CN106861745A - A kind of Fe N C/ α MnO2/β‑MnO2The preparation method of catalyst - Google Patents
A kind of Fe N C/ α MnO2/β‑MnO2The preparation method of catalyst Download PDFInfo
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- CN106861745A CN106861745A CN201710123924.4A CN201710123924A CN106861745A CN 106861745 A CN106861745 A CN 106861745A CN 201710123924 A CN201710123924 A CN 201710123924A CN 106861745 A CN106861745 A CN 106861745A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to fuel cell catalyst technical field, specifically related to a kind of preparation method of Fe N C/ α MnO2/ β MnO2 catalyst, the preparation method of new Fe N C/ α MnO2/ β MnO2 catalyst of the invention, using inexpensive raw material, synthetic route is simple and easy to apply, synthesis low cost, is adapted to mass industrialized production, obtained Fe N C/ α MnO2/β‑MnO2The catalysis activity of catalyst is high, stable performance, by the Fe N C/ α MnO prepared by the method for the present invention2/β‑MnO2Catalyst in the application of air cell or fuel cell, with very big development potentiality.
Description
Technical field
The present invention relates to fuel cell catalyst technical field, and in particular to a kind of Fe-N-C/ α-MnO2/ β-MnO2 catalysis
The preparation method of agent.
Background technology
Recent years, metal-air battery and fuel cell have energy density high because of it, using it is safe the advantages of, and be subject to
Extensive concern.One of core technology of metal-air battery and fuel cell is how to prepare cheap and excellent performance stabilization
Catalyst.
In metal-air battery or fuel cell, catalyst not only determines the performance of battery, also determines battery
Cost.Platinum is used as catalyst, although catalysis activity is good, but expensive, it is difficult to large-scale use；Noble silver, it may have
Good catalysis activity, but it is same because the reason for its is with high costs, causes to be difficult to large-scale use；Later Many researchers exist
In the oxide of manganese, suitable catalyst is found, the oxide of manganese is with low cost, but urging containing Mn oxide in the prior art
The catalysis activity of agent is unsatisfactory, needs further raising.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art providing a kind of new Fe-N-C/ α-MnO2/ β-MnO2
The preparation method of catalyst, using inexpensive raw material, synthetic route is simple and easy to apply, synthesizes low cost, is adapted to large-batch industrial
Production, obtained Fe-N-C/ α-MnO2/β-MnO2The catalysis activity of catalyst is high, stable performance.
The present invention is achieved through the following technical solutions the purpose：
A kind of preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst, comprises the following steps：
1) carbon material is chosen, then the carbon material is added to carbon material treatment fluid, 1~48h of stirring is carried out at activation
Reason, obtains mixture A after filtering；
2) by the compound and amino acids material or organic nitrogenous fertilizer class material of obtained mixture A and iron, by mole
Than being 1：0.01~0.125：0.0625~0.625 1~36h of mixing and ball milling, obtains mixture B；
3) by mixture B in N2500~1200 DEG C of constant temperature process 1~8h in atmosphere, then by dilute acid soln acidification 1
~12h, then suction filtration rinse to neutrality, obtain mixture C；
4) according to mass ratio it is 1~3 by the compound solution of mixture C and manganese：Reactor 1 is added separately to after 5 mixing
With reactor 2, the hydrothermal temperature of reactor 1 is 100~200 DEG C, and the reaction time is 1~3h, obtains mixture D 1；Reaction
The hydrothermal temperature of kettle 2 is 100~200 DEG C, and the reaction time is 3~12h, obtains mixture D 2；
5) by mixture D 1 and D2 in mass ratio 1：6~3：7 mixing, 100~150 DEG C of 1~48h of drying, 2~24h of ball milling,
Catalyst Fe-N-C/ α-MnO2/ β-MnO2 are obtained.
As preferred scheme, the step 1) in carbon material for graphite powder, carbon black, acetylene black, hard carbon, carbon fiber,
Any one in porous activated carbon or two or more mixtures.
