CN105344369A - Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof - Google Patents
Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof Download PDFInfo
- Publication number
- CN105344369A CN105344369A CN201510850949.5A CN201510850949A CN105344369A CN 105344369 A CN105344369 A CN 105344369A CN 201510850949 A CN201510850949 A CN 201510850949A CN 105344369 A CN105344369 A CN 105344369A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nitrogen
- preparation
- cobalt
- oxygen reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of a three-dimensional hierarchical porous structure and a preparation method. According to the preparation method, a bovine bone is used as a carbon precursor, in-situ nitrogen doped hierarchical porous carbon prepared through activation and carbonization is used as a carrier, vitamin B12 of a cobalt-nitrogen chelated structure is used as a cobalt and nitrogen precursor, and the cobalt and nitrogen codoped carbon-based catalyst is prepared by pyrolyzing the porous carbon and vitamin B12 under the inert atmosphere at the same time, wherein the content of doped cobalt is 0.005-4%, and the content of doped nitrogen is 0.5-5%. Compared with the prior art, the catalyst is high in oxygen reduction catalytic activity and stability, high in poison resistance and good in mass transfer performance, the preparation method is simple and controllable, the precursors are low in price, and the preparation process is environmentally friendly. The catalyst can be widely applied to the fields of proton exchange membrane fuel cells, metal-air fuel cells and the like.
Description
Technical field
The invention belongs to technical field of electrochemistry, the cobalt nitrogen co-doped charcoal base oxygen reduction catalyst that there is three-dimensional graded porous structure in particular to a kind of, its preparation and the application in Proton Exchange Membrane Fuel Cells, metal-air fuel cell thereof.
Background technology
Oxygen reduction reaction (Oxygenreductionreaction, ORR) be Proton Exchange Membrane Fuel Cells and metal-air battery cathode electrode reaction, course of reaction activation energy is high, overpotential is large, need to utilize efficient electrode catalyst to improve reaction rate, thus promote that battery performance promotes.At present, precious metals pt is the most frequently used class catalyst of ORR, but it is Pt scarcity of resources, expensive, and in course of reaction, easily there is poisoning and sintering, this seriously constrains the commercial applications of Proton Exchange Membrane Fuel Cells and metal-air battery, therefore, the non noble metal oxygen reduction catalyst designing and developing low cost has great importance.
In the non-precious metal catalyst studied, the charcoal base oxygen reduction catalyst (transition metal-nitrogen-charcoal of transition metal and N doping, be called for short Me-N-C, Me is Fe or Co) owing to having higher oxygen reduction catalytic activity, stability and anti methanol toxication ability, be considered to the class non-precious metal catalyst being hopeful most to replace precious metals pt.But catalyst based compared to Pt, the catalytic activity of such catalyst is still lower, still can not meet the requirement of fuel cell practical application.Research shows, increasing number of active sites, optimizing pore passage structure is the key method improving such catalyst activity.In the process of preparation Me-N-C catalyst, the metal in presoma-nitrogen coordination structure (Me-N
x) and carbon surface chemical combination, inlay and enter carbon network, form Me-N on surface
xavtive spot, this process is mainly carried out in the micropore of below 2nm, and thus the final number of active sites formed affects larger by the micropore specific area of presoma; On the other hand, be communicated with mesoporous in the mesoporous and macropore strengthening mass transfer of the performance needs connection of Me-N-C catalytic activity, the active sites of maximum number fully contacted with reactant, thus improves the utilization rate of avtive spot.But the customary preparation methods of current Me-N-C catalyst relates to direct pyrolysis carbon source (common high-area carbon is if CNT, VulcanXC-72, Graphene etc. or Small molecular carbon source are as phenolic resins etc.), nitrogenous source (as ethylenediamine, aniline, pyridine, acetonitrile and polymer with nitrogen) and transition metal source (as cobalt chloride, ferric nitrate etc.).This preparation method, owing to taking carbon source that pore structure is comparatively single as high-area carbon, causes catalyst pore structure not easy-regulating; On the other hand, the Me-N that formed of the presoma of the transition metal that uses of above-mentioned preparation method and nitrogen
xcoordination bond energy is lower, the dissociating of nitrogen easily occurs under high temperature, volatilizees, cause the catalyst activity bits number prepared to decline, thus be difficult to obtain higher catalytic activity.Therefore, the base metal Me-N-C Catalysts and its preparation method with three-dimensional graded porous structure of research and development high activity, low cost is significant.
