CN107507985A - A kind of three-dimensional Fe N C oxygen reduction catalysts of new high effectively iron load and preparation method thereof - Google Patents
A kind of three-dimensional Fe N C oxygen reduction catalysts of new high effectively iron load and preparation method thereof Download PDFInfo
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- CN107507985A CN107507985A CN201710785645.4A CN201710785645A CN107507985A CN 107507985 A CN107507985 A CN 107507985A CN 201710785645 A CN201710785645 A CN 201710785645A CN 107507985 A CN107507985 A CN 107507985A
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- oxygen reduction
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M4/96—Carbon-based electrodes
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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
Fe N C are as a kind of new oxygen reduction catalyst, it has the potential close to even better than commercial catalyst (Pt/C) catalytic activity, in addition it also has synthetic material wide material sources, cost is cheap, synthetic route is simple, possess the features such as scale and benefit, thus be believed to substitute traditional Pt/C catalyst, turn into commercially viable oxygen reduction catalyst of future generation.The invention discloses a kind of three-dimensional Fe N C oxygen reduction catalysts of new high effectively iron load and preparation method thereof.This method uses frerrous chloride, and melamine, graphene oxide, carboxylation CNT is raw material, by freeze-drying, solvent thermal reaction, heat treatment, acid pickling step, has obtained the three-dimensional Fe N C oxygen reduction catalysts with high effectively iron load.This method is raw materials used cheap and easy to get, and reaction scheme is simple, non-environmental-pollution.And its DTPA-Fe of the catalyst of this method preparation is higher, its catalytic activity is better than the Pt/C catalyst of traditional commerce.
Description
Technical field
The invention belongs to inorganic, organic crossing domain, is related to Fe-N coordination synthesis, more particularly to a kind of new high effectively
Iron loads the one-pot synthesis method of three-dimensional Fe-N-C oxygen reduction catalysts.
Background technology
Fuel cell is a kind of electrochemical appliance that electrochemistry is directly switched to electric energy.So that water or methanol are fuel as an example,
Its chemical reaction product non-environmental-pollution, it is a kind of clean energy resource；When energy converts in fuel cell, do not limited by Carnot cycle
System, possesses the features such as theoretical energy conversion ratio is high.
In fuel cell, the oxygen reduction reaction of negative electrode and the hydroxide chemical reaction of anode are substantially carried out.Due to dynamics
Upper Cathodic oxygen reduction is much slower than anode hydroxide reaction, and therefore, catalysis improves the speed of Cathodic oxygen reduction for carrying
The influence of high whole fuel battery performance is most important.
At present, the oxygen reduction catalyst studied and be most widely used is Pt base catalyst.But Pt bases catalyst due to
It is with high costs, limited source, in actual applications easily occur catalyst anthracemia the problems such as, it is further to limit its
Development and commercial promote.
Non noble metal oxygen reduction catalyst using Fe-N-C as representative, because its material source is extensive, cost is cheap, performance
It is quite even more excellent with Pt bases catalyst, and as the ideal chose of oxygen reduction catalyst of future generation.
At present, Fe-N in the catalyst of Fe-N-C types is generally believedxIt is the chief active site of hydrogen reduction, therefore with this
The iron that kind mode combines is considered as effective iron.
At present, the phthalocyanines for the still big ring that its source metal of synthesis and nitrogen source on Metal-N-C are mainly chosen is organic
Compound, its is costly, seriously hinders its commercialization and carries out.And phthalocyanine-like compound has fixed element ratio, nothing
Method regulates and controls the content of effective metal.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to providing a kind of new high effectively iron loads three-dimensional Fe-N-C
Oxygen reduction catalyst and preparation method thereof, the present invention is first using inorganic source of iron and organic molecule nitrogen-containing compound as nitrogen
Source, and using graphene and the CNT self assembly mixture of carboxylation as three-dimensional carrier, prepared with high effective iron
The Fe-N-C oxygen reduction catalysts of load.
The preparation method of the three-dimensional Fe-N-C oxygen reduction catalysts of the new high effectively iron load of the present invention, including following step
Suddenly：
1) take graphene oxide and CNT to be scattered in respectively in deionized water, ultrasound, obtain graphene oxide and carboxylic respectively
The dispersion liquid of carbon nano tube；After two kinds of dispersion liquids are mixed, ultrasound obtains dispersed graphene oxide and carboxylation carbon
The mixed dispersion liquid of nanotube；
2) added using organic molecule nitrogen-containing compound as nitrogen source in the mixed dispersion liquid in step 1), after ultrasonic mixing, then
Inorganic source of iron is added thereto, ultrasonic mixing, obtains mixed solution；
3) after the mixed solution in step 2) being quenched into pre-freeze in liquid nitrogen, it is placed in freeze drier, is dried under vacuum to ice cube
Distillation completely, obtain three-dimensional sample；Carboxylation CNT is uniformly scattered in the piece interlayer of graphene oxide, forms three-dimensional knot
Structure, source of iron, the load of nitrogen source and carrier three-dimensional structure are realized simultaneously in this step；
4) three-dimensional sample of gained in step 3) is placed in tube furnace, in the atmosphere of ammonia, in 700-800 DEG C of calcining at least
3 hours, after naturally cooling to room temperature, take out；
5) watery hydrochloric acid that mass fraction is 1% is prepared, the sample that step 4) obtains is rinsed, filtered several times, by dilute
The pickling of hydrochloric acid will can not form Fe-N in loading processxPart catalytically inactive even have to catalytic activity it is negative
The iron and ferrous-carbide of face effect remove, then with deionized water lavage specimens product several times；It is placed in baking oven, under conditions of room temperature
Drying, obtain the three-dimensional Fe-N-C oxygen reduction catalysts of new high effectively iron load.
In above-mentioned technical proposal, described organic molecule nitrogen-containing compound is melamine；Described inorganic source of iron is
Iron dichloride tetrahydrate；In such scheme, described nitrogen source uses melamine, and described source of iron is that four chloride hydrates are sub-
Iron, and the mass ratio of nitrogen source and source of iron is 20-30:1.
The invention has the advantages that：
1) using the nitrogen source of inorganic source of iron and small molecule, the load of high effectively iron is not only realized, and reduces Fe-N-C
The preparation cost of class catalyst, and the ratio of source of iron and nitrogen source is adjustable.
2) using the carrier of graphene oxide and the CNT self assembly mixture of carboxylation as Fe-N-C class catalyst, carboxylation
CNT is uniformly scattered in the piece interlayer of graphene oxide, forms three-dimensional structure, not only efficiently solves graphene
Agglomeration traits, more sites also are provided for the combination of itself and nitrogen source, add the content of effective iron.
3) present invention realizes source of iron, the load of nitrogen source and carrier three-dimensional structure simultaneously using freeze-drying in a step
Formed, avoid the destruction of carrier three-dimensional structure in multistep synthetic procedure, and because the destruction such as collapse of three-dimensional structure is brought
The negative effect to its catalytic activity.
Brief description of the drawings
SEMs of the Fig. 1 for CNT and graphene oxide after compound schemes；
TEMs of the Fig. 2 for CNT and graphene oxide after compound schemes；
Fig. 3 is the SEM figures of the Fe-N-C catalyst of synthesis；
Fig. 4 is the TEM figures of the Fe-N-C catalyst of synthesis；
Fig. 5 is the performance comparison figure of the product of the embodiment of the present invention 1 and commercialization Pt/C.
Embodiment
Embodiment 1
50mg graphene oxides and 50mg CNTs is taken to be scattered in respectively in isometric deionized water, ultrasound 1 hour, respectively
The dispersion liquid of graphene oxide and carboxylation CNT is obtained, both dispersion liquids are mixed, continues ultrasound 2 hours, is obtained equal
The mixed solution of even scattered graphene oxide and carboxylation CNT, melamine 0.08g is added, ultrasound 1 hour, adds four
Chloride hydrate ferrous iron 3.46mg, continues ultrasound 2 hours, obtains uniform dispersion, pre-freeze is quenched in liquid nitrogen, is placed in freeze-drying
In machine, it is dried under vacuum to ice cube and distils completely.Then, sample is placed in tube furnace, in ammonia atmosphere, carries out 750 DEG C of heat
After processing 3 hours, room temperature is naturally cooled in tube furnace.Finally, sample is taken out, is stirred with the watery hydrochloric acid of mass fraction 1%
Washing, vacuum filtration 5 times, then with after deionized water rinsing 5 times, be placed in vacuum oven, obtain novel three-dimensional Fe-N-C
Oxygen reduction catalyst.
Its EDS analysis results such as following table:
Comparative example 1
50mg graphene oxides and 50mg CNTs is taken to be scattered in respectively in isometric deionized water, ultrasound 1 hour, respectively
The dispersion liquid of graphene oxide and carboxylation CNT is obtained, both dispersion liquids are mixed, uniform dispersion is obtained, in liquid nitrogen
Middle quenching pre-freeze, is placed in freeze drier, is dried under vacuum to ice cube and distils completely.Then, sample is placed in tube furnace,
In ammonia atmosphere, it is heat-treated 3 hours at 750 DEG C, room temperature is naturally cooled in tube furnace.Take out sample and be put into quartz boat,
3mg ferrous phthalocyanines are added, in ammonia atmosphere, is heat-treated 3 hours at 750 DEG C, room temperature is naturally cooled in tube furnace.Most
Afterwards, sample is taken out, with the watery hydrochloric acid agitator treating of mass fraction 1%, is filtered by vacuum 5 times, then with after deionized water rinsing 5 times,
Vacuum oven is placed in, obtains novel three-dimensional Fe-N-C oxygen reduction catalysts.
Its EDS analysis results such as following table:
As can be seen that this comparative example uses the phthalocyanines organic compound ferrous phthalocyanine of big ring, as nitrogen source and source of iron, its is effective
Iron content is significantly lower than the result of the inventive method (embodiment 1).
Comparative example 2
50mg graphene oxides and 50mg CNTs is taken to be scattered in respectively in isometric deionized water, ultrasound 1 hour, respectively
The dispersion liquid of graphene oxide and carboxylation CNT is obtained, both dispersion liquids are mixed, continues ultrasound 2 hours, is obtained equal
The mixed solution of even scattered graphene oxide and carboxylation CNT, melamine 0.08g is added, ultrasound 1 hour, adds chlorine
Change iron 3.8mg, continue ultrasound 2 hours, obtain uniform dispersion, pre-freeze is quenched in liquid nitrogen, is placed in freeze drier, vacuum
Drying distils completely to ice cube.Then, sample is placed in tube furnace, in ammonia atmosphere, carries out 750 DEG C and be heat-treated 3 hours
Afterwards, room temperature is naturally cooled in tube furnace.Finally, sample is taken out, with the watery hydrochloric acid agitator treating of mass fraction 1%, vacuum
Filter 5 times, then with after deionized water rinsing 5 times, be placed in vacuum oven, obtain novel three-dimensional Fe-N-C hydrogen reduction catalysis
Agent.
Its EDS analysis result is as follows:
As can be seen that compared with Example 1, the source of iron content added in this example is slightly more, but in product effective iron amount it is still bright
The aobvious result being less than in embodiment 1.
Comparative example 3
50mg graphene oxides and 50mg CNTs is taken to be scattered in respectively in isometric deionized water, ultrasound 1 hour, respectively
The dispersion liquid of graphene oxide and carboxylation CNT is obtained, both dispersion liquids are mixed, continues ultrasound 2 hours, is obtained equal
The mixed solution of even scattered graphene oxide and carboxylation CNT, urea 0.125g is added, ultrasound 1 hour, adds chlorination
Iron 3.8mg, continues ultrasound 2 hours, obtains uniform dispersion, pre-freeze is quenched in liquid nitrogen, is placed in freeze drier, vacuum is done
It is dry to be distilled completely to ice cube.Then, sample is placed in tube furnace, in ammonia atmosphere, after 750 DEG C of progress heat treatment 3 hours,
Room temperature is naturally cooled in tube furnace.Finally, sample is taken out, with the watery hydrochloric acid agitator treating of mass fraction 1%, vacuum filtration
5 times, then with after deionized water rinsing 5 times, be placed in vacuum oven, obtain novel three-dimensional Fe-N-C oxygen reduction catalysts.
Its EDS analysis results such as following table:
Embodiment 2
The sample 10mg of sample 10mg, commercialized Pt/C in Example 1, carry out following experiments, are added to 4ml water respectively
In the mixed solution of isopropanol, 4 μ L nafion solution is added, ultrasound 1 hour, tests its polarization curve, scanning voltage model
0~1.2V, sweep speed 10mV/s, rotating speed 900rpm are enclosed, in oxygen atmosphere, in 0.1MKOH solution.The sample of embodiment 1
Polarization curve such as Fig. 5 (a), be commercialized Pt/C polarization curve such as Fig. 5 (b), it is known that, using three-dimensional made from the inventive method
Fe-N-C performance of oxygen-reducing catalyst is no less than commercialization Pt/C.
Claims (5)
- A kind of 1. preparation method of the three-dimensional Fe-N-C oxygen reduction catalysts of new high effectively iron load, it is characterised in that including Following steps：1) take graphene oxide and CNT to be scattered in respectively in deionized water, ultrasound, obtain graphene oxide and carboxylic respectively The dispersion liquid of carbon nano tube；After two kinds of dispersion liquids are mixed, ultrasound obtains dispersed graphene oxide and carboxylation carbon The mixed dispersion liquid of nanotube；2) added using organic molecule nitrogen-containing compound as nitrogen source in the mixed dispersion liquid in step 1), after ultrasonic mixing, then Inorganic source of iron is added thereto, ultrasonic mixing, obtains mixed solution；3) after the mixed solution in step 2) being quenched into pre-freeze in liquid nitrogen, it is placed in freeze drier, is dried under vacuum to ice cube Distillation completely, obtain three-dimensional sample；4) three-dimensional sample of gained in step 3) is placed in tube furnace, in the atmosphere of ammonia, in 700-800 DEG C, be fired to It is few 3 hours, after naturally cooling to room temperature, take out；5) watery hydrochloric acid that mass fraction is 1% is prepared, the sample that step 4) obtains is rinsed, filtered several times, then is spent Ionized water rinses sample several times；It is placed in baking oven, under conditions of room temperature, drying, that is, obtains new high effectively iron load Three-dimensional Fe-N-C oxygen reduction catalysts.
- 2. the preparation method of the three-dimensional Fe-N-C oxygen reduction catalysts of new high effectively iron load according to claim 1, Characterized in that, described organic molecule nitrogen-containing compound is melamine.
- 3. the preparation method of the three-dimensional Fe-N-C oxygen reduction catalysts of new high effectively iron load according to claim 1, Characterized in that, described inorganic source of iron is Iron dichloride tetrahydrate.
- 4. the preparation method of the three-dimensional Fe-N-C oxygen reduction catalysts of new high effectively iron load according to claim 1, Characterized in that, described nitrogen source uses melamine, described source of iron is Iron dichloride tetrahydrate, and the matter of nitrogen source and source of iron It is 20-30 to measure ratio:1.
- 5. a kind of three-dimensional Fe-N-C oxygen reduction catalysts of new high effectively iron load, it is characterised in that using such as claim Method described in any one of 1-4 is prepared.
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Cited By (2)
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| CN110010907A (en) * | 2019-03-25 | 2019-07-12 | 华中科技大学 | The method and product of Fe-N-CNT catalyst are prepared using waste plastics |
| CN112366326A (en) * | 2020-10-22 | 2021-02-12 | 广东省科学院稀有金属研究所 | Preparation method and application of carbon-coated nickel aerogel material |
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Application publication date: 20171222 |