CN108543545A - A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications - Google Patents
A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 229910002555 FeNi Inorganic materials 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229960002413 ferric citrate Drugs 0.000 claims abstract description 28
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 20
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000003792 electrolyte Substances 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 16
- 238000000197 pyrolysis Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000013313 FeNO test Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 4
- 239000000203 mixture Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 230000010287 polarization Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 238000007605 air drying Methods 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229940021013 electrolyte solution Drugs 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 206010054949 Metaplasia Diseases 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000015689 metaplastic ossification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910002546 FeCo Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GLMQHZPGHAPYIO-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [NH4+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O GLMQHZPGHAPYIO-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/33—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
-
- 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
Abstract
A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications, belong to energy and material and electrochemical field.The catalyst with dicyandiamide be the sources C and the sources N, ferric citrate, NiCl2·6H2O is source metal, using " one kettle way " be pyrolyzed in two stages a step be made.FeNi metallics in catalyst are largely uniformly wrapped in the carbon nanotube tube wall of " Bamboo-shaped " N doping, are distributed in carbon nanotube tip on a small quantity.Compared with common metal alloy oxygen reduction reaction and oxygen evolution reaction bifunctional catalyst, which also shows good oxygen evolution reaction activity and stability under alkaline condition；And preparation method is simple, it is raw materials used it is at low cost, source is wide；The fields such as Proton Exchange Membrane Fuel Cells, electrolysis water, metal-air battery are can be widely applied to, there is high value of practical.
Description
Technical field
The invention belongs to energy and material and electrochemical fields, are related to a kind of applied to fuel cell, electrolysis water and metal-sky
The elctro-catalyst and preparation method of pneumoelectric pond oxygen reduction reaction and oxygen evolution reaction, and in particular to a kind of tri- doped carbon of Fe, Ni, N is received
Mitron cladded type FeNi@NCNT catalyst, preparation method and applications.
Background technology
Fuel cell, electrolysis water and metal-air battery etc. are the hot spots of recent domestic scholar research.However, oxygen
It is fast that the bottleneck that electrode reaction (oxygen reduction reaction (ORR) and oxygen evolution reaction (OER)) dynamics is slow problem strongly limits it
Speed development, there is an urgent need for research and development effective catalysts to improve reaction rate, reduces overpotential.Currently, Pt base catalyst is acknowledged as urging
Change the most outstanding catalyst of ORR, but its OER performance is poor；IrO2、RuO2Although catalyst OER performances are higher, its ORR
Performance is very low.Moreover, these noble metals of Pt, Ir, Ru are expensive, reserves are limited, stability is poor, big rule are cannot be satisfied
Mould commercial applications demand.Therefore, there is an urgent need to develop with high catalytic activity, low cost and good stability ORR and
The difunctional non-precious metal catalysts of OER.
Transition metal (such as Fe, Co, Ni) base elctro-catalyst is lived due to cheap, rich reserves, environmental-friendly, catalysis
Property is higher etc., it is considered to be the catalyst of most potential alternative precious metal catalyst ORR and OER.Especially bimetallic base is urged
Agent, it is possible to provide abundant variation of valence is of great significance to improving ORR and OER performances.However, transition metal base is catalyzed
Agent poorly conductive is easily reunited, and needs to further increase its catalytic performance.By in the carbon with high-specific surface area and high conductivity
Or anchor in situ closes the strategy of metal_based material on hetero atom (N, P, S etc.) doping carbon material, can greatly improve catalyst conduction
Property while may additionally facilitate the dispersion of metal, improve electronics conduction, molecular/ionic mass transfer ability, and Heteroatom doping carbon
Material also advantageously improves ORR activity, thus is a kind of very effective side for improving ORR and OER bifunctional catalyst performances
Method.
