CN109360992A - A kind of metal-nitrogen-carbon nanosheet preparation method and application of three-dimensional continuous carbon skeleton adulteration - Google Patents
A kind of metal-nitrogen-carbon nanosheet preparation method and application of three-dimensional continuous carbon skeleton adulteration Download PDFInfo
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- CN109360992A CN109360992A CN201811281542.5A CN201811281542A CN109360992A CN 109360992 A CN109360992 A CN 109360992A CN 201811281542 A CN201811281542 A CN 201811281542A CN 109360992 A CN109360992 A CN 109360992A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002135 nanosheet Substances 0.000 title claims abstract description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 29
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004033 plastic Substances 0.000 claims abstract description 20
- 229920003023 plastic Polymers 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000767 polyaniline Polymers 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 salt Amine Chemical class 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006722 reduction reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical class [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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
- H01M4/90—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
-
- 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
-
- 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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
- H01M4/9041—Metals or alloys
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of metal-nitrogen-carbon nanosheet preparation method of three-dimensional continuous carbon skeleton adulteration with hierarchical porous structure, using melamine foamed plastic as template, in the solution containing metal salt by aniline in-situ polymerization be sheet polyaniline, and separate from melamine foamed plastic surface, high temperature cabonization is carried out again, obtains the porous metals-nitrogen-carbon composite with hierarchical structure.Compared with prior art, melamine foamed plastic and the polyaniline nano piece on its surface form three-dimensional structure, metal-the nitrogen formed after carbonization-carbon composite forms 3 D stereo hierarchical porous structure, the structure helps speed up mass transfer rate in reaction, make to expose more active sites, improves active sites utilization rate.Metal-nitrogen-carbon nanosheet material preparation method of three-dimensional continuous carbon skeleton adulteration of the present invention, have many advantages, such as that environmentally protective, easy, easy to implement, production cost is low and preparation process in the three-dimensional continuous carbon skeleton adulteration of gained metal-nitrogen-carbon nanosheet morphology and size uniformity it is good, when being used as fuel battery negative pole oxygen reduction reaction elctro-catalyst, the catalytic activity of catalyst is suitable with noble metal platinum.
Description
Technical field
The invention belongs to field of nano material preparation, more particularly to a kind of metal-of three-dimensional continuous carbon skeleton adulteration
Nitrogen-carbon nanosheet catalyst preparation method.
Background technique
Fuel battery negative pole oxygen reduction reaction dynamic process is slow, is widely used platinum based catalyst at present, however platinum resource
Limited, expensive, exploitation platinum alternative catalysts are imperative.Metal-nitrogen-doped carbon material is to fuel battery negative pole hydrogen reduction
Reaction has preferable catalytic activity.Traditional preparation method mainly will be before carbon containing and nitrogen organic matter and transition metal salt etc.
Body mixing is driven, is carbonized at high temperature later, obtains the carbon material containing metal and N doping.Using conventional method preparation
Contain a large amount of micropores in metal-nitrogen-doped carbon catalyst, easily leads to the problems such as mass-transfer efficiency is low in reaction.It is asked to solve this
It inscribes, graded porous carbon is mainly prepared by the porous template of addition, such as silica, metal organic frame (MOF) in report
Material.However, template that this method is related to is expensive, removing template is gone to take time and effort, and go template procedure non-ambient friendly
It is good.Melamine foamed plastic has three-dimensional net structure, carbon rich in and nitrogen, and cheap, can keep after carbonization
Three-dimensional net structure.Document (Angew.Chem.2013,125,1060-1064) by melamine foamed plastic three-dimensional macropore knot
Structure, and it is properly added the active carbon containing micropore, the carrier with hierarchical porous structure is constructed, further mixes it with molysite
Afterwards, the carbon material of iron and N doping is obtained through carbonization, which has good catalytic activity to oxygen reduction reaction.In this method
Melamine foamed plastic and active carbon after carbonization are physical mixeds, and interface resistance is big, the pore structure of formation and active bit distribution
Unevenly.Needing invention has the preparation of metal and nitrogen-doped carbon material of three-dimensional continuous uniform cellular structure, large specific surface area
Method.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of metal-nitrogen-of hierarchical structure three-dimensional continuous carbon skeleton adulteration
The preparation method of carbon nanosheet material.This method, as skeleton, is obtained using melamine foamed plastic in its in situ Polymerization aniline
Carbonization treatment is carried out to three-dimensional polyaniline nanometer sheet, and after mixing with metal salt, is obtained a kind of negative with three-dimensional continuous carbon skeleton
Metal-N doping carbon nanosheet material of load.The continuous carbon skeleton of the material provides express passway for electron-transport, porous
Structure provides good mass transfer channel for reactants and products, and is conducive to active site and comes into full contact with reactant, improves
To the catalytic activity of reaction.The preparation method can be improved the abundance of material pore structure, increase the specific surface area of material, and prepare
Simple process, product uniformity is good, is easy to produce in batches.
On the one hand, metal-nitrogen-carbon of the present invention provides a kind of three-dimensional continuous carbon skeleton adulteration with hierarchical structure is received
Rice piece, it is and to separate from melamine by by aniline in-situ polymerization being sheet polyaniline in the solution containing metal salt
Amine foam surface, then high temperature cabonization is carried out under an inert atmosphere, preparing has porous metals-nitrogen-carbon of hierarchical structure multiple
Condensation material.
On the other hand, metal-nitrogen-of the present invention also provides a kind of three-dimensional continuous carbon skeleton adulteration with hierarchical structure
The preparation method of carbon nanosheet catalyst characterized by comprising
(1) in the solution containing metal salt melamine foamed plastic surface by aniline in-situ polymerization be sheet polyphenyl
Amine；
(2) it is carried out high temperature cabonization under an inert atmosphere again, obtains having porous metals-nitrogen-carbon of hierarchical structure multiple
Condensation material.
In another aspect, the present invention also provides a kind of, porous metals-nitrogen-carbon composite with hierarchical structure can be used as
Fuel battery negative pole oxygen reduction reaction catalyst.
The preparation method of classifying porous carbon material of the present invention has environmentally protective, easy, easy to implement, production cost
It is low；And in preparation process the three-dimensional continuous carbon skeleton adulteration of gained metal-nitrogen-carbon nanosheet morphology and size uniformity it is good etc.
Advantage, when being used as oxygen reduction electro-catalyst, the oxygen reduction catalytic activity of catalyst is significantly improved.
Detailed description of the invention
Figure 1A is nitrogen adsorption-desorption isothermal curve of 1,2,3 sample of embodiment；
Figure 1B is the pore size distribution curve of 1,2,3 sample of embodiment；
Fig. 2 is the scanning electron microscopic picture of 3 sample of embodiment；
Fig. 3 is the oxygen reduction reaction polarization curve of comparative example and embodiment 1-4 sample；
Fig. 4 is embodiment 3, the oxygen reduction reaction polarization curve of 5-8 sample.
Specific implementation method
Below with reference to specific embodiment, the present invention is further explained.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Comparative example
Commodity 20%Pt/C catalyst (believes Wan Feng company in the U.S. village).
Embodiment 1
1 milliliter of aniline monomer and 2.49 grams of ammonium persulfates are added separately in 80 ml deionized waters, at room temperature instead
Answering makes aniline in-situ polymerization for 6 hours, and drying can be obtained polyaniline, then is warming up to 1050 degree in a nitrogen atmosphere and keeps the temperature 2 small
When, it can be obtained the carbon material of N doping.
Embodiment 2
By 50 milligrams of melamine foamed plastics, 1 milliliter of aniline monomer, 2.49 grams of ammonium persulfates be added separately to 80 milliliters go from
In sub- water, react makes aniline in melamine surface in-situ polymerization for 6 hours at room temperature, can be obtained Polyaniline-Supported after dry
Melamine foamed plastic, the melamine foamed plastic of Polyaniline-Supported is placed in tube furnace, is warming up to 1050 in a nitrogen atmosphere
It spends and keeps the temperature 2 hours, can be obtained the carbon material of the porous N doping with hierarchical structure.Compared in embodiment 1 not plus trimerization
The sample of cyanamide foam, the specific surface area of sample dramatically increases (Figure 1A) in embodiment 2, and mesoporous ratio significantly improves (Figure 1B).
Embodiment 3
By 50 milligrams of melamine foamed plastics, 1 milliliter of aniline monomer, 2.49 grams of ammonium persulfates and 50 milligrams of ferric trichloride difference
It is added in 80 ml deionized waters, react 6 hours makes aniline in melamine surface in-situ polymerization, 80 degree of dryings at room temperature
After obtain black powder, place it in tube furnace, be warming up in a nitrogen atmosphere 1050 degree and keep the temperature 2 hours, can be obtained
Porous iron-N doping carbon material with hierarchical structure.As seen from Figure 1, the sample of this method preparation has three-dimensional network shape
Structure (Fig. 2 a), net list EDS maps have three-dimensional laminated structure (Fig. 2 b-d).It is real compared to the sample for not adding iron in embodiment 2
The specific surface area for applying sample in example 3 slightly reduces (Figure 1A), and micropore ratio increases, and mesoporous ratio decreases (Figure 1B).
Embodiment 4
By 1 milliliter of aniline monomer, 2.49 grams of ammonium persulfates, 50 milligrams of melamine foamed plastics and 75 milligrams of ferric trichloride difference
It is added in 80 ml deionized waters, react 6 hours makes aniline in melamine surface in-situ polymerization, 80 degree of dryings at room temperature
After obtain black powder, place it in tube furnace, be warming up in a nitrogen atmosphere 1050 degree and keep the temperature 2 hours, can be obtained
Porous iron-N doping carbon material with hierarchical structure.
Embodiment 5
By 50 milligrams of melamine foamed plastics, 1 milliliter of aniline monomer, 50 milligrams of nickel nitrates, 2.49 grams of ammonium persulfates add respectively
Enter into 80 ml deionized waters, react 6 hours makes aniline after melamine surface in-situ polymerization, 80 degree of dryings at room temperature
Black powder is obtained, is placed it in tube furnace, be warming up to 1050 degree in a nitrogen atmosphere and keeps the temperature 2 hours, can be obtained tool
There is porous nickel-N doping carbon material of hierarchical structure.
Embodiment 6
By 50 milligrams of melamine foamed plastics, 1 milliliter of aniline monomer, 2.49 grams of ammonium persulfates and 25 milligrams of cobalt nitrates, respectively
It is added in 80 ml deionized waters, react 6 hours makes aniline in melamine surface in-situ polymerization, 80 degree of dryings at room temperature
After obtain black powder, place it in tube furnace, be warming up in a nitrogen atmosphere 1050 degree and keep the temperature 2 hours, can be obtained
The carbon material of porous cobalt-N doping with hierarchical structure.
Embodiment 7
By 50 milligrams of melamine foamed plastics, 1 milliliter of aniline monomer, 30 milligrams of copper chlorides, 2.49 grams of ammonium persulfates add respectively
Enter into 80 ml deionized waters, react 6 hours makes aniline after melamine surface in-situ polymerization, 80 degree of dryings at room temperature
Black powder is obtained, is placed it in tube furnace, be warming up to 1050 degree in a nitrogen atmosphere and keeps the temperature 2 hours, can be obtained tool
There is Porous Cu-nitrogen-doped carbon material of hierarchical structure.
Embodiment 8
By 50 milligrams of melamine foamed plastics, 1 milliliter of aniline monomer, 45 milligrams of manganese acetates, 2.49 grams of ammonium persulfates add respectively
Enter into 80 ml deionized waters, react 6 hours makes aniline after melamine surface in-situ polymerization, 80 degree of dryings at room temperature
Black powder is obtained, is placed it in tube furnace, be warming up to 1050 degree in a nitrogen atmosphere and keeps the temperature 2 hours, can be obtained tool
There is porous manganese-nitrogen-doped carbon material of hierarchical structure.
Effect example
Metal-nitrogen-carbon nanosheet of three-dimensional continuous carbon skeleton adulteration obtained is used for oxygen reduction reaction, test condition
Are as follows: 0.1mol L-1NaOH electrolyte, electrode rotary speed: 1600 revs/min, sweep speed 10mV s-1。
By Fig. 3 and Fig. 4 as it can be seen that metal-nitrogen-carbon nanosheet of prepared three-dimensional continuous carbon skeleton adulteration is being used as oxygen also
When former catalysts, excellent catalytic performance is shown, wherein the performance of embodiment 3 and 4 is urged with comparative example commercialization Pt/C
The performance of agent is close.
Embodiment described above is only that preferred embodiments of the present invention will be described, not to the scope of the present invention
It is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical solution of the present invention
The various changes and improvements made should all be fallen into the protection scope that claims of the present invention determines.
Claims (7)
1. a kind of metal-nitrogen-carbon nanosheet catalyst and preparation method of three-dimensional continuous carbon skeleton adulteration, it is characterised in that with three
Poly cyanamid foam is template, utilizes polymerizer by aniline in-situ polymerization at lamellar structure polyphenyl in the solution containing metal salt
Amine, and template surface is separated from, then carry out carbonization treatment under an inert atmosphere and obtain the gold with three-dimensional continuous carbon skeleton adulteration
Category-nitrogen-carbon nanosheet material.
2. preparation method as described in claim 1, it is characterised in that:
(1) by aniline in-situ polymerization it is sheet polyaniline using polymerizer in the solution containing metal salt, and separates from three
Poly cyanamid foam surface；
(2) it is carried out high temperature cabonization processing in a nitrogen atmosphere again, obtains having porous metals-nitrogen-carbon of hierarchical structure multiple
Condensation material.
3. preparation method as claimed in claim 2, it is characterised in that: the step (1) includes, by a certain amount of aniline list
Body, metal salt, ammonium persulfate and melamine foamed plastic are added separately in deionized water, make aniline in melamine at room temperature
In situ Polymerization can be obtained the three-dimensional sheet polyaniline of melamine foamed plastic load after dry.
4. preparation method as claimed in claim 2, it is characterised in that: the step (2) includes loading melamine foamed plastic
Polyaniline be placed in tube furnace, be warming up under an inert atmosphere certain temperature and keep the temperature a period of time, can be obtained have point
Porous metals-nitrogen-carbon composite of level structure.
5. preparation method as claimed in claim 1, which is characterized in that the metal salt is the chlorine of iron, nickel, cobalt, copper, manganese
Any one or more in salt, nitrate and sulfate.
6. preparation method as claimed in claim 1, which is characterized in that the temperature of the carbonization treatment can be 600-1100
Arbitrary temp between degree Celsius.
7. preparation method as claimed in claim 1, which is characterized in that the inert atmosphere can be nitrogen, argon gas, helium
One of atmosphere is a variety of.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811281542.5A CN109360992A (en) | 2018-10-23 | 2018-10-23 | A kind of metal-nitrogen-carbon nanosheet preparation method and application of three-dimensional continuous carbon skeleton adulteration |
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|---|---|---|---|
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| CN114735735A (en) * | 2022-05-10 | 2022-07-12 | 广东工业大学 | Hierarchical porous nano-alumina with adjustable morphology as well as preparation method and application thereof |
| CN115193465A (en) * | 2022-06-02 | 2022-10-18 | 河南省科学院化学研究所有限公司 | Nitrogen-doped carbon two-dimensional mesoporous catalyst and preparation method and application thereof |
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| CN116239905A (en) * | 2022-06-21 | 2023-06-09 | 青岛科技大学 | Preparation method of marine anti-corrosion and anti-fouling multi-effect coating material |
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