CN106925296A - A kind of nano composite material and its preparation method and application - Google Patents
A kind of nano composite material and its preparation method and application Download PDFInfo
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- CN106925296A CN106925296A CN201710193554.1A CN201710193554A CN106925296A CN 106925296 A CN106925296 A CN 106925296A CN 201710193554 A CN201710193554 A CN 201710193554A CN 106925296 A CN106925296 A CN 106925296A
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- ferrite
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000002787 reinforcement Effects 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 235000013339 cereals Nutrition 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- XRUZAHLMEKMYRG-UHFFFAOYSA-N iron;oxosilver Chemical compound [Fe].[Ag]=O XRUZAHLMEKMYRG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 229910000708 MFe2O4 Inorganic materials 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910003321 CoFe Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- RQCJDSANJOCRMV-UHFFFAOYSA-N [Mn].[Ag] Chemical compound [Mn].[Ag] RQCJDSANJOCRMV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- SQWDWSANCUIJGW-UHFFFAOYSA-N cobalt silver Chemical compound [Co].[Ag] SQWDWSANCUIJGW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- -1 ultrasonic 30min Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
-
- 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
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides graphene-supported silver-colored ferrite (the Ag MFe of one kind2O4) nano composite material and its preparation method and application, the nano composite material is formed by the graphene-supported silver-colored heterogeneous nano-particles reinforcement of ferrite.Its preparation method can both be directly loaded in the technique on Graphene using the silver-colored heterogeneous nano particle of ferrite, it would however also be possible to employ the technique that first particulate load is restored on graphene oxide.Graphene-supported silver-colored ferrite nano composite is high as elctro-catalyst good stability, methanol tolerant toxicity, electric conductivity and catalysis activity, its preparation process is simple, cost are relatively low, and reaction condition is easily-controllable, and resulting materials pattern is homogeneous, good dispersion, it is easy to expand large-scale production.
Description
Technical field
The invention belongs to new catalyst research and development field, specifically, it is related to a kind of novel nanocomposite materials and its system
Preparation Method and application.
Background technology
Commercialization platinum/carbon (Pt/C) catalyst has relatively costly, stability and resistance to poison at present, sternly
The large-scale application of associated batteries is constrained again.With developing rapidly for nanometer technology and materials chemistry, people begin attempt to grind
Novel nanocomposite materials are sent out to replace Pt/C catalyst.
In recent years, the ferrite (MFe of carbon load transitions state metal M (iron, manganese, cobalt, nickel, zinc, II)2O4) it is nanocrystalline due to
Its excellent oxygen reduction reaction (ORR) catalysis activity, gradually attracts attention.Additionally, silver (Ag) is nanocrystalline possesses excellent
Different electric conductivity and methanol tolerant toxicity, can play the work for improving electric conductivity and catalysis activity in terms of DMFC
With.By MFe2O4It is nanocrystalline it is nanocrystalline with Ag together be supported on conductive black, Ag/MFe can be prepared2O4/ C nano is combined
Material.The load effect of conductive black not only improves the brilliant dispersion of silver nanoparticle and pattern, and promotes MFe2O4It is nanocrystalline with
Electro transfer between Ag is nanocrystalline.Therefore, with MFe2O4/ C is compared with Ag/C, Ag/MFe2O4/ C nano composite material exhibits go out
Stronger electro catalytic activity.This nano composite material is inexpensive, easy large-scale production, the table in lithium ion battery and fuel cell
Reveal good application prospect.However, compared with commercial Pt/C, Ag/MFe2O4The catalysis activity of/C nano composite need
Improve.
The content of the invention
It is an object of the invention to provide the novel electro-catalytic agent high of a kind of good conductivity, catalysis activity.Current commercialization Pt/
C catalyst activity is high, but high cost, stability and resistance to poison are poor；Although Ag/MFe2O4/ C nano composite cost
Low, good stability, but its electric conductivity and catalysis activity are relatively low.The present invention is by silver-ferrite (Ag-MFe2O4) heterogeneous nanometer
Grain is combined with Graphene, there is provided a kind of high activity, low cost, stabilization and novel nanocomposite materials of resistance to poison and preparation method thereof
And application.
