CN105921163B - A kind of Fe N C oxygen reduction catalysts and its synthetic method and application - Google Patents
A kind of Fe N C oxygen reduction catalysts and its synthetic method and application Download PDFInfo
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- CN105921163B CN105921163B CN201610288312.6A CN201610288312A CN105921163B CN 105921163 B CN105921163 B CN 105921163B CN 201610288312 A CN201610288312 A CN 201610288312A CN 105921163 B CN105921163 B CN 105921163B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/24—Nitrogen 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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- 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 kind of synthetic method of Fe N C oxygen reduction catalysts and its preparation method and application, the synthetic method comprises the following steps:(1) carbon nitrogen presoma, pattern controlling agent and soluble ferric iron salt are added to the water, heating stirring is reacted, and is filtered after reacting completely, drying obtains solids;(2) solids that step (1) obtains is calcined, obtains catalyst precarsor;(3) catalyst precarsor that step (2) obtains is handled with acid, obtains described Fe N C oxygen reduction catalysts.The microstructure of the Fe N C compounds of this method synthesis, it is in blocks by substantial amounts of nanotube entanglement, it is stacked with again between lamella and forms the class multi-layer steamed bread shape structure of novelty, and the Fe metallic particles at the active center of nanotube internal package, obtained Fe N C oxygen reduction catalysts have preferable stability and activity.
Description
Technical field
The present invention relates to a kind of class multi-layer steamed bread shape for simply synthesizing novelty and stable efficient Fe-N-C bases in acidity
The method of cathodic oxygen reduction catalyst.
Background technology
Fuel cell is the device for electric energy by the chemical energy Efficient Conversion of fuel.With traditional with combustion of fossil fuel
Power generation process is compared, and dye cell not only can also have the characteristics of environment-friendly using reproducible fuel as energy source.
Inefficient Cathodic oxygen reduction (ORR) is the bottleneck for limiting the conversion of its high efficiency energy in fuel cell.Up to the present Pt
And catalyst is still maximally effective oxygen reduction catalyst, but due to Pt fancy prices, stability is poor, is easily poisoned by fuel
The problems such as, largely hinder widely using for fuel cell.
In order to reduce the cost of manufacture of fuel cell, stability test is improved, scientists are directed to out in recent ten years
Send out oxygen reduction catalyst various types of to reduce or replace the high Pt of price.Synthesis such as all kinds of alloys containing Pt can be certain
Pt application is reduced in degree.The focus for being developed into ORR catalyst researches of non-precious metal catalyst over nearest 5 years, wherein
Including non-metallic catalyst and transition-metal catalyst.In non-metal catalyst, the Carbon Materials of all kinds of Heteroatom dopings turn into should
The core of study hotspot.Wherein the Carbon Materials of azepine study the most extensive, the Carbon Materials phase of the various specific surface areas of various patterns
It is also relatively deep in terms of study mechanism after being reported.Carbon Materials based on these research Heteroatom dopings such as P, S are also synthesized
Research for ORR activity.Such shows the durability and fire-resistant material far above Pt base catalyst without metal carbon base catalyst
Poison ability, but its activity still suffers from larger gap relative to traditional Pt base catalyst.Especially in acid condition, no metal
Carbon base catalyst activity well below Pt base catalyst, acid electrolyte fuel battery (such as acid proton film can not be adapted to
Fuel cell) to the active demand of ORR catalyst.
And transition metal-type compound (Co, Fe, Ni, Mn) or compound show similar Pt base catalyst in acidity
Active and cost of material is low, is received much concern in ORR.Transition metal-nitrogen-charcoal (M-N-C) compound is in such catalyst
Outstanding person, and M-N-C bonding patterns are considered as living source.But for transition-metal catalyst, it is steady in sour environment
It is qualitative to turn into the key for limiting its application.It is to maintain transition gold that the transition metal active centres of activity, which are coated in graphite layer of charcoal,
The Perfected process of metal catalyst, for example, bag letter and seminar by XX nano particles be coated on CNT inside obtained it is high steady
Qualitatively ORR catalyst.But up to the present, how simply to synthesize with high stability, the transition-metal catalyst of high activity
It is still extremely urgent.
The content of the invention
The invention provides a kind of Fe-N-C oxygen reduction catalysts and its synthetic method and application, the Fe-N-C hydrogen reduction is urged
Agent is applied to fuel cell field, has excellent stability and ORR activity.
A kind of synthetic method of Fe-N-C oxygen reduction catalysts, comprises the following steps:
(1) carbon nitrogen presoma, pattern controlling agent and soluble ferric iron salt are added to the water, heating stirring is reacted, reaction
Filtered after completely, drying obtains solids;
Described carbon nitrogen presoma is used to provide carbon source and nitrogen source;
(2) solids that step (1) obtains is calcined, obtains catalyst precarsor;
(3) catalyst precarsor that step (2) obtains is handled with acid, obtains described Fe-N-C hydrogen reduction catalysis
Agent.