Document [Adv.Sustainable Syst.2017,1,1700020] is coated by solvent structure poly-dopamine
Metal precursor (FeM/PDA, M=Ni, Co), then the method for high temperature cabonization FeNi, FeCo coupling N doping in situ has been made
Porous carbon materials FeM/NPC (M=Ni, Co).The experimental results showed that FeM/NPC (M=Ni, Co) catalyst is in same electrolyte
In show good ORR, OER and HER activity.However, time-consuming for the catalyst preparation process, experiment condition is up for into one
Step is improved.Fu etc. [Adv.Funct.Mater. 2018,28,1705094] uses electrostatic spinning technique by polyvinylpyrrolidine
Ketone, polyacrylonitrile, Ni (NO3)2·6H2O and Co (NO3)2·6H2Nanofiber, subsequent high temperature pyrolysis is made in the mixed solution of O
The N dopen Nano fibers of NiCo alloys modification have been made.The experimental results showed that the catalyst show under alkaline condition it is higher
ORR and OER Activity and stabills.However, the nanofiber that electrostatic spinning technique is prepared is not readily separated, low yield, intensity
Difference, and the catalyst preparation process is complicated, is unfavorable for preparing on a large scale.
In conclusion the nitrogen-doped carbon material (MM '/NC) of bimetallic base modification shows good catalysis ORR and OER
The potential of process, but preparation process is up for being further simplified.So simplify preparation process, reduce cost and design be easy to big
The efficient MM ' of technical scale metaplasia production/NC catalyst has important practical significance and application value.
The present invention uses dicyandiamide cheap, that raw material sources are wide for the sources C and the sources N, ferric citrate and NiCl2·
6H2O is source metal, using a kind of " one kettle way " pyrogenically prepared tri- doped carbon nanometer pipe of Fe, Ni, N of substep under an inert atmosphere
FeNi@NCNT catalyst is coated, for being catalyzed ORR and OER processes.This method preparation process is simple, of low cost, is easy to amplify
Production, it is often more important that the FeNi@NCNT large specific surface areas of synthesis, metal are coated by carbon nanotube, are conducive to improve material
Catalytic activity and stability.
Invention content
In view of the problems of the existing technology, the present invention provides a kind of tri- doped carbon nanometer pipe cladded type FeNi@of Fe, Ni, N
NCNT catalyst, preparation method and applications, the catalyst use cheap dicyandiamide for the sources C and the sources N, ferric citrate
And NiCl2·6H2O is source metal, and using " one kettle way ", substep is pyrogenically prepared under an inert atmosphere.FeNi metals in catalyst
Particle is largely uniformly wrapped in the carbon nanotube tube wall of " Bamboo-shaped " N doping, is distributed in point inside carbon nanotube on a small quantity
End.FeNi nano-particles in tube wall contribute to regulating catalyst surface electronic to be distributed, and improve catalyst activity；It avoids simultaneously
FeNi nano-particles and electrolyte contacts inhibit the reunion of FeNi nano-particles, improve the stability of material.On the other hand, N
Doped carbon nanometer pipe can provide high specific surface area and electric conductivity, be conducive to the mass transport process of electronics conduction and reaction species.With
Common metal alloy oxygen reduction reaction is compared with oxygen evolution reaction bifunctional catalyst, which also shows under alkaline condition
Go out good oxygen evolution reaction activity and stability；And preparation method is simple, it is raw materials used it is at low cost, source is wide, be conducive to scale
Metaplasia is produced；The fields such as Proton Exchange Membrane Fuel Cells, electrolysis water, metal-air battery are can be widely applied to, there is higher reality
With value.
In order to achieve the above object, the technical solution of use of the invention is as follows：
A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, the catalyst are unique " ring
Shape " carbon nanotube, metal object phase FeNi alloys and Fe3O4It is coated in NCNT, and is mainly dispersed in the tube wall of NCNT
Portion, some particles are located at the tip inside pipe, effectively avoid being in direct contact for metallic and electrolyte in reaction process, help
In the stability for improving catalyst.The incorporation of hetero atom N can create more active sites；Bimetallic combination can provide abundant
Variation of valence can be catalyzed ORR and OER reactions simultaneously.
The preparation process of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of above-mentioned Fe, Ni, N is as follows：
1) dissolving metal salts are obtained to solution A in water, the mixed solution that dicyandiamide is dissolved in solution A and ethyl alcohol obtains
Solution B；Wherein, the molar ratio of dicyandiamide and metal salt (iron and nickel) is 10:1-80:1, iron nickel molar ratio is 1:0-1:10, water
Volume ratio with ethyl alcohol is 20:1-1:20.The metal salt includes ferric citrate (C6H11FeNO7, AFC) and NiCl2·
6H2O。
2) drying steps 1) obtained by solution B, catalyst pyrolytic precursors are made；
3) calcining step 2) in gained catalyst precarsor obtain FeNi@NCNT catalyst
Under inert gas shielding, 1-20 DEG C of min-1Temperature programming is to 400-600 DEG C of calcining 1-4h, then 3-10 DEG C of min-1
It is warming up to after calcining 1-10h at 650-1200 DEG C of pyrolysis temperature, FeNi@NCNT catalyst is obtained after natural cooling.
Ferric citrate described in step 1) or NiCl2·6H2O can be the transition metal such as Mn, Co, Ni, Cu or Zn
One or more of soluble-salt mixture.
Drying means described in step 2) is vacuum drying, dry, the inert atmosphere drying of air atmosphere etc., drying temperature
It is 0-150 DEG C, drying time 3-100h.
Tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of above-mentioned Fe, Ni, N is used as fuel cell, electrolysis water or gold
Cloudy (negative) pole ORR and/or the OER elctro-catalyst of category-air cell.
Compared with prior art, carbon nanotube cladded type FeNi@NCNT catalyst of the present invention and preparation method tool
There is following advantage：
1) tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalysis of Fe, Ni, N prepared by the method for the invention is used
Agent, pattern are bamboo-like carbon nano tubes, are conducive to provide high specific surface area and electric conductivity, increase catalyst (solid phase), oxygen,
The area of electrolyte three-phase reaction interface,
2) tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalysis of Fe, Ni, N prepared by the method for the invention is used
Agent, FeNi nano-particles are mainly dispersed in inside carbon nanotube tube wall, on the one hand FeNi nano-particles are altered by
The electronics distribution of surface graphene carbon nanotube walls influences the activity of catalyst, at the same FeNi active sites can to avoid electrolyte and
The corrosion of electrochemical process inhibits the reunion of metal nanoparticle, is conducive to the electro-chemical activity and stability that improve catalyst.
3) the FeNi@NCNT catalyst for using the method for the invention to prepare, by regulating and controlling raw material ingredient proportion and preparation
Process, such as the precursor type of metal source of iron and nickel source, content ratio, calcination temperature, the achievable catalysis dosage form of calcination time
The controllable preparation of looks, structure.
4) use FeNi@NCNT catalyst prepared by the method for the invention using dicyandiamide for the sources C and the sources N, citric acid
Iron ammonium and NiCl2·6H2O is source metal, and low in raw material price is easy to get, and helps to mass produce.
5) the FeNi@NCNT catalyst for using the method for the invention to prepare, using " one kettle way ", pyrolysis is primary stage by stage
It is prepared, preparation process is simple, economical, safe, reproducible, is conducive to the amplification production of the catalyst.
6) the FeNi@NCNT catalyst for using the method for the invention to prepare, shows good in alkaline electrolyte
ORR catalytic performances, and close to commercialization 20wt.%Pt/C catalyst, can be used for fuel cell, electrolysis water, metal-air electricity
Pond etc. is multi-field.
7) the FeNi@NCNT catalyst for using the method for the invention to prepare, shows good in alkaline electrolyte
OER catalytic performances, and OER performances are better than Pt/C catalyst, can be used as metal-air battery catalyst, apparatus for electrolyzing etc.
Catalyst extensive use.
8) the FeNi@NCNT catalyst for using the method for the invention to prepare is provided simultaneously with excellent ORR and OER catalysis
Activity is the devices such as chargeable metal-air battery there is an urgent need for double-function catalyzing material.
Description of the drawings：
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 2.
Fig. 2 is that transmission electron microscope (TEM) photo of sample is made according to embodiment 2 under the conditions of 100nm.
Fig. 3 is that transmission electron microscope (TEM) photo of sample is made according to embodiment 2 under the conditions of 20nm.
Fig. 4 (a) is the isothermal nitrogen adsorption desorption curve (BET) that sample is made according to embodiment 2；Fig. 4 (b) is according to BET
The pore distribution curve of sample is made in embodiment 2 obtained by (Fig. 4 (a)) figure.
Fig. 5 (a) is according to sample made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1 KOH
ORR polarization curves in electrolyte, test voltage ranging from -0.8~0.2V, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 5 (b) is according to sample made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1 KOH
OER polarization curves in electrolyte, test voltage ranging from 0~1V, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 6 (a) is according to sample and comparative example 1 made from embodiment 2,4,5 in room temperature, O20.1 mol L of saturation- 1ORR polarization curves in KOH electrolyte, test voltage ranging from -0.8~0.2V, sweep speed：10 mV s-1, rotating speed：
1600rpm。
Fig. 6 (b) is according to sample and comparative example 1 made from embodiment 2,4,5 in room temperature, O20.1 mol L of saturation- 1OER polarization curves in KOH electrolyte, test voltage ranging from 0~1V, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 7 (a) is according to sample and comparative example 1 made from embodiment 2,6,7 in room temperature, O20.1 mol L of saturation- 1ORR polarization curves in KOH electrolyte, test voltage ranging from -0.8~0.2V, sweep speed：10 mV s-1, rotating speed：
1600rpm。
Fig. 7 (b) is according to sample and comparative example 1 made from embodiment 2,6,7 in room temperature, O20.1 mol L of saturation- 1OER polarization curves in KOH electrolyte, test voltage ranging from 0~1V, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 8 be according to sample made from embodiment 2 at room temperature, respectively in O2Saturation and N20.1 mol L of saturation- 1CV figures in KOH electrolyte, sweep speed：50mV s-1。
Fig. 9 is according to sample made from embodiment 2 in room temperature, O2The 0.1mol L of saturation-1Linearly sweeping in KOH electrolyte
Volt-ampere (LSV) curve is retouched, speed is swept：10mV s-1, rotating speed：400rpm, 900rpm, 1600 rpm, 2500rpm.
Figure 10 is Koutecky-Levich (K-L) songs that the LSV curves (Fig. 9) of sample are made according to embodiment 2 and obtain
Line.
Figure 11 is according to sample made from embodiment 2 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH is electrolysed
Chronoamperogram in liquid, rotating speed：1600rpm, voltage constant is in -0.4V.
Figure 12 (a) is according to sample made from embodiment 2 in O2The 0.1moL L of saturation-18000 circles follow in KOH electrolyte
ORR activity comparison diagrams after ring, CV scanning range -0.4-0.1V sweep speed：10mV s-1, rotating speed：1600rpm；
Figure 12 (b) is according to sample made from embodiment 2 in O2The 0.1moL L of saturation-12000 circles follow in KOH electrolyte
OER activity comparison diagrams after ring, CV scanning range 0.2-0.7V sweep speed：10mV s-1, rotating speed：1600rpm.
Figure 13 is the N at room temperature of sample difference made from embodiment 22The 0.1mol L of saturation-1KOH electrolyte, O2Saturation
0.1mol L-1KOH electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1CV figures in KOH electrolyte, sweep speed：
10mV s-1。
Figure 14 be comparative example 1 be commercialized 20wt.%Pt/C catalyst respectively at room temperature, O20.1 mol L of saturation- 1KOH electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1CV figures in KOH electrolyte, sweep speed：10mV s-1。
Specific implementation mode
The present invention is explained in detail with reference to specific example, but the present invention is not limited only to these specific implementations
Example.
Embodiment 1：DA-Fe3(DA is dicyandiamide, Fe to Ni-8003Ni refers to ferric citrate and NiCl in raw material2·6H2O
Molal weight ratio be 3:1, DA and the molar ratio of metal Fe and Ni are about 40:1,800 finger pyrolysis temperature is 800 DEG C)
By the ferric citrate of 0.1103g and 0.0178g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in the mixed solution of A and 20mL absolute ethyl alcohols and obtains solution B, is stirred at 60 DEG C of oil bath
30min is mixed, is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinet dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling
Obtain Fe3Ni@NCNT-800 catalyst (DA-Fe3Ni-800)。
Embodiment 2：DA-FeNi-800(DA：Dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material2·6H2O's rubs
Your mass ratio is 1:1, DA and the molar ratio of metal Fe and Ni are about 40:1,800 finger pyrolysis temperature is 800 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in A and 20mL absolute ethyl alcohol mixed solutions and obtains solution B, is stirred at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinet dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling
Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
Embodiment 3：DA-FeNi3-800(DA：Dicyandiamide, FeNi3Refer to ferric citrate and NiCl in raw material2·6H2O's
Molal weight ratio is 1:3, DA and the molar ratio of metal Fe and Ni are about 40:1,800 finger pyrolysis temperature is 800 DEG C)
By the ferric citrate of 0.0367g and 0.0535g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in A and 20mL absolute ethyl alcohol mixed solutions and obtains solution B, is stirred at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinet dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling
Obtain FeNi3@NCNT-800 catalyst (DA-FeNi3-800)。
Embodiment 4：DA-FeNi-700(DA：Dicyandiamide, Fe3Ni refers to ferric citrate and NiCl in raw material2·6H2O's rubs
Your mass ratio is 1:1, DA and the molar ratio of metal Fe and Ni are about 40:1,700 finger pyrolysis temperature is 700 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in the mixed solution of A and 20mL absolute ethyl alcohols and obtains solution B, is stirred at 60 DEG C of oil bath
30min is mixed, is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinet dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 700 DEG C and calcines 1h again, after natural cooling
Obtain FeNi@NCNT-700 catalyst (DA-FeNi-700).
Embodiment 5：DA-FeNi-900(DA：Dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material2·6H2O's rubs
Your mass ratio is 1:1, DA and the molar ratio of metal Fe and Ni are about 40:1,900 finger pyrolysis temperature is 900 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in the mixed solution of A and 20mL absolute ethyl alcohols and obtains solution B, is stirred at 60 DEG C of oil bath
30min is mixed, is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinet dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 900 DEG C and calcines 1h again, after natural cooling
Obtain FeNi@NCNT-900 catalyst (DA-FeNi-900).
Embodiment 6：DA-Fe-800(DA：Dicyandiamide, Fe are ferric citrate, mole 0.15mM, DA and metal
The molar ratio of Fe is about 79:1,800 finger pyrolysis temperature is 800 DEG C)
The ferric citrate of 0.0735g is dissolved in 10mL deionized waters, solution A is obtained；The dicyandiamide of 1 g is weighed again
Solution B is obtained in the mixed solution being dissolved in A and 20mL absolute ethyl alcohols, 30min is stirred at 60 DEG C of oil bath, fully to dissolve
It is uniformly mixed；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets dry 11h, before obtaining catalyst
Body；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Program liter
Temperature is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, Fe@NCNT-800 are obtained after natural cooling and are urged
Agent (DA-Fe-800).
Embodiment 7：DA-Ni-800(DA：Dicyandiamide, Ni refer to NiCl2·6H2O, mole are 0.15 mM, DA and metal
The molar ratio of Ni is about 79:1,800 finger pyrolysis temperature is 800 DEG C)
By 0.0362g NiCl2·6H2O is dissolved in 10mL deionized waters, obtains solution A；The dicyandiamide of 1g is weighed again
It is dissolved in the mixed solution of A and 20mL absolute ethyl alcohols and obtains solution B, 30min is stirred at 60 DEG C of oil bath, it is mixed with abundant dissolving
It closes uniform；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets dry 11h, obtain catalyst precarsor；
Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming
1h are calcined to 550 DEG C, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, (DA-Ni-800) catalysis is obtained after natural cooling
Agent (DA-Ni-800).
Embodiment 8：DA-FeNi-800-Z(DA：Dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material2·6H2O's
Molal weight ratio is 1:1, DA and the molar ratio of metal Fe and Ni are about 40:1,800 finger pyrolysis temperature is 800 DEG C, and Z refers to vacuum
It is dry)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in A and 20mL absolute ethyl alcohol mixed solutions and obtains solution B, is stirred at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of vacuum drying chamber dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling
Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
Embodiment 9：DA19-FeNi-800(DA19- FeNi refers to dicyandiamide and ferric citrate and NiCl2·6H2O is total to rub
You are than about 19:1, FeNi molar ratio is 1:1,800 finger pyrolysis temperature is 800 DEG C)
By the ferric citrate of 0.1505g and 0.0713g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in A and 20mL absolute ethyl alcohol mixed solutions and obtains solution B, is stirred at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinet dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, after natural cooling
Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
Embodiment 10：DA-FeNi-800-2(DA：Dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material2·6H2O
Molal weight ratio be 1:1, DA and the molar ratio of metal Fe and Ni are about 40:1,800 finger pyrolysis temperature is 800 DEG C, and 2 refer to 800
2h is calcined at DEG C)
By the ferric citrate of 0.0395g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized waters, is obtained molten
Liquid A；The dicyandiamide for weighing 1g again is dissolved in A and 20mL absolute ethyl alcohol mixed solutions and obtains solution B, is stirred at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolving；Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinet dryings
11h obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in nitrogen protection
Lower 5 DEG C of min-1Temperature programming is to 550 DEG C of calcinings 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 2h again, after natural cooling
Obtain FeNi@NCNT-800 catalyst (DA-FeNi-800).
Comparative example 1：20wt.%Pt/C catalyst (Alfa Aesar) is commercialized).
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 2.By the PCPDF cards point of XRD spectra
The metal species that embodiment 2 known to analysis is made in sample contain two kinds of crystalline structures：(43.46 °, 50.38 °, 73.96 ° are spread out FeNi
It penetrates peak to be between Fe (PDF#52-0513) and Ni (PDF#04-0850), it is seen that form FeNi phases and be respectively belonging to
(111), (200), (220) crystal face), Fe3O4(PDF#75-0033,35.48 ° (3 1 1), 30.12 ° of (2 2 0), 62.63
(440)), corresponding peak position and intensity such as figure mark.In addition, the feature that 2 θ=26 ° or so are graphene (002) crystal face is spread out
Peak is penetrated, showing the material has good carbonization structure.
Fig. 2, Fig. 3 are transmission electron microscope (TEM) photo that sample is made according to embodiment 2.By Fig. 2, Fig. 3 it is found that embodiment
Sample made from 2 is that " Bamboo-shaped " carbon nano tube structure coats FeNi nano particle structures.Carbon nanotube diameter is in 40~130nm
It differs, length reaches several microns.Contain black particles in carbon nanotube, may be FeNi or Fe3O4, size is in 15~40nm ranges.
This clad structure can avoid being in direct contact for metallic and electrolyte solution, improve the stability of material.
Fig. 4 (a) is the isothermal nitrogen adsorption desorption curve (BET) that sample is made according to embodiment 2, the specific surface area of catalyst
Up to 163m2g-1.Sample aperture is distributed in 3.5nm and 20~50nm made from embodiment 2 known to Fig. 4 (b) pore size distribution curves.
Abundant meso-hole structure contributes to the mass transfer of oxygen, to be conducive to the progress of ORR/OER reactions.
Fig. 5 (a) is according to sample made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1 KOH
ORR polarization curves in electrolyte, test voltage ranging from -0.8~0.2V, sweep speed：10mV s-1, rotating speed：1600rpm.Fig. 5
(b) it is according to sample made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1OER in KOH electrolyte
Polarization curve, test voltage ranging from 0~1V, sweeps speed：10mV s-1, rotating speed：1600rpm.By Fig. 5 (a) and Fig. 5 (b) it is found that
Ferric citrate and NiCl2·6H2The rate of charge of O is affected to the ORR of catalyst.Ferric citrate and rate of charge are 1:1
When, ORR limiting current densities are larger, and take-off potential is 3 with rate of charge:Value when 1 is close；OER performances are 1 with rate of charge:3
When it is close.Consider from the difunctional angles of ORR and OER, ferric citrate and rate of charge are 1:When 1, overpotential minimum (Δ E=E
（jOER=10mA cm -2）-E（jOER=-3mA cm -2）0.85）V), ORR and OER best performances.
Fig. 6 (a) is according to sample and comparative example 1 made from embodiment 2,4,5 in room temperature, O20.1 mol L of saturation- 1ORR polarization curves in KOH electrolyte, test voltage ranging from -0.8~0.2V, sweep speed：10 mV s-1, rotating speed：
1600rpm.Fig. 6 (b) is according to sample and comparative example 1 made from embodiment 2,4,5 in room temperature, O2The 0.1mol L of saturation- 1OER polarization curves in KOH electrolyte, test voltage ranging from 0~1V, sweep speed：10mV s-1, rotating speed：1600rpm.By Fig. 6
It is found that calcination temperature is affected to ORR and OER performances, the half-wave electricity of ORR performances when calcining preparation temperature and being 800 DEG C
Position (- 0.176V) and limiting current density are maximum, ORR best performances；jOER=10mA cm-2It is maximum to locate voltage, OER performances are most
It is excellent.
Fig. 7 (a) is according to sample and comparative example 1 made from embodiment 2,6,7 in room temperature, O20.1 mol L of saturation- 1ORR polarization curves in KOH electrolyte, test voltage ranging from -0.8~0.2V, sweep speed：10 mV s-1, rotating speed：
1600rpm.Fig. 7 (b) is according to sample and comparative example 1 made from embodiment 2,6,7 in room temperature, O2The 0.1mol L of saturation- 1OER polarization curves in KOH electrolyte, test voltage ranging from 0~1V, sweep speed：10mV s-1, rotating speed：1600rpm.By Fig. 7
(a) it is found that the half wave potential (- 0.176V) of catalyst is made in embodiment 2, close to the half of commercialization 20wt.%Pt/C catalyst
Wave current potential (- 0.126 V) illustrates that the catalyst has good ORR catalytic performances under alkaline condition；By Fig. 7 (b) it is found that
Its OER current potential of catalyst (E is made in embodiment 2JOER=10mA cm -2=0.686V) it is better than 20wt.%Pt/C catalyst, show that this is urged
Agent also has good OER catalytic performances.
Fig. 8 is according to sample made from embodiment 2 at room temperature respectively in O2Saturation and N2The 0.1mol L of saturation-1KOH
The CV of electrolyte schemes, and sweeps speed：50mV s-1.As shown in Figure 8, catalyst made from embodiment 1 is in N2The 0.1mol L of saturation-1KOH
There is no ORR in electrolyte, in O2The 0.1mol L of saturation-1There are the peaks ORR in current potential for -0.18V or so in KOH electrolyte
Occur.
Fig. 9 is according to sample made from embodiment 2 in room temperature, O2The 0.1mol L of saturation-1Linearly sweeping in KOH electrolyte
Volt-ampere (LSV) curve is retouched, speed is swept：10mV s-1, rotating speed：400rpm、900rpm、1600 rpm、2500rpm.As shown in Figure 9, with
Rotating speed increase, ORR take-off potentials remain unchanged, and Limited diffusion current density constantly increases.
Figure 10 is Koutecky-Levich (K-L) songs that the LSV curves (Fig. 9) of sample are made according to embodiment 2 and obtain
Line.The electron transfer number that 2 surface catalysis ORR of embodiment is calculated according to K-L equations is 4 or so, shows the catalysis obtained of embodiment 2
Agent is catalyzed ORR with 4 electronic processes.
Figure 11 is according to sample made from embodiment 2 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH is electrolysed
Chronoamperogram in liquid, rotating speed：1600rpm, voltage constant is in -0.4V.By comparison it is found that in the timing by 1800s
After current stability test, catalyst activity decays to 98.16% made from embodiment 2；Under the same terms, commercialization
20wt.%Pt/C catalyst activities decay to 85.43%, illustrate that catalyst stability made from embodiment 2 is better than comparative example 1.
Figure 12 is according to sample made from embodiment 2 in O2The 0.1moL L of saturation-1The circles of (a) 8000 follow in KOH electrolyte
ORR activity comparison diagrams after ring, CV -0.4~0.1V of scanning range sweep speed：10mV s-1, rotating speed：1600rpm；(b) 2000 circle
OER activity comparison diagrams after cycle, 0.2~0.7 V of CV scanning ranges sweep speed：10mV s-1, rotating speed：1600rpm.By Figure 12
(a) it is found that catalyst is in O made from embodiment 22The 0.1moL L of saturation-1In KOH electrolyte solutions, recycled by 8000 circles
Afterwards, CV curves show that catalyst ORR stability made from embodiment 2 is preferable without significant change.By Figure 12 (b) it is found that embodiment
Catalyst is in O made from 22The 0.1moL L of saturation-1In KOH electrolyte solutions, after 2000 circle cycles, CV curves are without apparent
Variation, shows that catalyst OER stability made from embodiment 2 is preferable.
Figure 13 be embodiment 2 made from sample respectively at room temperature, O2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation
3mol L-1CH3OH+0.1mol L-1CV figures in KOH electrolyte, sweep speed： 10mV s-1.As shown in Figure 13, embodiment 2 is made
For the catalyst obtained in the electrolyte solution whether there is or not methanol, CV curves show catalyst made from embodiment 2 without significant change
It is influenced by methanol fuel smaller, may be used as methanol fuel cell cathode catalyst.
Figure 14 be comparative example 1 respectively at room temperature, O2The 0.1mol L of saturation-1KOH electrolyte, O2The 3mol L of saturation- 1CH3OH+0.1mol L-1CV figures in KOH electrolyte, sweep speed：10mV s-1.As shown in Figure 14, commercialization 20wt.%Pt/C is urged
There is apparent methanol oxidation current in the electrolyte solution for having methanol in agent, can catalysis methanol oxidation (- 0.4~
0.2V), show that comparative example 1 is poor to the selectivity of fuel, is easily influenced by methanol combustion.
Claims (7)
1. a kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, which is characterized in that the catalyst
It is tri- doped carbon nanometer pipe coated catalyst of Fe, Ni, N for unique " Bamboo-shaped " carbon nanotube；Metal object phase FeNi alloys
And Fe3O4It is coated in carbon nanotube NCNT, and is mainly dispersed in inside the tube wall of NCNT, some particles are located in pipe
The tip in portion can effectively avoid being in direct contact for metallic and electrolyte in reaction process, improve the stability of catalyst；
Bimetallic combination is capable of providing abundant variation of valence, while being catalyzed ORR and OER reactions.
2. the preparation side of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N described in claim 1
Method, it is characterised in that following steps：
1) dissolving metal salts are obtained to solution A in water, the mixed solution that dicyandiamide is dissolved in solution A and ethyl alcohol obtains solution
B；Wherein, the molar ratio of dicyandiamide and metal salt is 10:1-80:1, iron nickel molar ratio is 1:0-1:10, the volume of water and ethyl alcohol
Than being 20:1-1:20；The metal salt includes ferric citrate (C6H11FeNO7, AFC) and NiCl2·6H2O；
2) drying steps 1) obtained by solution B, catalyst pyrolytic precursors are made；
3) calcining step 2) in gained catalyst precarsor obtain FeNi@NCNT catalyst
Under inert gas shielding, room temperature is to 400-600 DEG C of calcining 1-4h, then is warming up at 650-1200 DEG C of pyrolysis temperature and forges
After burning 1-10h, FeNi@NCNT catalyst is obtained after natural cooling.
3. the preparation of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 2
Method, which is characterized in that the ferric citrate described in step 1) or NiCl2·6H2O can be Mn, Co, Ni, Cu or Zn transition
The mixture of one or more of the soluble-salt of metal.
4. tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 2 or 3
Preparation method, which is characterized in that drying means described in step 2) is vacuum drying, air atmosphere is dry or inert atmosphere is dry
Dry, drying temperature is 0-150 DEG C, drying time 3-100h.
5. tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 2 or 3
Preparation method, which is characterized in that it is 1-20 DEG C of min to be warming up in step 3) to 400-600 DEG C of heating rate-1；It is warming up to heat
The heating rate for solving 650-1200 DEG C of temperature is 3-10 DEG C of min-1。
6. the preparation of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 4
Method, which is characterized in that it is 1-20 DEG C of min to be warming up in step 3) to 400-600 DEG C of heating rate-1；It is warming up to pyrolysis temperature
The heating rate of 650-1200 DEG C of degree is 3-10 DEG C of min-1。
7. tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N described in claim 1 is used as fuel electricity
Pond, electrolysis water or metal-air battery cathode ORR and/or OER elctro-catalyst.
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