To achieve these goals, present invention design has synthesized a kind of graphene-supported silver-ferrite nano composite,
Its preparation method can both be directly loaded in the technique on Graphene using the heterogeneous nano particle of silver-ferrite, it would however also be possible to employ
The technique that first particulate load is restored on graphene oxide.
A kind of nano composite material, the nano composite material is by the graphene-supported heterogeneous nano particle of silver-ferrite
It is composited.
Wherein, the heterogeneous nano particle of silver-ferrite is the heterogeneous nano particle of ferrite of silver-transiting state metal M, by
The ferrite that particle diameter is the argent of 3~10nm and 1~3 particle diameter is 3~10nm transiting state metals M is combined to form.This is heterogeneous
The preparation method of nano particle is referring to number of patent application 201610506179.7, a kind of system of silver-ferrite composite nanometer particle
Preparation Method.
The transiting state metal M is the one kind in iron, manganese, cobalt, nickel, zinc, and wherein transiting state metal M is II valencys.
Technique one：The technique on Graphene is directly loaded in using the heterogeneous nano particle of silver-ferrite：Under room temperature condition,
It is 1 according to mass ratio by the heterogeneous nano particle of silver-ferrite and Graphene:2~5 disperse in organic solvent, and ultrasound 10~
60min, stirs 12~24h, and Magneto separate obtains graphene-supported silver-ferrite nano composite.
Technique two：Formation graphene oxide on graphene oxide is first supported on using the heterogeneous nano particle of silver-ferrite to bear
Silver-ferrite nano composite is carried, the technique for being made graphene-supported silver-ferrite nano composite is then restored：
Under room temperature condition, the dividing in water by the heterogeneous nano particle of silver-ferrite dispersion liquid in organic solvent and graphene oxide
Dispersion liquid is 1 according to the mass ratio of the wherein heterogeneous nano particle of silver-ferrite and Graphene:2~5 mixing；10~60min of ultrasound,
12~24h of stirring, phase Magneto separate of fetching water, obtains graphene oxide-loaded silver-ferrite nano composite.The material with water is washed
Wash 3~5 times, be dispersed in ethylene glycol, 30~60min of ultrasound adjusts pH=13 with NaOH, and lower 130 DEG C of argon gas atmosphere is returned
Stream 2~3h of reaction, Magneto separate obtains graphene-supported silver-ferrite nano composite.
The heterogeneous nano particle of silver-ferrite is the heterogeneous nano particle of ferrite of silver-transiting state metal M, by particle diameter
For the argent of 3~10nm is combined to form with the ferrite that 1~3 particle diameter is 3~10nm transiting state metals M.
The transiting state metal M is the one kind in iron, manganese, cobalt, nickel, zinc, and wherein transiting state metal M is II valencys.
Described organic solvent uses non-polar organic solvent.
The non-polar organic solvent is the one kind in n-hexane, hexamethylene, toluene.
Application of the above-mentioned nano composite material in terms of elctro-catalyst.
Graphene-supported silver-ferrite nano composite prepared by the present invention, on the one hand, Graphene is negative as New Type of Carbon
Carrier material, can preferably embody the reactivity site of nano material；The dilute hydrogel network of three-dimensional graphite being self-assembly of
Structure abundant buffer area for electrolyte is provided, is conducive to the diffusion of electrolyte in electrochemical reaction process；Three-dimensional grapheme
High connductivity characteristic ensures that the electronics of each reaction site redox transmission is quickly transmitted on electrode, accelerates the transmission of electronics
Speed.On the other hand, Ag-MFe2O4Cooperative effect between difference is nanocrystalline in heterogeneous nano particle can significantly improve it and urge
Change activity.Therefore, graphene-supported Ag-MFe2O4Nano composite material is that a kind of good conductivity, catalysis activity Novel electric high are urged
Agent.
Compared with existing catalyst, graphene-supported silver-ferrite nano composite as elctro-catalyst good stability,
Methanol tolerant toxicity, electric conductivity and catalysis activity are high, and its preparation process is simple, cost are relatively low, and reaction condition is easily-controllable, resulting materials shape
Looks are homogeneous, good dispersion, it is easy to expand large-scale production.
A series of concept of reduced forms is introduced in Summary, this will enter in specific embodiment part
One step is described in detail.The key that present invention part is not meant to attempt to limit technical scheme required for protection is special
Seek peace essential features, the protection domain for attempting to determine technical scheme required for protection is not meant that more.
Below in conjunction with accompanying drawing, advantages and features of the invention are described in detail.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 is graphene oxide-loaded Ag-MnFe prepared by the embodiment of the present invention 12O4The transmission electron microscope of nano composite material
Image；
Fig. 2 is graphene-supported Ag-MnFe prepared by the embodiment of the present invention 12O4The transmission electron microscope imaging of nano composite material
Figure；
Fig. 3 is graphene-supported Ag-MnFe prepared by the embodiment of the present invention 12O4Nano composite material is in 0.1mol/LKOH
ORR catalytic performance test results in solution；
Fig. 4 is graphene-supported Ag-CoFe prepared by the embodiment of the present invention 22O4The transmission electron microscope imaging of nano composite material
Figure；
Fig. 5 is graphene-supported Ag-CoFe prepared by the embodiment of the present invention 22O4Nano composite material is in 0.1mol/LKOH
ORR catalytic performance test results in solution.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with drawings and Examples pair
The present invention is described in further detail.It should be appreciated that embodiment described herein is only used to explain the present invention, and without
It is of the invention in limiting.
Nano composite material disclosed in the embodiment of the present invention is by graphene-supported silver-ferrite (Ag-MFe2O4) heterogeneous receive
Rice grain is composited, and its preparation method can be both directly loaded on Graphene using the heterogeneous nano particle of silver-ferrite
Technique, it would however also be possible to employ the technique that first particulate load is restored on graphene oxide.
Embodiment 1：
Under room temperature condition, 30mg silver-Manganese Ferrite (Ag-MnFe is taken2O4) heterogeneous nano particle is dispersed in 10mL n-hexanes；
100mg graphene oxides are taken to be dispersed in 10 ml deionized waters；Two kinds of solution are mixed and ultrasound 30min, 12h is stirred, taken
Water phase Magneto separate, obtains graphene oxide-loaded Ag-MnFe2O4Nano composite material, its transmission electron microscope photo such as Fig. 1
It is shown, Ag-MnFe2O4Heterogeneous nano particle is equably supported on graphene oxide.The material is washed with deionized 3 times, point
It is dispersed in 10mL ethylene glycol, ultrasonic 30min, dispersion liquid pH=13, argon gas gas is adjusted with the ethylene glycol solution of 2.5mol/LNaOH
The lower 130 DEG C of back flow reaction 3h of atmosphere, Magneto separate obtains the graphene-supported Ag-MnFe of favorable dispersibility2O4Nano composite material, its
Transmission electron microscope photo is as shown in Fig. 2 granule-morphology is held essentially constant in nano composite material.The material deionization
Washing 3 times, 80 DEG C of ORR catalytic performance test results being dried into after powder are as shown in Figure 3.When rotating speed is 1600rpm, the material
In -0.21V, limiting current density is about 6.5mA cm to half crest location of stockline scanning curve-2, it is a kind of electric conductivity and to urge
Change activity new catalyst higher.
Embodiment 2：
Under room temperature condition, 30mg silver-cobalt ferrite (Ag-CoFe is taken2O4) heterogeneous nano particle and 100mg graphene dispersions exist
In 10mL toluene；Ultrasonic 60min, stirs 12h, and Magneto separate obtains graphene-supported Ag-CoFe2O4Nano composite material, its is saturating
Electron micrograph is penetrated as shown in figure 4, Ag-CoFe2O4Heterogeneous nano particle is equably supported on Graphene, material after being combined
The favorable dispersibility of material.The material ethanol is washed 3 times, 80 DEG C of ORR catalytic performance tests result such as Fig. 5 institutes being dried into after powder
Show.When rotating speed is 1600rpm, in -0.26V, limiting current density is about half crest location of the linear scanning curve of the material
6.4mA cm-2, it is a kind of electric conductivity and catalysis activity new catalyst higher.