As preferred scheme, the step 1) in carbon material treatment fluid be K2CO3Solution, KOH solution or hydrogen peroxide.
As preferred scheme, the K2CO3The concentration of solution, KOH solution or hydrogen peroxide is 10%~saturation.
As preferred scheme, the step 2) in iron compound be FeCl2·4H2O、FeSO4Or Fe (Ac)2。
As preferred scheme, the step 2) in amino acids material be glycine or Pidolidone.
As preferred scheme, the step 2) in organic nitrogenous fertilizer class material be urea or ammonium sulfate.
As preferred scheme, the step 3) in dilute acid soln be sulfuric acid, hydrochloric acid or salpeter solution.
Used as preferred scheme, the concentration of the sulfuric acid, hydrochloric acid or salpeter solution is 0.1~2mol/L.
As preferred scheme, the step 4) in manganese compound solution for liquor potassic permanganate or manganese oxalate it is molten
Liquid.
Relative to prior art, beneficial effects of the present invention are：New Fe-N-C/ α-MnO2/ β-MnO2 of the invention
The preparation method of catalyst, using inexpensive raw material, synthetic route is simple and easy to apply, synthesizes low cost, is adapted to large-batch industrial
Production, obtained Fe-N-C/ α-MnO2/β-MnO2The catalysis activity of catalyst is high, stable performance.
Brief description of the drawings
Fig. 1 is Fe-N-C/ α-MnO2/ β-MnO2 catalyst of the invention and noble metal catalyst in the prior art
The polarization curve comparison diagram of 50wt.%Pt/C.
Specific embodiment
Below in conjunction with drawings and the specific embodiments, the present invention will be described in detail.
Embodiment 1.
1) graphite powder, the three kinds of carbon material mixing of acetylene black and carbon black are chosen, it is 5% that then mixture is added to concentration
K2CO3Solution, stirring 48h carries out activation process, and mixture A is obtained after filtering；
2) by mixture A, FeCl2·4H2O and glycine are according to 1：0.06：0.25 ratio mixing and ball milling 36h, obtains
To mixture B；
3) by mixture B in N2500 DEG C of constant temperature treatment 8h in atmosphere, then by 2mol/L HCl treatment 1h, then suction filtration
Rinsing obtains mixture C to neutrality；
4) by the compound solution of mixture C and manganese according to 3：5 ratio mixing, adds to reactor 1 and reactor 2,
The hydrothermal temperature of reactor 1 is 100~200 DEG C, and the reaction time is 1~3h, obtains mixture D 1；The hydro-thermal of reactor 2
Reaction temperature is 100~200 DEG C, and the reaction time is 3~12h, obtains mixture D 2；
5) by D1 and D2 in mass ratio 1：6 mixing, 100~150 DEG C of 1~48h of drying, 2~24h of ball milling are obtained catalyst
Fe-N-C/α-MnO2/β-MnO2。
Embodiment 2.
1) hard carbon, the three kinds of carbon material mixing of carbon fiber and porous activated carbon are chosen, then mixture is added to concentration
It is 30% KOH solution, stirring 12h carries out activation process, and mixture A is obtained after filtering；
2) by mixture A, FeSO4And urea is according to 1：0.1：0.5 ratio mixing and ball milling 24h, obtains mixture B；
3) by mixture B in N21000 DEG C of constant temperature treatment 5h in atmosphere, then by 1mol/L HCl treatment 6h, then suction filtration
Rinsing obtains mixture C to neutrality；
4) by the compound solution of mixture C and manganese according to 2：5 ratio mixing, adds to reactor 1 and reactor 2,
The hydrothermal temperature of reactor 1 is 100~200 DEG C, and the reaction time is 1~3h, obtains mixture D 1；The hydro-thermal of reactor 2
Reaction temperature is 100~200 DEG C, and the reaction time is 3~12h, obtains mixture D 2；
5) by D1 and D2 in mass ratio 3：5 mixing, 100~150 DEG C of 1~48h of drying, 2~24h of ball milling are obtained catalyst
Fe-N-C/α-MnO2/β-MnO2。
Embodiment 3.
1) graphite powder, the three kinds of carbon material mixing of carbon black and porous activated carbon are chosen, then mixture is added to concentration
It is the hydrogen peroxide solution of saturation, stirring 1h carries out activation process, and mixture A is obtained after filtering；
2) by mixture A, Fe (Ac)2And Pidolidone is according to 1：0.125：0.525 ratio mixing and ball milling 1h, obtains
To mixture B；
3) by mixture B in N21200 DEG C of constant temperature treatment 1h in atmosphere, then by 0.2mol/L HCl treatment 12h, then
Suction filtration is rinsed to neutrality, obtains mixture C；
4) by the compound solution of mixture C and manganese according to 1：5 ratio mixing, adds to reactor 1 and reactor 2,
The hydrothermal temperature of reactor 1 is 100~200 DEG C, and the reaction time is 1~3h, obtains mixture D 1；The hydro-thermal of reactor 2
Reaction temperature is 100~200 DEG C, and the reaction time is 3~12h, obtains mixture D 2；
5) by D1 and D2 in mass ratio 3：7 mixing, 100~150 DEG C of 1~48h of drying, 2~24h of ball milling are obtained catalyst
Fe-N-C/α-MnO2/β-MnO2。
Compliance test result test.
Experiment material 1：Fe-N-C/ α-MnO prepared by the present invention2/β-MnO2Catalyst.
Experiment material 2：50wt.%Pt/C catalyst of the prior art.
Above-mentioned experiment material 1,2 is measured under the conditions of oxygen atmosphere, room temperature, alkaline electrolyte polarization curve respectively
Figure, as shown in Figure 1.
Test result indicate that：Fe-N-C/ α-MnO of the invention2/β-MnO2Catalyst shows excellent hydrogen reduction performance.
Under the conditions of current potential is -0.6V, limiting current density can reach 5.1mAcm-2, and show excellent electric current platform, table
Understand and maintain a complete mass transfer conditions in the case where potential range is -0.3V~-0.8V.For take-off potential, and
50wt.%Pt/C catalyst is compared, Fe-N-C/ α-MnO2/β-MnO2Catalyst only has the deviation of 80mV, closely platinum
Catalysis activity.Therefore, by the Fe-N-C/ α-MnO prepared by the method for the present invention2/β-MnO2Catalyst is in air cell or combustion
Expect in the application of battery, with very big development potentiality.
Embodiment described above only expresses some embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst, it is characterised in that comprise the following steps：
1) carbon material is chosen, then the carbon material is added to carbon material treatment fluid, 1~48h of stirring carries out activation process, mistake
Mixture A is obtained after filter；
2) by the compound and amino acids material or organic nitrogenous fertilizer class material of obtained mixture A and iron, in molar ratio for
1：0.01~0.125：0.0625~0.625 1~36h of mixing and ball milling, obtains mixture B；
3) by mixture B in N2500~1200 DEG C of constant temperature process 1~8h in atmosphere, then by dilute acid soln acidification 1~
12h, then suction filtration rinse to neutrality, obtain mixture C；
4) according to mass ratio it is 1~3 by the compound solution of mixture C and manganese：Reactor 1 and anti-is added separately to after 5 mixing
Kettle 2 is answered, the hydrothermal temperature of reactor 1 is 100~200 DEG C, and the reaction time is 1~3h, obtains mixture D 1；Reactor 2
Hydrothermal temperature be 100~200 DEG C, the reaction time be 3~12h, obtain mixture D 2；
5) by mixture D 1 and D2 in mass ratio 1：6~3：7 mixing, 100~150 DEG C of 1~48h of drying, 2~24h of ball milling are obtained
Catalyst Fe-N-C/ α-MnO2/ β-MnO2.
2. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 1, it is characterised in that described
Step 1) in carbon material be any one in graphite powder, carbon black, acetylene black, hard carbon, carbon fiber, porous activated carbon or two kinds
Mixture above.
3. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 1, it is characterised in that described
Step 1) in carbon material treatment fluid be K2CO3Solution, KOH solution or hydrogen peroxide.
4. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 3, it is characterised in that described
K2CO3The concentration of solution, KOH solution or hydrogen peroxide is 5%~saturation.
5. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 1, it is characterised in that described
Step 2) in iron compound be FeCl2·4H2O、FeSO4Or Fe (Ac)2。
6. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 1, it is characterised in that described
Step 2) in amino acids material be glycine or Pidolidone.
7. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 1, it is characterised in that described
Step 2) in organic nitrogenous fertilizer class material be urea or ammonium sulfate.
8. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 1, it is characterised in that described
Step 3) in dilute acid soln be sulfuric acid, hydrochloric acid or salpeter solution.
9. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 8, it is characterised in that described
The concentration of sulfuric acid, hydrochloric acid or salpeter solution is 0.1~2mol/L.
10. the preparation method of Fe-N-C/ α-MnO2/ β-MnO2 catalyst according to claim 1, it is characterised in that institute
State step 4) in manganese compound solution be liquor potassic permanganate or oxalic acid manganese solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767281A (en) * | 2018-06-28 | 2018-11-06 | 湖南工业大学 | A kind of oxygen reduction catalyst Fe-Mn/N-KB and its preparation method and application |
| CN109888318A (en) * | 2019-02-13 | 2019-06-14 | 上海交通大学 | A kind of preparation method and application of the nitrogen co-doped C-base composte material of metal- |
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| CN104916852A (en) * | 2015-07-02 | 2015-09-16 | 中国第一汽车股份有限公司 | Preparation method of air battery cathode catalyst |
| CN105921163A (en) * | 2016-05-03 | 2016-09-07 | 浙江大学 | Fe-N-C oxygen reduction catalyst and synthesizing method and application thereof |
| CN106215965A (en) * | 2016-07-05 | 2016-12-14 | 首都师范大学 | Application in the preparation of Fe N C meso-porous carbon material and oxygen reduction reaction thereof |
| CN106391082A (en) * | 2016-09-06 | 2017-02-15 | 南京航空航天大学 | Co-N-C catalyst, and preparation method and applications thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916852A (en) * | 2015-07-02 | 2015-09-16 | 中国第一汽车股份有限公司 | Preparation method of air battery cathode catalyst |
| CN105921163A (en) * | 2016-05-03 | 2016-09-07 | 浙江大学 | Fe-N-C oxygen reduction catalyst and synthesizing method and application thereof |
| CN106215965A (en) * | 2016-07-05 | 2016-12-14 | 首都师范大学 | Application in the preparation of Fe N C meso-porous carbon material and oxygen reduction reaction thereof |
| CN106391082A (en) * | 2016-09-06 | 2017-02-15 | 南京航空航天大学 | Co-N-C catalyst, and preparation method and applications thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767281A (en) * | 2018-06-28 | 2018-11-06 | 湖南工业大学 | A kind of oxygen reduction catalyst Fe-Mn/N-KB and its preparation method and application |
| CN109888318A (en) * | 2019-02-13 | 2019-06-14 | 上海交通大学 | A kind of preparation method and application of the nitrogen co-doped C-base composte material of metal- |
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Effective date of registration: 20230118 Address after: 418000 Xinhuang Industrial Development Zone (Qianfeng Industrial Park), Yushi Town, Xinhuang Dong Autonomous County, Huaihua City, Hunan Province Patentee after: Changsha daoshang Recycling Technology Co.,Ltd. Address before: 510000 No. 31 Kefeng Road, Guangzhou High-tech Industrial Development Zone, Guangzhou, Guangdong Province Patentee before: GUANGZHOU DAODONG NEW ENERGY Co.,Ltd. |