CN110534752A - A kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst and preparation method thereof - Google Patents
A kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN110534752A CN110534752A CN201910754635.3A CN201910754635A CN110534752A CN 110534752 A CN110534752 A CN 110534752A CN 201910754635 A CN201910754635 A CN 201910754635A CN 110534752 A CN110534752 A CN 110534752A
- Authority
- CN
- China
- Prior art keywords
- carbon
- transference
- oxygen reduction
- cycle
- reduction catalyst
- 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
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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 present invention relates to a kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst, preparation method is that carbon carrier is dissolved in organic solvent, and ultrasonic disperse is uniform, and soluble ferric iron salt is added under stirring condition, is uniformly mixed and obtains mixed solution；The mixed solution is transferred to reaction kettle, is reacted under stirring condition, the reaction solution after reaction obtains solid material through separation of solid and liquid, washing, drying, and the solid material and nitrogen source mixed grinding obtain Means of Pyrolyzed Precursor；The Means of Pyrolyzed Precursor is roasted under an inert atmosphere and obtains the Fe-Mn cycle and transference carbon oxygen reduction catalyst；Wherein, the carbon carrier is Ketjen black nano-particle carbon.Compared with prior art, the present invention have many advantages, such as redox catalysis activity is high, electrochemical stability is good, the preparation method it is simple it is controllable, the period is short, and raw material rich reserves, at low cost, it can be achieved that large-scale production.
Description
Technical field
The present invention relates to catalyst preparation technical fields, more particularly, to a kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst
And preparation method thereof.
Background technique
The advantages that fuel cell is with its high power density, high efficiency, reliable environmental protection, shows the wide of substitute fossil fuels
Prospect.Electrochemical oxygen reduction plays an important role in these renewable energy converting systems.Fuel battery negative pole oxygen is also
Former reaction energy barrier is higher, needs efficient catalyst degradation reaction activity, improves reaction rate.This reaction needs efficiently to urge
Agent, wherein based on noble metal platinum-base material.But platinum based catalyst price is high, and supply is unsustainable, and durability is poor, vulnerable to first
The influence of alcohol cross effect and CO poisoning.In addition, over time, the dissolution of the burn into platinum of carbon, nanoparticle maturation
It will lead to the deterioration of performance with falling off.These serious problems hinder the widespread commercial of fuel cell technology.Therefore, it develops
It is cheap, and the non noble metal oxygen reduction catalyst with high activity, high stability is of great significance.
In non noble metal oxygen reduction catalyst, the research of the activity and durability of M-N/C catalyst has been continued
Nearly 60 years, many team reported largely about the method and mentality of designing for preparing new catalyst.Currently, M-N/
C catalyst generallys use presoma (such as second of mixed metal salt (such as sulfate, nitrate, acetate and chloride etc.), nitrogen
Nitrile, aniline and melamine etc.) and carbon carrier (such as Vulcan XC-72, Ketjenblack, Black Pearls etc.) etc., so
The method being pyrolyzed afterwards obtains catalyst product.Although the active site of current M-N/C catalytic oxidation-reduction process and specific mechanism are also
There is disputes, but by developing and rationally designing synthetic route, select new metal salt, nitrogen carbon matrix precursor, heat treatment item
Part and atmosphere can significantly improve the catalytic activity and durability of thermal decomposition product.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of Fe-Mn cycle and transference carbon
Oxygen reduction catalyst and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst, comprising the following steps:
Carbon carrier is dissolved in organic solvent, ultrasonic disperse is uniform, and soluble ferric iron salt is added under stirring condition, is uniformly mixed
Obtain mixed solution；
The mixed solution is transferred to reaction kettle, is reacted under stirring condition, the reaction solution after reaction is through solid-liquid point
Solid material is obtained from, washing, drying, the solid material and nitrogen source mixed grinding obtain Means of Pyrolyzed Precursor；
The Means of Pyrolyzed Precursor is roasted under an inert atmosphere and obtains the Fe-Mn cycle and transference carbon oxygen reduction catalyst；
Wherein, the carbon carrier is Ketjen black nano-particle carbon.
Source of iron of the present invention, nitrogen source, mixture that Ketjen black nano-particle carbon is carrier are by high temperature pyrolysis, by iron atom
Fe-N/C nano material is formed with nitrogen-atoms incorporation carbon matrix；The carbonization of source of iron high temperature pyrolysis generates Fe2C、Fe3C, active site are high
Degree is exposed and evenly dispersed, and there is also Fe-N for material surfacex；Various active site synergistic effect improves the oxygen of nano-particle carbon
Restore electro catalytic activity.
Carrier present invention preferably employs Ketjen black nano-particle carbon as catalyst, with aperture, adjustable, pattern can
The advantages that control, large specific surface area, diversified metal and ligand.And in pyrolytic process, the carbon black granules as carrier can be with
Make doping metallic atom and nitrogen-atoms while be uniformly distributed with micropore and mesoporous microscopic appearance, be conducive to reactant and
The mass transfer of product, and pyrolytic process structure is not easy to collapse, and not will lead to the reduction of large specific surface area width；In addition, pyrolytic process is not easy
Occur metal nanoparticle reunion and cause ferro element to be unevenly distributed, catalytic active site dot density reduce the phenomenon that.
The average diameter of the Ketjen black nano-particle carbon is 50~100nm.
The specific surface area of the Ketjen black nano-particle carbon is greater than 1300m2/g。
The nitrogen source is guanidine hydrochloride, and the ratio of the nitrogen source and the solid material is 1.2~1.7:1, preferably 1.5:
1。
Nitrogen source of the invention is preferably guanidine hydrochloride, and traditional gaseous nitrogen source such as ammonia can skin ambustion, eyes, respiratory apparatus
Mucous membrane, people's sucking is excessive, can cause lung swelling, so that dead；Skin is corroded in solid nitrogen source such as cyanamide, the compound polar stimulation
Skin, respiratory tract, mucous membrane, suck or eat make face instantaneously redden, have a headache strongly, dizziness, accelerated breathing, tachycardia, blood pressure
Too low, after exposure, symptom can hide 1~2 day.Relative to above nitrogen presoma, guanidine hydrochloride be it is a kind of low cost, stabilization can
It leans on, be easily obtained, environmental-friendly compound, and guanidine hydrochloride has high nitrogen content, is a kind of ideal nitrogen source.
In the mixed solution, the concentration of the soluble ferric iron salt is 0.01~1molL-1, preferably 0.1molL-1；
The concentration of the carbon carrier is 3.6~4.4gL-1, preferably 4gL-1；The soluble ferric iron salt is ferric nitrate.
The organic solvent is selected from one or more of ethyl alcohol, methanol, propylene glycol.
The inert atmosphere is argon gas or nitrogen, and the method for the roasting is with 1-10 DEG C of min-1Heating rate heating
To 700~900 DEG C, 1~3h is kept the temperature；Preferably with 5 DEG C of min-1Heating rate to 800 DEG C, keep the temperature 1h.
Maturing temperature of the invention is more important to final catalyst performance, and maturing temperature influences final Fe-C compound
Structure proportion, experiments have shown that, maturing temperature is excessively high or too low, and half wave potential can reduce, and is unfavorable for the electro-catalysis of catalyst
Activity.Test proves that 800 DEG C are optimum calcination temperatures after optimization.
The temperature when drying is 60-80 DEG C, drying time 6-12h.
The catalyst is that iron atom and nitrogen-atoms are mixed the Fe-N/C nano material that carbon matrix is formed, and surface has Fe-
Nx、Fe3C and/or Fe2C active site.
Cathodic oxygen reduction of the catalyst for alkaline fuel cell reacts.
The method generallyd use in the prior art is to select the carbon material of nitrogen presoma, metal salt dopping, by changing nitrogen
The type of presoma, metal salt, and according to the fusing point of different fuse salts, in thermal decomposition product nitrogen element content and there are shapes
Formula (pyrroles's nitrogen, pyridine nitrogen, graphitization nitrogen etc.) and Fe-Nx、Fe3C and/or Fe2C active site is further regulated and controled.Phase
Than in the prior art by using raw material in carbon source be glucose, nitrogen source is melamine, carbon carrier is that multi wall carbon is received
Mitron (MCNTs), and it is added to the method that catalyst is prepared as soft template in Surfactant SDS, this
Invention uses Ketjen black nano-particle carbon as carrier first, and MCNTs's involves great expense, and the market price is about 100~300
Member/g, and the price of the EC600JD Ketjen black nano-particle carbon of Japanese lion princes and dukes department used in the present invention is only 500~600
Member/kg, it can be found that method of the invention has more economy.Compared to use lauryl sodium sulfate as soft template, and
And hydro-thermal method is used to regulate and control the mixed process of metal salt and carbon carrier；The present invention uses infusion process, at normal temperature magnetic
Power stirring is impregnated into ferric nitrate on KB powder particle, and penetrates into inner surface, comes into full contact with each object in mixture mutually,
Even mixing.In general, hydro-thermal method needs high temperature and pressure step, keep it stronger to the dependence of production equipment, equipment requirement is high, skill
Art is complicated for operation, poor safety performance, and infusion process experiment condition is mild, easy to operate, securely and reliably.Therefore, the present invention passes through
Many experiments, have preferably obtained the preparation method of nitrogen source and carbon carrier engaged therewith and dipping, and system optimization has obtained one
A economic, efficient preparation process, has more promotional value.
Compared with prior art, the invention has the following advantages that
(1) Fe-N/C material prepared by the present invention is made using metal salt, nitrogen source and one step pyrolysismethod of carbon carrier, preparation side
Method process optimization, simple, the period is short, and raw material rich reserves, at low cost, adjustable, morphology controllable, specific surface area with aperture
Greatly, pore structure is abundant, metal center and the advantages that ligand diversity, and the catalyst that high temperature pyrolysis is carbonized can inherit forerunner
The structure and pattern of body form the evenly dispersed advantageous cellular structure of active site and mass transfer, so that it is anti-to accelerate oxygen reduction
Rate is answered, electro catalytic activity is improved；
(2) Fe-Mn cycle and transference carbon oxygen reduction catalyst prepared by the present invention has sufficiently exposure and evenly dispersed activity
Site and the micropore-mesopore hierarchical porous structure for being conducive to mass transfer, and low in cost, oxygen reduction catalytic activity and electrochemically stable
Property is close to Pt/C catalyst；
(3) preparation method of the present invention is simple, the period is short, and raw material rich reserves, it is at low cost, it can be achieved that large-scale production.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of the Fe-Mn cycle and transference carbon oxygen reduction catalyst in embodiment 1；
Fig. 2 is the X-ray diffractogram of Fe-Mn cycle and transference carbon oxygen reduction catalyst in embodiment 1；
Fig. 3 is Fe-Mn cycle and transference carbon oxygen reduction catalyst in embodiment 1, Ketjen black nano-particle carbon and Pt/C catalysis
The polarization curve of agent；
Fig. 4 is the X-ray diffractogram of Fe-Mn cycle and transference carbon oxygen reduction catalyst in embodiment 2；
Fig. 5 is Fe-Mn cycle and transference carbon oxygen reduction catalyst in embodiment 2, Ketjen black nano-particle carbon and Pt/C catalysis
The polarization curve of agent；
Fig. 6 is the X-ray diffractogram of Fe-Mn cycle and transference carbon oxygen reduction catalyst in embodiment 3；
Fig. 7 is Fe-Mn cycle and transference carbon oxygen reduction catalyst in embodiment 3, Ketjen black nano-particle carbon and Pt/C catalysis
The polarization curve of agent.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst, the catalyst are received with Fe(NO3)39H2O, guanidine hydrochloride and Ketjen black
The Fe-Mn cycle and transference carbon oxygen reduction catalyst that the mixture of rice carbon black pellet is prepared as presoma high temperature pyrolysis, including
Following steps:
(1) it is dissolved in 0.2g Ketjen black nano-particle carbon as carbon carrier in 50ml organic solvent ethyl alcohol, ultrasonic dissolution
And be uniformly dispersed, ferric nitrate is added under agitation, is sufficiently mixed acquisition mixed solution, is then transferred in reaction kettle, it will
Reaction kettle, which is placed under room temperature, to be stirred for 24 hours, is filtered by vacuum and is dried after being washed repeatedly with organic solvent ethyl alcohol, and nitrogen source hydrochloric acid is added
Mixed grinding after guanidine, obtains Means of Pyrolyzed Precursor；Wherein, the concentration of ferric nitrate in the solution is 0.1molL-1, the use of guanidine hydrochloride
Amount is 3.03g, and drying temperature is 60 DEG C, drying time 12h；, generally tested according to BET, the ratio of Ketjen black nano-particle carbon
Surface area actual measurement is 1351m2/ g, the theoretical value for buying product is 1400m2/g。
(2) by the precursor mixture of above-mentioned preparation under inert atmosphere argon gas with 5 DEG C of min-1Heating rate heating
To 800 DEG C, 1h is kept the temperature, grinding obtains Fe-Mn cycle and transference carbon oxygen reduction catalyst after being cooled to room temperature.
Fe-N/C catalyst is obtained to the present embodiment and has carried out scanning electron microscope and XRD analysis, used Ketjen black nanometer
Graininess is presented in hydrocarbon black powder pattern, and average diameter is about 50-100nm, as shown in Figure 1, iron, the nitrogen of pyrolysis carbonization preparation are co-doped with
Miscellaneous C catalyst inherits the graininess pattern of Ketjen black nano carbon black；The structure of the catalyst is characterized, it is found that this is urged
Agent is shown containing a large amount of Fe2The map structure of C active site, as shown in Figure 2；Further to the hydrogen reduction of the catalyst
It can be carried out test, as shown in figure 3, Fig. 3 shows that the catalyst has the electro-catalysis better than commercialization Ketjen black nano-particle carbon
Activity, half wave potential are more than 115mV, and close to the electro catalytic activity of business 20%Pt/C, half wave potential differs 53mV, and
Electrochemical stability is better than Pt/C catalyst.
Embodiment 2
The present embodiment is a kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst, which uses system similar to Example 1
Standby process, the difference is that, during Means of Pyrolyzed Precursor, reaction temperature is improved to 900 DEG C.
The structure of the catalyst is characterized, its XRD spectrum is obtained, as shown in figure 4, Fig. 4 shows the catalyst of preparation
Contain a large amount of Fe3C；Hydrogen reduction performance test further is carried out to the catalyst of pyrolysis carbonization preparation, as shown in figure 5, showing this
Catalyst has the electro catalytic activity better than commercialization Ketjen black nano-particle carbon, and half wave potential is more than 114mV；Close to quotient
The electro catalytic activity of industry Pt/C catalyst, half wave potential differ 54mV, reduce 1mV compared with embodiment 1, and electrochemical stability is better than
It is commercialized 20%Pt/C.
Embodiment 3
The present embodiment is a kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst, which uses system similar to Example 1
Standby process, the difference is that, during Means of Pyrolyzed Precursor, reaction temperature is down to 700 DEG C.
The structure of the catalyst is characterized, its XRD spectrum is obtained, as shown in fig. 6, iron, the nitrogen of pyrolysis carbonization preparation
Codope C catalyst is shown containing a large amount of Fe2The map structure of C active site；Further to the catalysis of pyrolysis carbonization preparation
Agent carries out hydrogen reduction performance test, as shown in fig. 7, showing that the catalyst has better than commercialization Ketjen black nano-particle carbon
Electro catalytic activity, half wave potential are more than 45mV；With the electro catalytic activity close to business 20%Pt/C, half wave potential difference
123mV declines 70mV compared with embodiment 1.
Embodiment 4
A kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst, the catalyst are received with Fe(NO3)39H2O, guanidine hydrochloride and Ketjen black
The Fe-Mn cycle and transference carbon oxygen reduction catalyst that the mixture of rice carbon black pellet is prepared as presoma high temperature pyrolysis, including
Following steps:
(1) it is dissolved in Ketjen black nano-particle carbon 0.18g as carbon carrier in 50ml organic solvent methanol, ultrasonic dissolution
And be uniformly dispersed, ferric nitrate is added under agitation, is sufficiently mixed acquisition mixed solution, is then transferred in reaction kettle, it will
Reaction kettle, which is placed under room temperature, to be stirred for 24 hours, is filtered by vacuum and is dried after being washed repeatedly with organic solvent ethyl alcohol, and nitrogen source hydrochloric acid is added
Mixed grinding after guanidine, obtains Means of Pyrolyzed Precursor；Wherein, the concentration of ferric nitrate in the solution is 0.01molL-1, the use of guanidine hydrochloride
Amount is 3.03g, and the partial size of Ketjen black nano-particle carbon is 50nm, and drying temperature is 60 DEG C, drying time 12h；
(2) by the precursor mixture of above-mentioned preparation under inert atmosphere argon gas with 1 DEG C of min-1Heating rate heating
To 800 DEG C, 3h is kept the temperature, grinding obtains Fe-Mn cycle and transference carbon oxygen reduction catalyst after being cooled to room temperature, measures the catalyst
's.
Embodiment 5
A kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst, the catalyst are received with Fe(NO3)39H2O, guanidine hydrochloride and Ketjen black
The Fe-Mn cycle and transference carbon oxygen reduction catalyst that the mixture of rice carbon black pellet is prepared as presoma high temperature pyrolysis, including
Following steps:
(1) it is dissolved in Ketjen black nano-particle carbon 0.22g as carbon carrier in 50ml organic solvent propylene glycol, ultrasound is molten
It solves and is uniformly dispersed, ferric nitrate is added under agitation, be sufficiently mixed acquisition mixed solution, be then transferred in reaction kettle,
Reaction kettle is placed under room temperature and is stirred for 24 hours, be filtered by vacuum and is dried after being washed repeatedly with organic solvent propylene glycol, nitrogen source is added
Mixed grinding after guanidine hydrochloride, obtains Means of Pyrolyzed Precursor；Wherein, the concentration of ferric nitrate in the solution is 1molL-1, guanidine hydrochloride
Dosage is 3.03g, and the partial size of Ketjen black nano-particle carbon is 100nm, and drying temperature is 80 DEG C, drying time 6h；
(2) by the precursor mixture of above-mentioned preparation under inert atmosphere argon gas with 10 DEG C of min-1Heating rate heating
To 800 DEG C, 3h is kept the temperature, grinding obtains Fe-Mn cycle and transference carbon oxygen reduction catalyst after being cooled to room temperature.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst, which comprises the following steps:
Carbon carrier is dissolved in organic solvent, ultrasonic disperse is uniform, and soluble ferric iron salt is added under stirring condition, is uniformly mixed and obtains
Mixed solution；
The mixed solution is transferred to reaction kettle, is reacted under stirring condition, the reaction solution after reaction is separated by solid-liquid separation, is washed
It washs, dry and obtain solid material, the solid material and nitrogen source mixed grinding obtain Means of Pyrolyzed Precursor；
The Means of Pyrolyzed Precursor is roasted under an inert atmosphere and obtains the Fe-Mn cycle and transference carbon oxygen reduction catalyst；
Wherein, the carbon carrier is Ketjen black nano-particle carbon.
2. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 1, which is characterized in that
The average diameter of the Ketjen black nano-particle carbon is 50~100nm.
3. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 1, which is characterized in that
The specific surface area of the Ketjen black nano-particle carbon is greater than 1300m2/g。
4. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 1, which is characterized in that
The nitrogen source is guanidine hydrochloride, and the mass ratio of the nitrogen source and the solid material is 1.2~1.7:1, preferably 1.5:1.
5. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 1, which is characterized in that
In the mixed solution, the concentration of the soluble ferric iron salt is 0.01~1molL-1, preferably 0.1molL-1, the carbon
The concentration of carrier is 3.6~4.4gL-1, preferably 4gL-1；The soluble ferric iron salt is ferric nitrate.
6. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 1, which is characterized in that
The organic solvent is selected from one or more of ethyl alcohol, methanol, propylene glycol.
7. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 1, which is characterized in that
The inert atmosphere is argon gas or nitrogen, and the method for the roasting is with 1-10 DEG C of min-1Heating rate be warming up to 700~
900 DEG C, keep the temperature 1~3h；Preferably with 5 DEG C of min-1Heating rate to 800 DEG C, keep the temperature 1h.
8. a kind of preparation method of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 1, which is characterized in that
The temperature when drying is 60~80 DEG C, and drying time is 6~12h.
9. a kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst that preparation method as described in claim 1 is prepared, feature
It is, which is that iron atom and nitrogen-atoms are mixed the Fe-N/C nano material that carbon matrix is formed, and surface has Fe-Nx、
Fe3C and/or Fe2C active site.
10. a kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst according to claim 9, which is characterized in that its feature exists
In cathodic oxygen reduction of the catalyst for alkaline fuel cell reacts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910754635.3A CN110534752B (en) | 2019-08-15 | 2019-08-15 | Iron and nitrogen co-doped carbon-oxygen reduction catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910754635.3A CN110534752B (en) | 2019-08-15 | 2019-08-15 | Iron and nitrogen co-doped carbon-oxygen reduction catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110534752A true CN110534752A (en) | 2019-12-03 |
| CN110534752B CN110534752B (en) | 2022-11-18 |
Family
ID=68663543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910754635.3A Active CN110534752B (en) | 2019-08-15 | 2019-08-15 | Iron and nitrogen co-doped carbon-oxygen reduction catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110534752B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961136A (en) * | 2019-12-18 | 2020-04-07 | 西安工业大学 | Fe with three-dimensional continuous structure3N-coated FeNCN compound and preparation method thereof |
| 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 |
| CN112121843A (en) * | 2020-10-15 | 2020-12-25 | 哈尔滨工业大学 | Preparation method and application of loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst |
| CN112259751A (en) * | 2020-10-27 | 2021-01-22 | 广东工业大学 | ORR and OER bifunctional catalyst, and preparation method and application thereof |
| CN112452346A (en) * | 2020-10-14 | 2021-03-09 | 浙江大学 | Universal method for preparing metal single-atom carbon-based catalyst and application |
| CN112490451A (en) * | 2020-11-05 | 2021-03-12 | 上海电力大学 | Cu-CoNCNs catalyst derived from folic acid, preparation and application thereof |
| CN113529125A (en) * | 2021-06-16 | 2021-10-22 | 佛山市格瑞芬新能源有限公司 | Iron phosphide composite material and preparation method and application thereof |
| CN114042456A (en) * | 2021-12-03 | 2022-02-15 | 浙江工业大学 | Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst |
| CN114289057A (en) * | 2022-01-14 | 2022-04-08 | 吉林大学 | Nitrogen-doped carbon-iron-based nanoparticle catalyst, preparation method and application thereof in Friedel-crafts acylation reaction |
| CN114477163A (en) * | 2022-01-25 | 2022-05-13 | 武汉大学 | Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof |
| CN114824322A (en) * | 2022-03-15 | 2022-07-29 | 湖北文理学院 | Method for preparing oxygen reduction catalyst |
| CN114824323A (en) * | 2022-03-15 | 2022-07-29 | 湖北文理学院 | Method for preparing oxygen reduction catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062478A (en) * | 2006-04-26 | 2007-10-31 | 中国科学院大连化学物理研究所 | Catalyst for carbon monoxide oxidation in hydrogen and preparation method thereof |
| CN101152625A (en) * | 2007-09-12 | 2008-04-02 | 浙江大学 | Non-metal N doped one-dimensional nano-structured Ti0* visible light catalyzer and method for producing the same |
| CN105289729A (en) * | 2015-11-09 | 2016-02-03 | 中国科学院化学研究所 | Non-precious metal oxygen reduction catalyst and preparing method and application thereof |
| CN106532073A (en) * | 2016-10-17 | 2017-03-22 | 西安建筑科技大学 | Nitrogen-sulfur-iron triple-doped carbon black catalyst and preparation method and application thereof |
-
2019
- 2019-08-15 CN CN201910754635.3A patent/CN110534752B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062478A (en) * | 2006-04-26 | 2007-10-31 | 中国科学院大连化学物理研究所 | Catalyst for carbon monoxide oxidation in hydrogen and preparation method thereof |
| CN101152625A (en) * | 2007-09-12 | 2008-04-02 | 浙江大学 | Non-metal N doped one-dimensional nano-structured Ti0* visible light catalyzer and method for producing the same |
| CN105289729A (en) * | 2015-11-09 | 2016-02-03 | 中国科学院化学研究所 | Non-precious metal oxygen reduction catalyst and preparing method and application thereof |
| CN106532073A (en) * | 2016-10-17 | 2017-03-22 | 西安建筑科技大学 | Nitrogen-sulfur-iron triple-doped carbon black catalyst and preparation method and application thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961136A (en) * | 2019-12-18 | 2020-04-07 | 西安工业大学 | Fe with three-dimensional continuous structure3N-coated FeNCN compound and preparation method thereof |
| 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 |
| CN112452346A (en) * | 2020-10-14 | 2021-03-09 | 浙江大学 | Universal method for preparing metal single-atom carbon-based catalyst and application |
| CN112121843A (en) * | 2020-10-15 | 2020-12-25 | 哈尔滨工业大学 | Preparation method and application of loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst |
| CN112121843B (en) * | 2020-10-15 | 2022-04-22 | 哈尔滨工业大学 | Preparation method and application of loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst |
| CN112259751B (en) * | 2020-10-27 | 2022-06-14 | 广东工业大学 | ORR and OER bifunctional catalyst, and preparation method and application thereof |
| CN112259751A (en) * | 2020-10-27 | 2021-01-22 | 广东工业大学 | ORR and OER bifunctional catalyst, and preparation method and application thereof |
| CN112490451A (en) * | 2020-11-05 | 2021-03-12 | 上海电力大学 | Cu-CoNCNs catalyst derived from folic acid, preparation and application thereof |
| CN113529125A (en) * | 2021-06-16 | 2021-10-22 | 佛山市格瑞芬新能源有限公司 | Iron phosphide composite material and preparation method and application thereof |
| CN114042456A (en) * | 2021-12-03 | 2022-02-15 | 浙江工业大学 | Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst |
| CN114042456B (en) * | 2021-12-03 | 2023-11-10 | 浙江工业大学 | Method for preparing Fe-based catalyst by taking biomass as raw material and application of Fe-based catalyst |
| CN114289057A (en) * | 2022-01-14 | 2022-04-08 | 吉林大学 | Nitrogen-doped carbon-iron-based nanoparticle catalyst, preparation method and application thereof in Friedel-crafts acylation reaction |
| CN114477163B (en) * | 2022-01-25 | 2023-10-20 | 武汉大学 | Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof |
| CN114477163A (en) * | 2022-01-25 | 2022-05-13 | 武汉大学 | Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof |
| CN114824322A (en) * | 2022-03-15 | 2022-07-29 | 湖北文理学院 | Method for preparing oxygen reduction catalyst |
| CN114824323A (en) * | 2022-03-15 | 2022-07-29 | 湖北文理学院 | Method for preparing oxygen reduction catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110534752B (en) | 2022-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110534752A (en) | A kind of Fe-Mn cycle and transference carbon oxygen reduction catalyst and preparation method thereof | |
| CN107803207B (en) | Carbon-based bimetallic composite material, preparation and application thereof | |
| CN104923204B (en) | A kind of preparation method and applications of graphene coated catalyst with metal nanoparticles | |
| CN109675599B (en) | Nitrogen-doped carbon-coated molybdenum carbide and preparation method and application thereof | |
| CN105749947B (en) | A kind of non noble metal oxygen reduction catalyst and its preparation and application | |
| CN106229521B (en) | A kind of FeCx@NC catalyst with core-casing structure and preparation method thereof | |
| CN109378482A (en) | The nucleocapsid catalyst of Non-precious Metal Catalysts material load, preparation method and applications | |
| CN111883792B (en) | Transition metal manganese and nitrogen-doped carbon oxygen reduction electrocatalyst and preparation method and application thereof | |
| CN107346826A (en) | A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron | |
| US8895467B2 (en) | Ag/MnyOx/C catalyst, preparation and application thereof | |
| CN102294255B (en) | Carbon gel catalyst and application thereof | |
| CN105244513A (en) | Graphite-phase carbon nitride-modified carbon black-loaded platinum-palladium alloy nano electrocatalyst and preparation method | |
| CN112007673B (en) | N-doped porous carbon-coated MoP nano rod material and preparation method and application thereof | |
| CN110354884A (en) | A kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC and its preparation method and application | |
| CN109794278A (en) | Nitrogen oxygen sulphur three adulterates porous carbon coating eight and vulcanizes nine cobalt composite catalysts and preparation method thereof | |
| CN106784896A (en) | The zinc-air battery transition metal oxide high dispersive porous C catalyst of doping | |
| CN108847494A (en) | A kind of transition metal/the sulphur can be used for fuel cell electro-catalyst/nitrogen co-doped carbon composite and preparation method thereof | |
| CN111036247A (en) | Cobalt iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material and preparation method and application thereof | |
| CN113270597A (en) | C3N4Coated carbon nano tube loaded NiFe dual-functional oxygen electrocatalyst and preparation method thereof | |
| CN110444772A (en) | A kind of bimetallic base Fe-Co-N-S codope C catalyst and the preparation method and application thereof | |
| CN109950563A (en) | A kind of non noble metal oxygen reduction catalysts and preparation method thereof of metal active position high dispersive | |
| Su et al. | Palladium nanoparticles immobilized in B, N doped porous carbon as electrocatalyst for ethanol oxidation reaction | |
| CN113437310A (en) | Mesoporous silica shell-coated metal-N co-doped/porous carbon composite material, and preparation method and application thereof | |
| CN103464211B (en) | A kind of MnOxthe preparation method of/C-PTFE catalyst mastic | |
| CN112007677A (en) | Nitrogen-doped iron nanotube, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |