noble metal and to reduce its carrying capacity, but this can not break away from the limitation of noble metal itself all the time.Therefore, exploitation cheap, the commercialization process of continuable, high performance non noble metal oxygen reduction catalyst to fuel cell have very important significance.
From the sixties in last century five, people just begin one's study oxygen reduction non-noble metal catalyst.Develop into so far, non-precious metal catalyst is broadly divided into following a few class: the material with carbon element of Heteroatom doping, based on the oxide of transition metal or sulphur compound or nitride or phosphide, the material with carbon element modified based on iron and nitrogen element.Be developed the conventional composite materials based on carbon nano-tube and graphite flake layer in advance.This kind of traditional material normally develops based on Heteroatom doping, and shows lower hydrogen reduction catalytic performance.In addition, this kind of traditional material first obtains carbon nano-tube and graphite flake layer often respectively, and then they are assembled into composite material; This process very complicated, and with high costs.Therefore, develop a kind of preparation that is simple, economic, that be suitable for large-scale production have high activity, stability the technology of novel non-noble metal nano composite material to restructure the use of energy and environmental protect problem has huge and profound significance.
Summary of the invention
The object of this invention is to provide a kind of carbon nano-tube and graphite flake layer complex carbon material, the complex carbon material that the present invention passes through can as oxygen reduction catalyst, therefore, it is possible to be applied in fuel cell field.
The preparation method of a kind of complex carbon material provided by the present invention, comprises the steps:
1) prepare presoma, described presoma is the mixture of carbon source, molysite and chlorate;
2) heat-treat after described presoma being mixed with nitrogenous source, obtain the heat-treated products containing described chlorate;
3) namely the described chlorate removed in described heat-treated products obtains described complex carbon material.
In above-mentioned preparation method, step 1) in, the step preparing described presoma is as follows:
Prepare the aqueous solution of described carbon source, described molysite and described chlorate, and each component is mixed, namely the moisture that the dry described aqueous solution is removed wherein with drying obtain described presoma.
In above-mentioned preparation method, described carbon source can be selected from least one in glucose, sucrose, maltose and fructose;
Described molysite can be selected from least one in iron chloride, ferric nitrate, ferric sulfate and ferric acetate;
Described chlorate can be selected from least one in sodium chloride, potassium chloride, lithium chloride, magnesium chloride and calcium chloride;
Described nitrogenous source can be selected from least one in melamine, nitrile ammonia and two nitrile ammonia.
In above-mentioned preparation method, the mass ratio that feeds intake of described carbon source and described molysite can be 1:0.5 ~ 3, specifically can be 1:1.2;
The mass ratio that feeds intake of described carbon source and described chlorate can be 1:1 ~ 30, specifically can be 1:1.8 ~ 22.4,1:7 ~ 22.4,1:1.8 ~ 7,1:1.8,1:7 or 1:22.4;
The mass ratio that feeds intake of described carbon source and described nitrogenous source can be 1:0.5 ~ 20, specifically can be 1:2.
In above-mentioned preparation method, step 2) in, described presoma is mixed by grinding with described nitrogenous source;
Described heat treatment is carried out in a nitrogen atmosphere.
In above-mentioned preparation method, step 2) in, described heat treated temperature can be 700 DEG C ~ 1000 DEG C, specifically can be 700 DEG C ~ 900 DEG C, 700 DEG C, 800 DEG C or 900 DEG C; The described heat treated time can be 0.5 hour ~ 8 hours, specifically can be 2 hours.
In above-mentioned preparation method, step 3) in, remove the described chlorate in described heat-treated products by washing.
Complex carbon material prepared by said method of the present invention, is made up of carbon nano-tube and graphite flake layer;
The diameter of described carbon nano-tube is 10 ~ 80nm, and length is 1 ~ 20 μm, and the thickness of described graphite flake layer is 0.5 ~ 5nm.
All doped with metallic iron and cementite nano particle in described carbon nano-tube and described graphite flake layer, wherein the doping of ferro element is 5 ~ 35% of described complex carbon material gross mass, as 28.05%.
The specific area of complex carbon material of the present invention is 100 ~ 400m
2/ g, has micropore and meso-hole structure, and aperture is 0.5 ~ 10 nanometer.
Complex carbon material provided by the present invention can as oxygen reduction catalyst, and its hydrogen reduction catalytic performance reaches or is better than business platinum C catalyst.
Preparation method provided by the invention is simple, with low cost, be suitable for large-scale production fuel cell oxygen reduction non-precious metal catalyst, this composite material exhibits goes out to reach or is better than the hydrogen reduction catalytic performance of business platinum carbon, the potential replacer as fuel cell oxygen reduction noble metal catalyst.
Preparation method provided by the invention mainly adopts the chlorate of solubility as dispersant and carrier, after it mixes with carbon source and source of iron, to be blended in tube furnace heat treatment a period of time under uniform temperature with nitrogenous source, then chlorate is removed in washing, obtains complex carbon material of the present invention.In complex carbon material of the present invention, graphite flake layer shows more avtive spot because of its two special nanostructures; Except providing avtive spot, carbon nano-tube also can stop piling up of graphite flake layer effectively, and can provide the passage of fast transport electronics; The three-D space structure of complex carbon material can promote the fast transfer of reactant and product; Be present in Potential Distributing and the density of states that metallic iron in carbon nano-tube and graphite flake layer or cementite nano particle can modify its carbon layer on surface, thus improve the catalytic activity of top layer active site.Based on above-mentioned numerous advantage, this kind of composite material exhibits goes out to reach or is better than the hydrogen reduction catalytic performance of business platinum carbon.
The present invention, compared with other prior art, has following characteristics:
1, the present invention adopts situ study to prepare carbon nano-tube and graphite flake layer composite material, and compare as being assembled into composite material again after synthesis of nano pipe respectively and graphite flake layer relative to other method, the method cost is low, is suitable for large-scale production.
2, adopt chlorate as dispersant and carrier in the present invention, can effectively disperse carbon source, source of iron and nitrogenous source, make their compounds evenly, thus effectively prevent iron atom from high temperature assembling and growing up.Meanwhile, the existence of chlorate can improve the degree of graphitization of material, is conducive to the maintenance of nitrogen-atoms and carbon atom, contributes to the generation of nano-pore.In addition, after prepared by material, chlorate has been recycled by recrystallization.
3, the carbon source that preparation method of the present invention adopts is simple organic molecule, and as the carbon source such as glucose, sucrose, with other complicated carbon source as compared with polyaniline, polypyrrole, the method cost is low, simple, convenient operation.
4, preparation method of the present invention adopts cheap melamine, cyanamide etc. be nitrogenous source, and with other nitrogenous source as compared with ammonia, hydrogen cyanide, doping process is relatively safe, and inventory is easy to control.
5, the catalytic performance of the carbon nano-tube prepared of the present invention and graphite flake layer complex carbon material is excellent, has higher oxygen reduction activity compared with other non-precious metal catalyst of bibliographical information.
6, preparation method's technique of the present invention is simple, economical, operation is convenient, be easy to large-scale production, has huge potential using value at many industrial catalysts or other scientific domain.
Accompanying drawing explanation
Fig. 1 is the carbon nano-tube of the embodiment of the present invention 1 preparation and the X-ray powder diffraction curve of graphite flake layer complex carbon material.
Fig. 2 is the carbon nano-tube prepared of the embodiment of the present invention 1 and the electron scanning micrograph (Fig. 2 (a)) of graphite flake layer complex carbon material and transmission electron microscope photo (Fig. 2 (b)-Fig. 2 (d)).
Fig. 3 is the carbon nano-tube of the embodiment of the present invention 1 preparation and the thermogravimetric curve of graphite flake layer complex carbon material.
Fig. 4 is the carbon nano-tube prepared of the embodiment of the present invention 1 and the specific area test curve (Fig. 4 (a)) of graphite flake layer complex carbon material and pore-size distribution test curve (Fig. 4 (b)).
Fig. 5 is that the carbon nano-tube of the embodiment of the present invention 1 preparation and the photoelectron spectroscopy of graphite flake layer complex carbon material sweep spectrogram entirely.
Fig. 6 is the hydrogen reduction empirical curve of the carbon nano-tube of the embodiment of the present invention 1 preparation and the carbon supported platinum catalyst of graphite flake layer complex carbon material and commercial use.
Fig. 7 is the methanol tolerance test experiments curve of the carbon nano-tube of the embodiment of the present invention 1 preparation and the carbon supported platinum catalyst of graphite flake layer complex carbon material and commercial use.
Fig. 8 is the stability test empirical curve of the carbon nano-tube of the embodiment of the present invention 1 preparation and the carbon supported platinum catalyst of graphite flake layer complex carbon material and commercial use.
Embodiment
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation and property test of embodiment 1, carbon nano-tube and graphite flake layer complex carbon material
Take 0.5 gram of glucose, 0.6 gram of nine water ferric nitrate and 3.5 grams of sodium chloride, mixture is added magnetic agitation in 10 ml deionized water and dissolve 0.5 hour, until completely dissolved, continue stirring 1 hour, solution is mixed; 100 ml beakers that above-mentioned solution is housed are put into drying box dry, after most deionized water is removed, again this beaker is transferred in vacuum drying chamber and continues vacuumize, after removing residual a small amount of moisture content, obtain the mixture of glucose, nine water ferric nitrates and sodium chloride; By this mixture and 1 gram of melamine ground and mixed evenly after, be transferred in crucible, and insert in the quartz ampoule of tube furnace, with argon gas except air half an hour, then be warming up to 800 DEG C, heat-treat 2 hours under argon shield after, obtain heat-treated products; Collect heat-treated products, porphyrize, is washed to till not having sodium chloride in product, at 60 DEG C after vacuumize, obtains carbon nano-tube and graphite flake layer complex carbon material.
The X-ray powder diffraction curve of complex carbon material prepared by the present embodiment as shown in Figure 1, as seen from the figure, except containing except graphitized carbon in complex carbon material prepared by the present embodiment, also contains metallic iron and cementite.
The electron scanning micrograph of complex carbon material prepared by the present embodiment and transmission electron microscope photo are as shown in Figure 2, wherein Fig. 2 (a) is electron scanning micrograph, and Fig. 2 (b), Fig. 2 (c) and Fig. 2 (d) are transmission electron microscope photo.From each figure, complex carbon material prepared by the present embodiment is made up of carbon nano-tube and graphite flake layer, and wherein the diameter of carbon nano-tube is about 10 ~ 80nm, and length is about 1 ~ 20 μm, and the thickness of graphite flake layer is about 0.5 ~ 5nm; Metallic iron and cementite nano particle are not only present in carbon nano-tube but also bury in graphite flake layer.
The thermogravimetric curve of complex carbon material prepared by the present embodiment as shown in Figure 3, the condition of thermogravimetric test is: carry out in air atmosphere, with the ramp of 10 DEG C/min, the mass percentage finally obtaining di-iron trioxide in complex carbon material is 40.10%, and the mass percentage through conversion ferro element is 28.05%.
As shown in Figure 4, wherein, Fig. 4 (a) is nitrogen adsorption-desorption curve to the specific area resolution chart of carbon nano-tube prepared by the present embodiment and graphite flake layer complex carbon material, and Fig. 4 (b) is pore-size distribution test curve.From each figure, complex carbon material prepared by the present embodiment has micropore and meso-hole structure, and its specific area is 192 square metres every gram.From pore size distribution curve, the most of scope in 0.5 ~ 10 nanometer in aperture in the hole in complex carbon material prepared by the present embodiment.
The photoelectron spectroscopy of carbon nano-tube prepared by the present embodiment and graphite flake layer complex carbon material sweeps spectrogram as shown in Figure 5 entirely, and as known in the figure, nitrogen element is successfully doped in carbonaceous layer, and the atomic percentage conc of nitrogen-atoms is 3.13.
From above-mentioned data, method provided by the invention can the complex carbon material of in-situ preparation of carbon nanotube and graphite flake layer, and wherein iron and cementite nano particle are not only present in carbon nano-tube but also bury in graphitization carbon-coating; Obtained composite material exhibits goes out higher specific area and more Jie's micropore, shows again higher N doping content simultaneously.Therefore, the cathodic oxygen reduction catalyst that this kind of composite material can be used as fuel cell uses.
The hydrogen reduction empirical curve of the carbon supported platinum catalyst of carbon nano-tube prepared by the present embodiment and graphite flake layer complex carbon material and commercial use as shown in Figure 6.Concrete test method is: hydrogen reduction empirical curve rotating ring disk electrode (r.r.d.e) is measured in the potassium hydroxide solution of 0.1 mol/L, and the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and curved scanning speed is 10 millivolts/second; In test process, ring electrode current potential is constant in 0.5 volt relative to silver/silver chloride reference electrode (electrolyte is the Klorvess Liquid of 3 moles often liter).
Contrasting with the carbon supported platinum catalyst of commercial use is buy to believe that the platinum weight percentage of ten thousand rich (Johnson-Matthey) (Shanghai) catalyst Co., Ltd is the business carbon supported platinum catalyst of 20% from the village.
Relatively two curves, can find out, the half wave potential of the complex carbon material that the present embodiment prepares performance in hydrogen reduction experiment is-0.096 volt, also higher 13 millivolts than half wave potential-0.109 volt of business carbon supported platinum catalyst, and on ring-disc electrode, the productive rate of hydrogen peroxide is suitable with the carbon supported platinum catalyst of commercial use, therefore shows better hydrogen reduction electro catalytic activity.
The methanol tolerance test experiments curve of the carbon supported platinum catalyst of carbon nano-tube prepared by the present embodiment and graphite flake layer complex carbon material and commercial use as shown in Figure 7.Concrete test method is: chrono-amperometric empirical curve rotating disk electrode (r.d.e) is measured in the potassium hydroxide solution of 0.1 mol/L containing 0.5 mol/L methyl alcohol, the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, constant potential is-0.2 volt, curved scanning speed is 10 millivolts/second, and test time is 100 seconds.
Curve relatively in two figure, can find out that the carbon nano-tube that the present embodiment prepares and graphite flake layer complex carbon material relative commercial carbon supported platinum catalyst have fabulous anti methanol toxication performance.
The stability test empirical curve of the carbon supported platinum catalyst of carbon nano-tube prepared by the present embodiment and graphite flake layer complex carbon material and commercial use as shown in Figure 8.Concrete test method is: chrono-amperometric empirical curve rotating disk electrode (r.d.e) is measured in the potassium hydroxide solution of saturated 0.1 mol/L of oxygen, the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, constant potential is-0.2 volt, curved scanning speed is 10 millivolts/second, and test time is 10000 seconds.
Relatively two curves, can find out that the carbon nano-tube that the present embodiment prepares and graphite flake layer complex carbon material relative commercial carbon supported platinum catalyst have better stability.
The preparation of embodiment 2, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially carbon nano-tube and graphite flake layer complex carbon material is prepared according to the method identical with embodiment 1, difference is: be changed to 900 DEG C by adopt during heat treatment 800 DEG C, it is suitable with the half wave potential that the composite material that embodiment 1 obtains obtains that the complex carbon material obtained tests half wave potential that hydrogen reduction curve obtains in the potassium hydroxide solution of 0.1 mole often liter, and the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity.
The preparation of embodiment 3, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially carbon nano-tube and graphite flake layer composite material is prepared according to the method identical with embodiment 1, difference is: be changed to 700 DEG C by adopt during heat treatment 800 DEG C, it is suitable with the half wave potential that the composite material that embodiment 1 obtains obtains that half wave potential that hydrogen reduction curve obtains tested by the composite material obtained in the potassium hydroxide solution of 0.1 mole often liter, and the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity.
The preparation of embodiment 4, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially prepare carbon nano-tube and graphite flake layer composite material according to the method identical with embodiment 1, difference is: adopt potassium chloride to substitute sodium chloride as dispersant and carrier, the composite material obtained forms the same with the catalyst that embodiment 1 obtains; In the potassium hydroxide solution of 0.1 mole often liter, test half wave potential that hydrogen reduction curve obtains suitable with the half wave potential that the composite material that embodiment 1 obtains obtains, the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity
The preparation of embodiment 5, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially prepare carbon nano-tube and graphite flake layer composite material according to the method identical with embodiment 1, difference is: adopt iron chloride to substitute ferric nitrate as molysite, the composite material obtained forms the same with the catalyst that embodiment 1 obtains; In the potassium hydroxide solution of 0.1 mole often liter, test half wave potential that hydrogen reduction curve obtains suitable with the half wave potential that the composite material that embodiment 1 obtains obtains, the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity
The preparation of embodiment 6, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially prepare carbon nano-tube and graphite flake layer composite material according to the method identical with embodiment 1, difference is: adopt cyanamide to substitute melamine as nitrogenous source, the catalyst obtained forms the same with the composite material that embodiment 1 obtains; In the potassium hydroxide solution of 0.1 mole often liter, test half wave potential that hydrogen reduction curve obtains suitable with the half wave potential that the composite material that embodiment 1 obtains obtains, the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity
The preparation of embodiment 7, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially prepare carbon nano-tube and graphite flake layer composite material according to the method identical with embodiment 1, difference is: adopt cane sugar substitution glucose as carbon source, the catalyst obtained forms the same with the composite material that embodiment 1 obtains; In the potassium hydroxide solution of 0.1 mole often liter, test half wave potential that hydrogen reduction curve obtains suitable with the half wave potential that the composite material that embodiment 1 obtains obtains, the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity
The preparation of embodiment 8, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially non noble metal oxygen reduction catalyst is prepared according to the method identical with embodiment 1, difference is: the inventory of sodium chloride changes 0.9 gram into by 3.5 grams, it is suitable with the half wave potential that the composite material that embodiment 1 obtains obtains that half wave potential that hydrogen reduction curve obtains tested by the catalyst obtained in the potassium hydroxide solution of 0.1 mole often liter, and the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity.
The preparation of embodiment 9, carbon nano-tube and graphite flake layer complex carbon material and reducing property test
Substantially non noble metal oxygen reduction catalyst is prepared according to the method identical with embodiment 1, difference is that the inventory of sodium chloride changes 11.2 grams into by 3.5 grams, it is suitable with the half wave potential that the composite material that embodiment 1 obtains obtains that half wave potential that hydrogen reduction curve obtains tested by the catalyst obtained in the potassium hydroxide solution of 0.1 mole often liter, and the carbon supported platinum catalyst of more commercial use shows better hydrogen reduction electro catalytic activity.
It should be noted that, above-described embodiment is only used to technical characteristic of the present invention is described, is not used to limit the claimed scope of the present invention.The carbon source related in such as embodiment, nitrogenous source, molysite, chlorate etc., also can use other reactant, but this type of carbon nano-tube and graphite flake layer composite material still belong to the claimed category of the present invention.
Claims (10)
1. a preparation method for complex carbon material, comprises the steps:
1) prepare presoma, described presoma is the mixture of carbon source, molysite and chlorate;
2) heat-treat after described presoma being mixed with nitrogenous source, obtain the heat-treated products containing described chlorate;
3) namely the described chlorate removed in described heat-treated products obtains described complex carbon material.
2. preparation method according to claim 1, is characterized in that: step 1) in, the step preparing described presoma is as follows:
Prepare the aqueous solution of described carbon source, described molysite and described chlorate, namely the moisture that the dry described aqueous solution is removed wherein with drying obtain described presoma.
3. preparation method according to claim 1 and 2, is characterized in that: described carbon source is selected from least one in glucose, sucrose, maltose and fructose;
Described molysite is selected from least one in iron chloride, ferric nitrate, ferric sulfate and ferric acetate;
Described chlorate is selected from least one in sodium chloride, potassium chloride, lithium chloride, magnesium chloride and calcium chloride;
Described nitrogenous source is selected from least one in melamine, nitrile ammonia and two nitrile ammonia.
4. the preparation method according to any one of claim 1-3, is characterized in that: the mass ratio that feeds intake of described carbon source and described molysite is 1:0.5 ~ 3;
The mass ratio that feeds intake of described carbon source and described chlorate is 1:1 ~ 30;
The mass ratio that feeds intake of described carbon source and described nitrogenous source is 1:0.5 ~ 20.
5. the preparation method according to any one of claim 1-4, is characterized in that: step 2) in, described presoma is mixed by grinding with described nitrogenous source;
Described heat treatment is carried out in a nitrogen atmosphere.
6. the preparation method according to any one of claim 1-5, is characterized in that: step 2) in, described heat treated temperature is 700 DEG C ~ 1000 DEG C; The described heat treated time is 0.5 hour ~ 8 hours.
7. the preparation method according to any one of claim 1-6, is characterized in that: step 3) in, remove the described chlorate in described heat-treated products by washing.
8. the complex carbon material prepared of method according to any one of claim 1-7.
9. complex carbon material according to claim 8, is characterized in that: described complex carbon material is made up of carbon nano-tube and graphite flake layer;
All doped with metallic iron and cementite nano particle in described carbon nano-tube and described graphite flake layer.
10. complex carbon material described in claim 8 or 9 is as the application in oxygen reduction catalyst.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106379882A (en) * | 2016-08-25 | 2017-02-08 | 陕西科技大学 | Preparation method of multi-level three-dimensional chain carbon nano net |
| CN109103469A (en) * | 2018-08-22 | 2018-12-28 | 广东工业大学 | A kind of Co3O4-CeO2/ N-CNTs oxygen reduction catalyst and its preparation method and application |
| CN109364978A (en) * | 2018-12-06 | 2019-02-22 | 滨州学院 | Class fenton catalyst preparation method and its application in treatment of Organic Wastewater |
| CN109546162A (en) * | 2018-10-26 | 2019-03-29 | 江苏大学 | A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material |
| CN109573983A (en) * | 2019-01-25 | 2019-04-05 | 青岛科技大学 | A kind of transition metal filling carbon nano-pipe, preparation method and application |
| CN110518265A (en) * | 2019-07-16 | 2019-11-29 | 南京工业大学 | A kind of platinum alloy catalyst, fused salt hot preparation method and Proton Exchange Membrane Fuel Cells |
| CN110635140A (en) * | 2019-08-14 | 2019-12-31 | 电子科技大学 | P-O doped Fe-N-C nanosheet and preparation method thereof |
| CN111554945A (en) * | 2020-05-27 | 2020-08-18 | 青岛科技大学 | High-efficiency carbon-based electrocatalyst and preparation method and application thereof |
| CN113845104A (en) * | 2021-08-11 | 2021-12-28 | 上海大学 | Nitrogen-doped carbon nanosheet-supported ferrous oxide quantum dot oxygen reduction electrocatalyst, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015792A (en) * | 2007-03-08 | 2007-08-15 | 复旦大学 | Titanium dioxide perforated micro-pipe photocatalyst modified by silver and its prodn. method |
| CN103706388A (en) * | 2013-12-30 | 2014-04-09 | 中国科学院化学研究所 | Composite material of nitrogen-doped porous carbon-wrapped carbon nano tube as well as preparation method and application of material |
| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
-
2015
- 2015-12-29 CN CN201511008255.3A patent/CN105470532B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015792A (en) * | 2007-03-08 | 2007-08-15 | 复旦大学 | Titanium dioxide perforated micro-pipe photocatalyst modified by silver and its prodn. method |
| CN103706388A (en) * | 2013-12-30 | 2014-04-09 | 中国科学院化学研究所 | Composite material of nitrogen-doped porous carbon-wrapped carbon nano tube as well as preparation method and application of material |
| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
Non-Patent Citations (1)
| Title |
|---|
| 江文杰: "高性能非贵金属燃料电池阴极催化剂的制备及性能研究", 《万方数据知识服务平台》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106379882A (en) * | 2016-08-25 | 2017-02-08 | 陕西科技大学 | Preparation method of multi-level three-dimensional chain carbon nano net |
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