In the present invention, the Fe-N-C hydrogen reduction that the class multi-layer steamed bread shape of novelty can be prepared by simple building-up process is catalyzed
Agent, material activity regulation and control are simple, and ORR activity is high in acid medium and stability is good.
Preferably, in step (1), described carbon nitrogen presoma is melamine or dicyanodiamine, before both carbon nitrogen
It is cheap to drive body wide material sources, price.
Preferably, in step (1), described pattern controlling agent is oxalic acid, can preferably controlled material using oxalic acid
Microscopic appearance.
Preferably, in step (1), described soluble ferric iron salt is FeCl3、Fe(NO3)3Or Fe (CH3COO)3。
Preferably, in step (1), the mol ratio of described carbon nitrogen presoma, pattern controlling agent and soluble ferric iron salt is
1:1~50:0.05~0.1, preferably 1:1~10:0.1~0.2, by heating stirring, source of iron can be made uniformly to be mixed in carbon
In nitrogen presoma.
The present invention can be by changing the specific surface area and nitrogen content of calcination procedure controlled material, preferably, step (2)
In, calcination process temperature is 700-1200 DEG C, preferably 800-1000 DEG C.
In step (3), readily soluble unstability composition can be removed by carrying out processing using acid, preferably, described acid
For H2SO4、HCl or HNO3Solution, mass percent concentration are 5~30%;
Processing time is 0-24h, Best Times 5-10h.
Present invention also offers the Fe-N-C oxygen reduction catalysts that a kind of described synthetic method obtains, wherein, Fe elements
Mass percentage content be 0-30%;Preferably 5~20%.The microstructure of the Fe-N-C compounds of this method synthesis, it is
It is in blocks by substantial amounts of nanotube entanglement, it is stacked with again between lamella and forms the class multi-layer steamed bread shape structure of novelty, and nanotube
The Fe metallic particles at the active center of internal package.The structure can effectively protect stability of the Fe in acid medium.
Present invention also offers a kind of application of described Fe-N-C oxygen reduction catalysts in fuel cell is prepared.
Compared with the existing technology, beneficial effects of the present invention are:
(1) raw material sources used in are extensive, cheap, reduce the production cost of ORR catalyst;
(2) the ORR catalyst materials of novel pattern can be prepared without template, whole building-up process is simple, yield is high, can
Batch synthesizes, and requires low to synthesis device;
(3) the Fe-N-C materials synthesized in the present invention superior activity in acid medium and alkaline medium, and stability
It is high;
(4) activity of material can be entered by the ratio and calcining heat of carbon nitrogen presoma, acid and molysite in the present invention
Row regulation and control.
Brief description of the drawings
Fig. 1 is that embodiment 1 obtains the scanning electron microscope (SEM) photograph of material, wherein, right figure is the enlarged drawing in region in left figure square frame.
Fig. 2 is the obtained material of embodiment 1 in 0.1M HClO4In ORR performance comparison figures, the left side be ORR activity it is right
Than the right contrasts for stability.
Embodiment
The present invention is more comprehensively described using specific embodiment below.
Embodiment 1
By 2g melamines, 4g oxalic acid, 1g Fe (NO3)3·9H2O is added in 50ml water, is stirred in 80 DEG C in oil bath
Flow back 6h.After well mixed, mixture is filtered, in atmosphere 70 DEG C of drying.In N2In 800 DEG C of Muffles under atmosphere protection
Calcined in stove.0.5M H will be placed in after sample grinding after calcining2SO4Middle processing 9h is to remove diffluent Fe compositions.Acid is removed
Product afterwards is filtered, and is repeatedly washed using deionized water, and drying in atmosphere obtains Fe-N-C compounds.
0.008g Fe-N-C compounds are weighed, are dissolved in 10:5%Nafion (perfluorinated sulfonic acid) and the ethanol mixing of 1 volume ratio
Solution, ultrasonic mixing is uniform, and using platinized platinum as to electrode, calomel electrode is as reference electrode test material in 0.1M HClO4In
ORR activity.ORR take-off potential is 0.472V (VS.SCE), limiting current density 5.5mAcm-2.
Fig. 1 is that the present embodiment obtains the scanning electron microscopic picture of material, and Fig. 2 is material that the present embodiment obtains in 0.1M
HClO4In ORR performance comparison figures.
Embodiment 2
By 3g dicyanodiamines, 4g oxalic acid, 0.7g FeCl3·6H20 is added in 50ml water, is stirred in 80 DEG C in oil bath
Flow back 6h.After well mixed, mixture is filtered, in atmosphere 70 DEG C of drying.In N2In 900 DEG C of Muffles under atmosphere protection
Calcined in stove.0.5M H will be placed in after sample grinding after calcining2SO4Middle processing 9h is to remove diffluent Fe compositions.Acid is removed
Product afterwards is filtered, and is repeatedly washed using deionized water, dried in atmosphere.
Ultrasonic mixing is uniform after the Fe-N-C compounds that will be obtained, 5%Nafion and ethanol mix in certain proportion, with
Platinized platinum is used as to electrode, and calomel electrode is as reference electrode test material in 0.1M HClO4In ORR activity.ORR starting
Current potential is 0.46V0 (VS.SCE), limiting current density 5.4mA.cm-2。
Claims (7)
1. a kind of synthetic method of Fe-N-C oxygen reduction catalysts, it is characterised in that comprise the following steps:
(1) carbon nitrogen presoma, pattern controlling agent and soluble ferric iron salt are added to the water, heating stirring is reacted, and reaction is complete
After filter, drying obtain solids;
Described pattern controlling agent is oxalic acid;The mol ratio of described carbon nitrogen presoma, pattern controlling agent and soluble ferric iron salt is
1:1~50:0.05~0.1;
Described carbon nitrogen presoma is used to provide carbon source and nitrogen source;
(2) solids that step (1) obtains is calcined, obtains catalyst precarsor;
(3) catalyst precarsor that step (2) obtains is handled with acid, obtains described Fe-N-C oxygen reduction catalysts.
2. the synthetic method of Fe-N-C oxygen reduction catalysts according to claim 1, it is characterised in that in step (1), institute
The carbon nitrogen presoma stated is melamine or dicyanodiamine.
3. the synthetic method of Fe-N-C oxygen reduction catalysts according to claim 1, it is characterised in that in step (1), institute
The soluble ferric iron salt stated is FeCl3、Fe(NO3)3Or Fe (CH3COO)3。
4. the synthetic method of Fe-N-C oxygen reduction catalysts according to claim 1, it is characterised in that in step (2), forge
It is 700-1200 DEG C to burn process temperature.
5. the synthetic method of Fe-N-C oxygen reduction catalysts according to claim 1, it is characterised in that in step (3), institute
The acid stated is H2SO4、HCl or HNO3Solution, mass percent concentration are 5~30%;Processing time is 1-24h.
6. the Fe-N-C oxygen reduction catalysts that a kind of synthetic method as described in any one of Claims 1 to 5 obtains, its feature exist
In the mass percentage content of Fe elements is 0.1-30%.
A kind of 7. application of the Fe-N-C oxygen reduction catalysts in fuel cell is prepared as claimed in claim 6.
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CN106450355A (en) * | 2016-11-01 | 2017-02-22 | 首都师范大学 | Oxygen reduction catalyst and preparation method thereof |
CN106602080B (en) * | 2016-11-22 | 2019-04-09 | 大连理工大学 | It is a kind of based on cetyl trimethylammonium bromide be carbon material pore creating material three-dimensional porous Fe-N-C catalyst and preparation method |
CN106784888B (en) * | 2016-12-09 | 2019-06-25 | 新乡医学院 | A kind of metal air fuel cell oxygen reduction catalyst and preparation method thereof |
CN106824245A (en) * | 2017-02-20 | 2017-06-13 | 天津理工大学 | A kind of method for preparing oxygen reduction catalyst as raw material with insect wing |
CN106861745B (en) * | 2017-03-03 | 2019-04-19 | 广州道动新能源有限公司 | A kind of Fe-N-C/ α-MnO2/β-MnO2The preparation method of catalyst |
CN107069048A (en) * | 2017-03-14 | 2017-08-18 | 中南大学 | A kind of preparation method of Fe N C oxygen reduction catalysts |
CN109305880B (en) * | 2017-07-28 | 2021-09-07 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
CN108470916B (en) * | 2018-02-07 | 2020-09-01 | 深圳大学 | Fuel cell oxygen reduction catalyst taking three-dimensional porous carbon material as raw material and preparation method thereof |
CN109037713A (en) * | 2018-07-23 | 2018-12-18 | 重庆大学 | The preparation method of Novel iron N doping mesoporous biological carbon oxygen reduction catalyst |
CN109078649B (en) * | 2018-08-01 | 2021-07-16 | 陕西师范大学 | Transition metal-nitrogen doped carbon-based composite material and preparation method thereof |
CN109473628B (en) * | 2018-11-14 | 2021-08-10 | 东华大学 | Silicon-carbon nitride composite negative electrode material and preparation and application thereof |
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 |
CN114632546B (en) * | 2022-02-22 | 2023-10-17 | 新乡医学院 | Preparation method of sulfur-and nitrogen-containing iron-based metal organic framework microsphere oxygen reduction catalyst |
CN115207378B (en) * | 2022-07-25 | 2023-09-05 | 陕西科技大学 | Polypyrrole nanotube electrocatalyst and preparation method and application thereof |
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