Summary of the invention
A kind of effective method is the object of the present invention is to provide to have the cobalt nitrogen co-doped charcoal base oxygen reduction catalyst of three-dimensional graded porous structure, with the raising of promoting catalyst activity with preparation.The preparation method that this catalyst adopts is simple and easy to control, presoma abundance, cheap, and preparation process environmental friendliness, can realize large-scale production.
For achieving the above object, this catalyst adopts natural composite organic-inorganic material---and ox bone is as carbon precursor, ox bone is dispersed in the organic matter of collagen based on nanoscale in order by inorganic compounds such as nanometer hydroxyapatites, has exquisite orderly classification layered nano-structure and composition sequence.Wherein carbon source protein phosphorus content is high, and is rich in the functional groups such as hydroxyl, carboxyl, amino and sulfydryl, realizes in-situ surface doping porous charcoal by regulation and control carbonisation; And the inorganic matters such as nanometer hydroxyapatite can be used as native template, by the control regulation and control Crystal Structure of Hydroxyapatite of calcining heat, pickling can realize the regulation and control of pore structure after removing template; In ox bone carbonisation, adopt co-activating carbonization method, by controlling the ratio of activator and carbonized product, the pore structure of regulation and control porous charcoal, increases micropore ratio, is conducive to the formation of three-dimensional hierarchical porous structure, increasing specific surface area.In addition; adopt the vitamin B12 with cobalt-nitrogen chelate structure as unique presoma of cobalt, nitrogen; by preparing cobalt nitrogen co-doped charcoal base oxygen reduction catalyst with the pyrolysis simultaneously under inert atmosphere protection of classifying porous charcoal; wherein cation doping content is 0.005 ~ 4%, and the content of doping nitrogen is 0.5 ~ 5%.This catalyst has three-dimensional graded porous structure, i.e. the pore passage structure that is interconnected of macropore, mesoporous, micropore, and wherein micropore is conducive to grappling Co-N
xavtive spot, mesoporous and macropore is conducive to reactant and product mass transfer, thus improves the catalytic activity of catalyst further.
The technical solution used in the present invention is as follows:
(1), after ox bone being cleaned, being ground into bone meal, be positioned in tube furnace, pass into inert gas, raised temperature to 300 ~ 500
oc carbonization, obtains pre-carbonized product.Wherein heating rate is 1 ~ 10
ocmin
-1, temperature retention time is 1 ~ 3h;
(2) by above-mentioned pre-carbonized product and activator ground and mixed evenly after, with 1 ~ 10 under inert gas shielding
ocmin
-1be warming up to 600 ~ 1200
oc, insulation 1 ~ 3h, obtain activating carbonized product.Wherein the ratio of pre-carbonized product and activator is 1:0.5 ~ 1:3;
(3) above-mentioned cooled carbonized product is placed in salpeter solution stirring and pickling 8 ~ 15h, then after washing, drying, obtains classifying porous charcoal.Described salpeter solution concentration is 1 ~ 3M, and baking temperature is 100 ~ 120
oc, drying time is 12 ~ 24h;
(4) get appropriate vitamin B12 fully mix with above-mentioned porous charcoal and be dispersed in a certain amount of solvent, ultrasonic, stir after, evaporate to dryness obtains the homogeneous mixture of porous charcoal and vitamin B12;
(5) by the mixture of porous charcoal and vitamin B12 under inert gas shielding with 3 ~ 6
ocmin
-1be warming up to 600 ~ 1000
oc, insulation 1 ~ 3h, to be cooled to room temperature, obtain the carbon base catalyst that cobalt is nitrogen co-doped after grinding.
In a preferred embodiment of the present invention, described activator is potassium hydroxide.
In a preferred embodiment of the present invention, described inert atmosphere is by the mixed atmosphere of nitrogen or argon gas atmosphere or above-mentioned two kinds of gases.
In a preferred embodiment of the present invention, the quality of described appropriate vitamin B12 and the mass ratio of porous charcoal are 0.2 ~ 5.
In a preferred embodiment of the present invention, described solvent is water or ethanol, and evaporate to dryness method is rotary evaporation.
The present invention also relates to the catalyst prepared by described method on the other hand, the three-dimensional graded porous structure that its pattern is macropore, mesoporous, micropore is interconnected, the aperture of described macropore is 50 ~ 500nm, mesoporous pore size is 2 ~ 50nm, the hole wall of described macropore has pore diameter range at the micropore of 0.5 ~ 2nm.
Described catalyst can be used for the oxygen reduction catalyst of Proton Exchange Membrane Fuel Cells, metal-air battery.
Compared with prior art, the present invention at least have the following advantages in one or more or all:
1. excellent oxygen reduction catalytic activity and electrochemical stability.The present invention creatively introduces natural organic/inorganic composite material---and ox bone, as carbon precursor, prepares by pre-carbonization, activation carbonization the nitrogenous porous charcoal that high surface has three-dimensional hierarchical porous structure; And using there is the vitamin B12 of cobalt-nitrogen chelate structure as cobalt, nitrogen presoma, with nitrogenous porous charcoal copyrolysis, realizing avtive spot and being evenly anchored in porous charcoal substrate.
2. excellent mass-transfer performance.Adopt catalyst prepared by the method for the invention, because this catalyst has hierarchical porous structure and the high surface of three-dimensional communication, compared to conventional carbon substrate (as VulcanXC-72), the avtive spot of maximum number can be made fully to contact with reactant, and mass-transfer performance is more excellent.
3. excellent anti methanol toxication performance.By comparing the chronoa mperometric plot added before and after methyl alcohol, catalyst prepared by the embodiment of the present invention does not change substantially.
4. presoma is common is easy to get, with low cost, environmental friendliness, and preparation process is easy to control, simple to operate, is easy to batch production.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of Fig. 1 to be ox bone be classifying porous charcoal of presoma (HPC);
Fig. 2 is the scanning electron microscope (SEM) photograph of the nitrogen co-doped carbon base catalyst of cobalt with three-dimensional graded porous structure;
Fig. 3 is the cobalt nitrogen co-doped carbon base catalyst Co-N-HPC-1 polarization curve with three-dimensional graded porous structure, and illustration is cyclic voltammetry scan figure;
Fig. 4 is the nitrogen adsorption desorption curve of the nitrogen co-doped carbon base catalyst Co-N-HPC-2 of cobalt with three-dimensional graded porous structure;
Fig. 5 be there is the nitrogen co-doped charcoal of three-dimensional graded porous structure cobalt (Co-N-HPC-2), the linear scan figure of the nitrogen co-doped charcoal of cobalt (Co-N-C) that VulcanXC-72 is carrier, commercialization 20%Pt/C catalyst;
Fig. 6 is the chronoamperogram of the operation 10000s with the nitrogen co-doped charcoal of three-dimensional graded porous structure cobalt (Co-N-HPC-3) and commercialization 20%Pt/C catalyst;
Fig. 7 has the nitrogen co-doped charcoal of three-dimensional graded porous structure cobalt (Co-N-HPC-3) and poisons curve with the methanol tolerance of commercialization 20%Pt/C catalyst.
Detailed description of the invention
The preparation of the classifying porous charcoal of embodiment 1
After being cleaned by ox bone, being ground into bone meal, placing in tube furnace, is 200sccmin at flow
-1high-purity argon gas protection under, with 5
oCmin
-1be warming up to 400
oc carbonization, stops heating after insulation 3h, naturally cools to room temperature, obtain pre-carbonized product; Take the pre-carbonized product of 5g more even than ground and mixed by 1:1 quality with activator KOH, with 2.5 under argon shield
oCmin
-1be warming up to 850
oC, naturally cool to room temperature after insulation 1h, obtain activating carbonized product; Then above-mentioned activation carbonized product is placed in 2MHNO
3in solution, stirring and pickling 12h, then spends deionized water, and 110
oafter the dry 12h of C, obtain classifying porous charcoal, its stereoscan photograph is shown in Fig. 1.
The preparation of the nitrogen co-doped classifying porous Pd/carbon catalyst of cobalt
Take 0.4g vitamin B12 and the classifying porous charcoal of 0.2g fully mixes dispersion in ethanol, ultrasonic 30min, stir 30min, use Rotary Evaporators in 80
oc solvent evaporated, by the compound of said vitamin B12 and classifying porous charcoal under argon shield with 5
ocmin
-1ramp to 800
oc, naturally cool after insulation 2h, obtain the cobalt nitrogen co-doped charcoal base oxygen reduction catalyst Co-N-HPC-1 with three-dimensional hierarchical porous structure, its stereoscan photograph is shown in Fig. 2.This catalyst shows excellent oxygen reduction catalytic activity, sees Fig. 3.
Embodiment 2
Adopt the preparation process of embodiment 1, be with its difference, the use amount of classifying porous charcoal is increased to 0.4g, obtained CATALYST Co-N-HPC-2.Tested by Fig. 3 nitrogen adsorption desorption curve and show that this catalyst has higher specific area, reach 859.1m
2g
-1, wherein, micropore accounting 28.7%, mesoporous accounting 65.8%, macropore accounting 5.5%.Its catalytic oxidation-reduction reactivity curve is shown in Fig. 4, and compared to the Co-N-C catalyst adopting common high-area carbon VulcanXC-72 to prepare, this catalyst has higher half wave potential and dynamics electric current, shows excellent oxygen reduction catalytic activity; In addition, this catalyst also has larger limiting diffusion current, and mass-transfer performance is excellent.
Embodiment 3
Adopt the preparation process of embodiment 1, be with its difference, the heat treatment temperature of vitamin B12 and classifying porous charcoal is reduced to 700
oc prepares CATALYST Co-N-HPC-3, and this catalyst not only has excellent oxygen reduction catalytic activity, and shows outstanding electrochemical stability and anti methanol toxication ability, sees Fig. 6,7.
Above to invention has been exemplary description; obvious realization of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all in protection scope of the present invention without to improve.
Claims (10)
1. have a cobalt nitrogen co-doped charcoal base oxygen reduction catalyst for three-dimensional graded porous structure, cation doping content is 0.005 ~ 4%, and the content of doping nitrogen is 0.5 ~ 5%; It is characterized in that the three-dimensional graded porous structure that its pattern is macropore, mesoporous, micropore is interconnected, the aperture of described macropore is 50 ~ 500nm, and mesoporous pore size is 2 ~ 50nm, the hole wall of described macropore has pore diameter range at the micropore of 0.5 ~ 2nm.
2. catalyst according to claim 1, is characterized in that described specific surface area of catalyst is between 700-1000m
2g
-1between.
3. catalyst according to claim 2, is characterized in that macropore, 5-10%, 60-70% and the 25-40% that mesoporous, micropore is respectively catalyst volume.
4. the preparation method of the catalyst described in claim 1-3 any one, is characterized in that comprising following preparation process:
(1), after ox bone being cleaned, shattering into bone meal, be positioned in tube furnace, pass into inert gas, raised temperature to 300 ~ 500
oc carbonization, obtains pre-carbonized product, and wherein heating rate is 1 ~ 10
ocmin
-1, temperature retention time is 1 ~ 3h;
(2) by above-mentioned pre-carbonized product and activator ground and mixed evenly after, with 1 ~ 10 under inert gas shielding
ocmin
-1be warming up to 600 ~ 1200
oc, insulation 1 ~ 3h, obtain activating carbonized product, and wherein the ratio of pre-carbonized product and activator is 1:0.5 ~ 1:3;
(3) above-mentioned cooled carbonized product is placed in salpeter solution stirring and pickling 8 ~ 15h, then after washing, drying, obtain classifying porous charcoal, described salpeter solution concentration is 1 ~ 3M, and baking temperature is 50 ~ 80
oc, drying time is 4 ~ 24h;
(4) get appropriate vitamin B12 fully mix with above-mentioned porous charcoal and be dispersed in a certain amount of solvent, ultrasonic, stir after, evaporate to dryness obtains the homogeneous mixture of porous charcoal and vitamin B12;
(5) by the mixture of porous charcoal and vitamin B12 under inert gas shielding with 3 ~ 6
ocmin
-1be warming up to 600 ~ 1000
oc, insulation 1 ~ 3h, to be cooled to room temperature, obtain the carbon base catalyst that cobalt is nitrogen co-doped after grinding.
5., according to the preparation method described in claim 4, it is characterized in that described activator is potassium hydroxide.
6., according to the preparation method described in claim 4, it is characterized in that described inert atmosphere is the mixed atmosphere of nitrogen or argon gas atmosphere or above-mentioned two kinds of gases.
7., according to the preparation method described in claim 4, it is characterized in that the mass ratio of described vitamin B12 and porous charcoal is 0.2 ~ 5:1.
8., according to the preparation method described in claim 4, it is characterized in that described solvent is water and/or ethanol.
9. the nitrogen co-doped charcoal base of the cobalt with the three-dimensional graded porous structure oxygen reduction catalyst prepared by the preparation method described in claim 4-8 any one.