Current commercialization Pt/C good catalyst activities, but high cost, stability and resistance to poison are poor；Although Ag/
MFe2O4/ C nano composite low cost, good stability, but its electric conductivity and catalysis activity are poor.The present invention is by silver-iron oxygen
The heterogeneous nano particle of body is supported on Graphene, prepares graphene-supported silver-ferrite nano composite, and this kind of material can
As the novel electro-catalytic agent high of a kind of environment-friendly, good conductivity, catalysis activity.
The above, is only presently preferred embodiments of the present invention, is not the limitation for making other forms to the present invention, is appointed
What those skilled in the art changed possibly also with the technology contents of the disclosure above or be modified as equivalent variations etc.
Effect embodiment.But it is every without departing from technical solution of the present invention content, according to technical spirit of the invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of nano composite material, it is characterised in that：The nano composite material is heterogeneous by graphene-supported silver-ferrite
Nano-particles reinforcement is formed.
2. nano composite material according to claim 1, it is characterised in that：The heterogeneous nano particle of silver-ferrite for silver-
The heterogeneous nano particle of ferrite of transiting state metal M, is 3~10nm by argent and 1~3 particle diameter that particle diameter is 3~10nm
The ferrite of transiting state metal M is combined to form.
3. nano composite material according to claim 2, it is characterised in that：The transiting state metal M be iron, manganese, cobalt, nickel,
One kind in zinc, wherein transiting state metal M are II valencys.
4. the preparation method of nano composite material described in a kind of claim 1, it is characterised in that：Received using silver-ferrite is heterogeneous
Rice grain is directly loaded in the technique on Graphene：Under room temperature condition, by the heterogeneous nano particle of silver-ferrite and Graphene according to
Mass ratio is 1:In organic solvent, 10~60min of ultrasound stirs 12~24h, and Magneto separate obtains Graphene and bears for 2~5 dispersions
Carry silver-ferrite nano composite.
5. the preparation method of nano composite material described in a kind of claim 1, it is characterised in that：Received using silver-ferrite is heterogeneous
Rice grain is first supported on graphene oxide and forms graphene oxide-loaded silver-ferrite nano composite, then restores
It is made the technique of graphene-supported silver-ferrite nano composite：Under room temperature condition, by the heterogeneous nano particle of silver-ferrite
Dispersion liquid in organic solvent is with dispersion liquid of the graphene oxide in water according to the heterogeneous nano particle of silver-ferrite and graphite
The mass ratio of alkene is 1:2~5 mixing；10~60min of ultrasound, stirs 12~24h, phase Magneto separate of fetching water, and obtains graphene oxide
Load silver-ferrite nano composite；The material with water is washed 3-5 times, is dispersed in ethylene glycol, 30~60min of ultrasound, is used
NaOH adjusts pH=13, and the lower 130 DEG C of 2~3h of back flow reaction of argon gas atmosphere, Magneto separate obtains graphene-supported silver-iron oxygen
Body nano composite material.
6. according to claim 4 or 5 nano composite material preparation method, it is characterised in that：Silver-the ferrite is heterogeneous
Nano particle is the heterogeneous nano particle of ferrite of silver-transiting state metal M, by argent that particle diameter is 3~10nm and 1~3
Particle diameter is that the ferrite of 3~10nm transiting state metals M is combined to form.
7. the preparation method of nano composite material according to claim 6, it is characterised in that：The transiting state metal M be iron,
One kind in manganese, cobalt, nickel, zinc, wherein transiting state metal M are II valencys.
8. according to claim 4 or 5 nano composite material preparation method, it is characterised in that：Described organic solvent is adopted
Use non-polar organic solvent.
9. the preparation method of nano composite material according to claim 8, it is characterised in that：The non-polar organic solvent is
One kind in n-hexane, hexamethylene, toluene.
10. application of the nano composite material in terms of elctro-catalyst any one of the claims 1~3.
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| CN111592744A (en) * | 2020-06-29 | 2020-08-28 | 江西伟普科技有限公司 | Metal-loaded carbon/polymer-based electromagnetic shielding material and preparation method thereof |
| CN111777063A (en) * | 2020-07-09 | 2020-10-16 | 西安交通大学 | Preparation method of nano material |
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