10. the application of claim 1-3 and the catalyst described in 9 any one, is characterized in that the oxygen reduction reaction of described catalyst for Proton Exchange Membrane Fuel Cells, metal-air battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510850949.5A CN105344369B (en) | 2015-11-30 | 2015-11-30 | The nitrogen co-doped charcoal base oxygen reduction catalyst of cobalt and its preparation and application with three-dimensional graded porous structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510850949.5A CN105344369B (en) | 2015-11-30 | 2015-11-30 | The nitrogen co-doped charcoal base oxygen reduction catalyst of cobalt and its preparation and application with three-dimensional graded porous structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105344369A true CN105344369A (en) | 2016-02-24 |
| CN105344369B CN105344369B (en) | 2017-12-12 |
Family
ID=55320511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510850949.5A Active CN105344369B (en) | 2015-11-30 | 2015-11-30 | The nitrogen co-doped charcoal base oxygen reduction catalyst of cobalt and its preparation and application with three-dimensional graded porous structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105344369B (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106207197A (en) * | 2016-07-08 | 2016-12-07 | 北京化工大学 | A kind of method using hair to prepare bifunctional electrocatalyst |
| CN107176598A (en) * | 2016-03-08 | 2017-09-19 | 中国科学院青岛生物能源与过程研究所 | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application |
| CN108155371A (en) * | 2017-12-25 | 2018-06-12 | 哈尔滨师范大学 | The method that nanoscale antimony base transition metal oxide sodium ion battery electrode material is prepared using discarded animal organic matter as template |
| CN108199053A (en) * | 2018-01-04 | 2018-06-22 | 吉林大学 | A kind of preparation method of high efficiency, low cost oxygen reduction catalyst |
| CN108232208A (en) * | 2016-12-22 | 2018-06-29 | 现代自动车株式会社 | Method for the mixed catalyst of fuel cell and for manufacturing it |
| CN108232205A (en) * | 2016-12-21 | 2018-06-29 | 现代自动车株式会社 | Base metal class catalyst and its manufacturing method |
| WO2018120067A1 (en) * | 2016-12-30 | 2018-07-05 | The University Of Hong Kong | Waste biomass-derived metal-free catalysts for oxygen reduction reaction |
| CN108970577A (en) * | 2018-07-17 | 2018-12-11 | 西北农林科技大学 | A kind of mesoporous carbon nanosheet of Co/N codope and preparation method and application |
| CN109174157A (en) * | 2018-09-27 | 2019-01-11 | 合肥工业大学 | A kind of preparation method of the nitrogen co-doped biomass carbon oxidation reduction catalyst of cobalt |
| CN109304204A (en) * | 2018-11-06 | 2019-02-05 | 中国人民解放军陆军勤务学院 | The graphite-phase nitrogen carbide composite material of phosphorus doping Cobaltosic oxide quantum dot modification, and its preparation method and application |
| CN110400936A (en) * | 2019-08-15 | 2019-11-01 | 中国科学技术大学 | A kind of high power fuel cell membrane electrode, preparation method and application |
| CN111001427A (en) * | 2019-12-24 | 2020-04-14 | 山西大学 | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof |
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111697239A (en) * | 2020-06-28 | 2020-09-22 | 全球能源互联网研究院有限公司 | Cobalt-iron alloy and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof |
| CN111729684A (en) * | 2020-07-21 | 2020-10-02 | 南京大学 | Hierarchical porous Co-N-C type catalyst and preparation method and application thereof |
| CN113363508A (en) * | 2021-02-02 | 2021-09-07 | 井冈山大学 | Electrocatalyst for fuel cell and preparation method thereof |
| CN113457708A (en) * | 2021-06-30 | 2021-10-01 | 常州大学 | CoN @ C porous material, preparation method thereof and application of CoN @ C porous material in synthesis of aromatic nitrile compound |
| CN113546664A (en) * | 2021-07-25 | 2021-10-26 | 湘潭大学 | Cobalt-nitrogen co-doped fish scale biochar catalyst and preparation method and application thereof |
| CN113809341A (en) * | 2021-07-30 | 2021-12-17 | 五邑大学 | Cu-N-C oxygen reduction catalyst and preparation method thereof |
| CN115266895A (en) * | 2022-07-27 | 2022-11-01 | 南京信息工程大学 | Preparation method and application of novel bimetallic Co/CoFe heterostructure carbon material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811775A (en) * | 2014-03-06 | 2014-05-21 | 南开大学 | Porous nano composite material for fuel cell oxygen reduction catalyst |
| CN104258892A (en) * | 2014-09-02 | 2015-01-07 | 中国科学院上海硅酸盐研究所 | N-doped meso-macro hierarchical porous carbon oxygen reduction catalyst material and preparation method thereof |
| WO2015040638A1 (en) * | 2013-09-19 | 2015-03-26 | Council Of Scientific & Industrial Research | N-doped porous carbon electrocatalyst and process for preparation thereof |
| CN104953135A (en) * | 2015-04-30 | 2015-09-30 | 北京化工大学 | N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof |
-
2015
- 2015-11-30 CN CN201510850949.5A patent/CN105344369B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015040638A1 (en) * | 2013-09-19 | 2015-03-26 | Council Of Scientific & Industrial Research | N-doped porous carbon electrocatalyst and process for preparation thereof |
| CN103811775A (en) * | 2014-03-06 | 2014-05-21 | 南开大学 | Porous nano composite material for fuel cell oxygen reduction catalyst |
| CN104258892A (en) * | 2014-09-02 | 2015-01-07 | 中国科学院上海硅酸盐研究所 | N-doped meso-macro hierarchical porous carbon oxygen reduction catalyst material and preparation method thereof |
| CN104953135A (en) * | 2015-04-30 | 2015-09-30 | 北京化工大学 | N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HONGLIANG JIANG ET AL.: "Nitrogen and Phosphorus Dual-Doped Hierarchical Porous Carbon Foams as Efficient Metal-Free Electrocatalysts for Oxygen Reduction Reactions", 《CHEM. EUR. J.》 * |
| SHUJUN CHAO ET AL.: "Hollowed-out octahedral Co/N-codoped carbon as a highly efficient non-precious metal catalyst for oxygen reduction reaction", 《CARBON》 * |
| 张蓉 等: "过渡金属/氮掺杂石墨催化剂的制备及电催化氧还原", 《分子催化》 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107176598A (en) * | 2016-03-08 | 2017-09-19 | 中国科学院青岛生物能源与过程研究所 | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application |
| CN106207197A (en) * | 2016-07-08 | 2016-12-07 | 北京化工大学 | A kind of method using hair to prepare bifunctional electrocatalyst |
| CN108232205A (en) * | 2016-12-21 | 2018-06-29 | 现代自动车株式会社 | Base metal class catalyst and its manufacturing method |
| CN108232205B (en) * | 2016-12-21 | 2022-10-11 | 现代自动车株式会社 | Non-noble metal catalyst and process for producing the same |
| CN108232208A (en) * | 2016-12-22 | 2018-06-29 | 现代自动车株式会社 | Method for the mixed catalyst of fuel cell and for manufacturing it |
| WO2018120067A1 (en) * | 2016-12-30 | 2018-07-05 | The University Of Hong Kong | Waste biomass-derived metal-free catalysts for oxygen reduction reaction |
| CN108155371A (en) * | 2017-12-25 | 2018-06-12 | 哈尔滨师范大学 | The method that nanoscale antimony base transition metal oxide sodium ion battery electrode material is prepared using discarded animal organic matter as template |
| CN108199053A (en) * | 2018-01-04 | 2018-06-22 | 吉林大学 | A kind of preparation method of high efficiency, low cost oxygen reduction catalyst |
| CN108199053B (en) * | 2018-01-04 | 2020-06-09 | 吉林大学 | Preparation method of oxygen reduction catalyst |
| CN108970577A (en) * | 2018-07-17 | 2018-12-11 | 西北农林科技大学 | A kind of mesoporous carbon nanosheet of Co/N codope and preparation method and application |
| CN108970577B (en) * | 2018-07-17 | 2021-05-11 | 西北农林科技大学 | Application of Co/N Co-doped mesoporous carbon nanosheet |
| CN109174157A (en) * | 2018-09-27 | 2019-01-11 | 合肥工业大学 | A kind of preparation method of the nitrogen co-doped biomass carbon oxidation reduction catalyst of cobalt |
| CN109304204B (en) * | 2018-11-06 | 2021-04-02 | 中国人民解放军陆军勤务学院 | Phosphorus-doped cobaltosic oxide quantum dot modified graphite phase nitrogen carbide composite material, and preparation method and application thereof |
| CN109304204A (en) * | 2018-11-06 | 2019-02-05 | 中国人民解放军陆军勤务学院 | The graphite-phase nitrogen carbide composite material of phosphorus doping Cobaltosic oxide quantum dot modification, and its preparation method and application |
| CN110400936A (en) * | 2019-08-15 | 2019-11-01 | 中国科学技术大学 | A kind of high power fuel cell membrane electrode, preparation method and application |
| CN111001427A (en) * | 2019-12-24 | 2020-04-14 | 山西大学 | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof |
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111250008B (en) * | 2020-02-08 | 2021-09-21 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111697239A (en) * | 2020-06-28 | 2020-09-22 | 全球能源互联网研究院有限公司 | Cobalt-iron alloy and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof |
| CN111729684A (en) * | 2020-07-21 | 2020-10-02 | 南京大学 | Hierarchical porous Co-N-C type catalyst and preparation method and application thereof |
| CN113363508A (en) * | 2021-02-02 | 2021-09-07 | 井冈山大学 | Electrocatalyst for fuel cell and preparation method thereof |
| CN113457708A (en) * | 2021-06-30 | 2021-10-01 | 常州大学 | CoN @ C porous material, preparation method thereof and application of CoN @ C porous material in synthesis of aromatic nitrile compound |
| CN113457708B (en) * | 2021-06-30 | 2023-10-20 | 常州大学 | CoN@C porous material, preparation method thereof and application thereof in synthesis of aromatic nitrile compound |
| CN113546664A (en) * | 2021-07-25 | 2021-10-26 | 湘潭大学 | Cobalt-nitrogen co-doped fish scale biochar catalyst and preparation method and application thereof |
| CN113809341A (en) * | 2021-07-30 | 2021-12-17 | 五邑大学 | Cu-N-C oxygen reduction catalyst and preparation method thereof |
| CN115266895A (en) * | 2022-07-27 | 2022-11-01 | 南京信息工程大学 | Preparation method and application of novel bimetallic Co/CoFe heterostructure carbon material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105344369B (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105344369A (en) | Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof | |
| CN110752380A (en) | ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof | |
| CN108754531B (en) | Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material | |
| Ma et al. | MOF-derived N-doped carbon coated CoP/carbon nanotube Pt-based catalyst for efficient methanol oxidation | |
| GB2603717A (en) | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof | |
| Kong et al. | Atomically dispersed Mn–N 4 electrocatalyst with high oxygen reduction reaction catalytic activity from metal–organic framework ZIF-8 by minimal-water-assisted mechanochemical synthesis | |
| CN112652780B (en) | Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst | |
| CN108579718B (en) | Preparation method and application of indium-doped nano porous carbon material | |
| CN103515624A (en) | Carbon supported non-noble metal oxygen reduction compound catalyst, and preparation method and application thereof | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN112736257B (en) | Embedded porous Fe-NxPreparation method of @ Pd-NC nanorod, nanorod prepared by preparation method and application of nanorod | |
| CN104645989A (en) | Heteroatom-doping porous carbon material and preparation method thereof | |
| Wu et al. | A graphene-based electrocatalyst co-doped with nitrogen and cobalt for oxygen reduction reaction | |
| CN113105645A (en) | Preparation method, product and application of nickel-based metal organic framework compound | |
| CN113594479A (en) | Preparation method of Fe and N co-doped porous carbon zinc air battery catalyst | |
| CN112357902A (en) | Mesoporous carbon material with high specific surface area, and preparation method and application thereof | |
| CN108649237A (en) | A kind of cobalt-nitrogen-doped carbon composite material and preparation method and application based on gel pyrolysis | |
| CN113430554B (en) | Monoatomic nickel-nitrogen coordination co-doped porous carbon/nano zirconia composite electrode and preparation method and application thereof | |
| An et al. | Engineering gC 3 N 4 composited Fe-UIO-66 to in situ generate robust single-atom Fe sites for high-performance PEMFC and Zn–air battery | |
| Quílez-Bermejo et al. | Easy enrichment of graphitic nitrogen to prepare highly catalytic carbons for oxygen reduction reaction | |
| CN101181679B (en) | Meso-porous C/WO3 electro-catalyst and preparation method thereof | |
| CN114574894A (en) | Ruthenium-molybdenum carbide composite material and preparation method and application thereof | |
| CN102810678A (en) | Direct methanol fuel cell catalyst and preparation method thereof | |
| CN111193039B (en) | Method for preparing oxygen reduction catalyst from biomass and product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |