CN108543545B - 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 109
- 229910002555 FeNi Inorganic materials 0.000 title claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229960002413 ferric citrate Drugs 0.000 claims abstract description 26
- 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 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 18
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 15
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 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 37
- 239000003792 electrolyte Substances 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000000197 pyrolysis Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 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
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 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
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 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
- 239000007788 liquid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000010287 polarization Effects 0.000 description 11
- 229960000935 dehydrated alcohol Drugs 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000227 grinding Methods 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
- 238000007605 air drying Methods 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
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- 230000003197 catalytic effect Effects 0.000 description 7
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- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 229910021389 graphene Inorganic materials 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 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
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing 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
- 238000011065 in-situ storage Methods 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 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
- 229910052725 zinc Inorganic materials 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 source C and the source N, ferric citrate, NiCl2·6H2O is source metal, using " one kettle way " be pyrolyzed in two stages a step be made.FeNi metallic in catalyst is largely uniformly wrapped in the carbon nanotube tube wall of " Bamboo-shaped " N doping, is 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;It can be widely applied to the fields such as Proton Exchange Membrane Fuel Cells, electrolysis water, metal-air battery, 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 technique
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 needs research and development effective catalyst and improves 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 performance is higher, its ORR
Performance is very low.Moreover, these noble metals of Pt, Ir, Ru are expensive, reserves are limited, stability is poor, it is unable to satisfy extensive
Commercial applications demand.Therefore, there is an urgent need to develop with high catalytic activity, low cost and good stability ORR and OER it is bis-
Function non-precious metal catalyst.
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 variation of valence abundant is of great significance to ORR and OER performance is improved.However, transition metal base is catalyzed
It is agent poorly conductive, easy to reunite, need to further increase its catalytic performance.By in the carbon with high-specific surface area and high conductivity
Or original position anchor 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 the mass transfer ability of electronics conduction, molecular/ionic, 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 performance
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 has been made FeNi, FeCo and has coupled N doping in situ
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] using electrostatic spinning technique by polyvinylpyrrolidone,
Polyacrylonitrile, Ni (NO3)2·6H2O and Co (NO3)2·6H2Nanofiber is made in the mixed solution of O, and subsequent high temperature pyrolysis is made
The N dopen Nano fiber of NiCo alloy modification.The experimental results showed that the catalyst shows higher ORR under alkaline condition
With OER Activity and stabill.However, the nanofiber that electrostatic spinning technique is prepared is not readily separated, low yield, intensity difference,
And the catalyst preparation process is many and diverse, is unfavorable for large scale preparation.
In conclusion the nitrogen-doped carbon material (MM '/NC) of bimetallic base modification shows good catalysis ORR and OER mistake
The potential of journey, but preparation process is up for being further simplified.So simplify preparation process, reduce cost and design be easy to advise greatly
The efficient MM ' of mould industrialized production/NC catalyst has important practical significance and application value.
The present invention uses dicyandiamide cheap, that raw material sources are wide for the source C and the source 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 process.This method preparation process is simple, low in cost, is easy to amplify
Production, it is often more important that the FeNi@NCNT large specific surface area of synthesis, metal are coated by carbon nanotube, are conducive to improve material
Catalytic activity and stability.
Summary of the invention
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 source C and the source N, ferric citrate
And NiCl2·6H2O is source metal, and using " one kettle way ", substep is pyrogenically prepared under an inert atmosphere.FeNi metal 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 nanoparticle in tube wall facilitates the distribution of regulating catalyst surface electronic, improves catalyst activity;It avoids simultaneously
FeNi nanoparticle and electrolyte contacts inhibit the reunion of FeNi nanoparticle, improve the stability of material.On the other hand, N mixes
Miscellaneous carbon nanotube can provide high specific surface area and electric conductivity, be conducive to the mass transport process of electronics conduction and reaction species.With it is normal
The metal alloy oxygen reduction reaction seen is compared with oxygen evolution reaction bifunctional catalyst, which also shows under alkaline condition
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
Production;It can be widely applied to the fields such as Proton Exchange Membrane Fuel Cells, electrolysis water, metal-air battery, it is with higher practical
Value.
In order to achieve the above object, of the invention the technical solution adopted 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 alloy 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 metallic in reaction process from contacting with the direct of electrolyte, 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 reaction simultaneously.
The preparation step of above-mentioned tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N is as follows:
1) dissolving metal salts Yu Shuizhong is obtained into solution A, the mixed solution that dicyandiamide is dissolved in solution A and ethyl alcohol is obtained
Solution B;Wherein, the molar ratio of dicyandiamide and metal salt (iron and nickel) is 10:1-80:1, and 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 ((NH4)3FeC12H10O14, AFC) and
NiCl2·6H2O。
2) drying steps 1) resulting 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
The mixture of one or more of soluble-salt.
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.
Above-mentioned tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N is used as fuel cell, electrolysis water or gold
Negative (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) the tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N prepared using the method for the invention,
Pattern is bamboo-like carbon nano tubes, is conducive to provide high specific surface area and electric conductivity, increases catalyst (solid phase), oxygen, electricity
The area of liquid three-phase reaction interface is solved,
2) the tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N prepared using the method for the invention,
FeNi nanoparticle is mainly dispersed in inside carbon nanotube tube wall, and FeNi nanoparticle on the one hand may be by changing surface
The electronics distribution of graphene carbon nanotube walls influences the activity of catalyst, while FeNi active sites can be to avoid electrolyte and electrification
The corrosion of process inhibits the reunion of metal nanoparticle, is conducive to the electro-chemical activity and stability that improve catalyst.
3) using the FeNi@NCNT catalyst of the method for the invention preparation, pass through regulation raw material ingredient proportion and preparation
Process, such as precursor type, content ratio, calcination temperature, the achievable catalysis dosage form of calcination time of metal source of iron and nickel source
The controllable preparation of looks, structure.
4) the FeNi@NCNT catalyst for using the method for the invention to prepare is using dicyandiamide for the source C and the source N, citric acid
Iron ammonium and NiCl2·6H2O is source metal, and low in raw material price is easy to get, and helps to be mass produced.
5) using the FeNi@NCNT catalyst of the method for the invention preparation, 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) it using the FeNi@NCNT catalyst of the method for the invention preparation, is shown in alkaline electrolyte good
ORR catalytic performance, and close to commercialization 20wt.%Pt/C catalyst, it can be used for fuel cell, electrolysis water, metal-air electricity
Pond etc. is multi-field.
7) it using the FeNi@NCNT catalyst of the method for the invention preparation, is shown in alkaline electrolyte good
OER catalytic performance, and OER performance is better than Pt/C catalyst, can be used as metal-air battery catalyst, apparatus for electrolyzing etc.
Catalyst be widely applied.
8) using the FeNi@NCNT catalyst of the method for the invention preparation, excellent ORR and OER catalysis are provided simultaneously with
Activity is the double-function catalyzing material that the devices such as chargeable metal-air battery need.
Detailed description of the invention:
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 the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electricity
The ORR polarization curve in liquid is solved, test voltage range is -0.8~0.2V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 5 (b) is the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electricity
The OER polarization curve in liquid is solved, test voltage range is 0~1V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 6 (a) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH
ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 6 (b) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH
OER polarization curve in electrolyte, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 7 (a) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH
ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 7 (b) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH
OER polarization curve in electrolyte, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 8 be the sample according to made from embodiment 2 at room temperature, respectively in O2Saturation and N2The 0.1mol L of saturation-1KOH
CV figure in electrolyte, sweeps speed: 50mV s-1。
Fig. 9 is the sample according to made from embodiment 2 in room temperature, O2The 0.1mol L of saturation-1Linearly sweeping in KOH electrolyte
Volt-ampere (LSV) curve is retouched, sweeps speed: 10mV s-1, revolving speed: 400rpm, 900rpm, 1600rpm, 2500rpm.
Figure 10 is Koutecky-Levich (K-L) song obtained according to the LSV curve (Fig. 9) that sample is made in embodiment 2
Line.
Figure 11 is the sample according to made from embodiment 2 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte
In chronoamperogram, revolving speed: 1600rpm, voltage are constant in -0.4V.
Figure 12 (a) is the sample according to made from embodiment 2 in O2The 0.1moL L of saturation-18000 circles follow in KOH electrolyte
ORR activity comparison diagram after ring, CV scanning range -0.4-0.1V sweep speed: 10mV s-1, revolving speed: 1600rpm;
Figure 12 (b) is the sample according to made from embodiment 2 in O2The 0.1moL L of saturation-12000 circles follow in KOH electrolyte
OER activity comparison diagram after ring, CV scanning range 0.2-0.7V sweep speed: 10mV s-1, revolving speed: 1600rpm.
Figure 13 is the difference of sample made from embodiment 2 N at room temperature2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation
0.1mol L-1KOH electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1CV figure in KOH electrolyte, sweeps speed:
10mV s-1。
Figure 14 be comparative example 1 be commercialized 20wt.%Pt/C catalyst respectively at room temperature, O2The 0.1mol L of saturation-1KOH
Electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1CV figure in KOH electrolyte, sweeps speed: 10mV s-1。
Specific embodiment
The present invention is explained in detail below 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's
Molal weight ratio is 3:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C)
By the ferric citrate of 0.1103g and 0.0178g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in the mixed solution of A and 20mL dehydrated alcohol, obtains solution B, stirs at 60 DEG C of oil bath
30min is mixed, is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry
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 calcining 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)。
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 2:DA-FeNi-8002·6H2O's rubs
Your mass ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry
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 calcining 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, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C)
By the ferric citrate of 0.0367g and 0.0535g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry
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 calcining 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, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 700 refer to that pyrolysis temperatures are 700 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in the mixed solution of A and 20mL dehydrated alcohol, obtains solution B, stirs at 60 DEG C of oil bath
30min is mixed, is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry
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 calcining 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).
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 5:DA-FeNi-9002·6H2O's rubs
Your mass ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 900 refer to that pyrolysis temperatures are 900 DEG C)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in the mixed solution of A and 20mL dehydrated alcohol, obtains solution B, stirs at 60 DEG C of oil bath
30min is mixed, is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry
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 calcining 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).
(DA: dicyandiamide, Fe are ferric citrate, mole 0.15mM, DA and metal to embodiment 6:DA-Fe-800
The molar ratio of Fe is about 79:1, and 800 refer to that pyrolysis temperature is 800 DEG C)
The ferric citrate of 0.0735g is dissolved in 10mL deionized water, solution A is obtained;The dicyandiamide of 1g is weighed again
Solution B is obtained in the mixed solution being dissolved in A and 20mL dehydrated alcohol, 30min is stirred at 60 DEG C of oil bath, sufficiently to dissolve
It is uniformly mixed;Uniformly mixed solution B is transferred in culture dish, the dry 11h of 60 DEG C of air drying cabinets, 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 calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, Fe@NCNT-800 is obtained after natural cooling and is urged
Agent (DA-Fe-800).
(DA: dicyandiamide, Ni refer to NiCl to embodiment 7:DA-Ni-8002·6H2O, mole 0.15mM, DA and metal
The molar ratio of Ni is about 79:1, and 800 refer to that pyrolysis temperature is 800 DEG C)
By 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, obtains solution A;The dicyandiamide for weighing 1g again is molten
Solution obtains solution B in the mixed solution of A and 20mL dehydrated alcohol, stirs 30min at 60 DEG C of oil bath, with abundant dissolution mixing
Uniformly;Uniformly mixed solution B is transferred in culture dish, the dry 11h of 60 DEG C of air drying cabinets obtains catalyst precarsor;It will
Drying gained precursor is placed in mortar, and grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming is extremely
550 DEG C of calcining 1h, then 3 DEG C of min-1It is warming up at 800 DEG C and calcines 1h again, (DA-Ni-800) catalyst is obtained after natural cooling
(DA-Ni-800)。
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 8:DA-FeNi-800-Z2·6H2O's
Molal weight ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C, and Z refers to that vacuum is dry
It is dry)
By the ferric citrate of 0.0735g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of vacuum ovens are dry
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 calcining 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 being about 19:1, and FeNi molar ratio is 1:1, and 800 refer to that pyrolysis temperature is 800 DEG C)
By the ferric citrate of 0.1505g and 0.0713g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry
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 calcining 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).
(DA: dicyandiamide, FeNi refer to ferric citrate and NiCl in raw material to embodiment 10:DA-FeNi-800-22·6H2O's
Molal weight ratio is 1:1, and the molar ratio of DA and metal Fe and Ni are about 40:1, and 800 refer to that pyrolysis temperatures are 800 DEG C, and 2 refer to 800 DEG C
Lower calcining 2h)
By the ferric citrate of 0.0395g and 0.0362g NiCl2·6H2O is dissolved in 10mL deionized water, is obtained molten
Liquid A;The dicyandiamide for weighing 1g again, which is dissolved in A and 20mL dehydrated alcohol mixed solution, obtains solution B, stirs at 60 DEG C of oil bath
30min is uniformly mixed with abundant dissolution;Uniformly mixed solution B is transferred in culture dish, 60 DEG C of air drying cabinets are dry
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 calcining 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: commercialization 20wt.%Pt/C catalyst (Alfa Aesar)).
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 2.It is analyzed by the PCPDF card of XRD spectra
The metal species for knowing that embodiment 2 is made in sample contain two kinds of crystalline structures: FeNi (43.46 °, 50.38 °, 73.96 ° of diffraction
Peak is between Fe (PDF#52-0513) and Ni (PDF#04-0850), it is seen that form FeNi phase be respectively belonging to (111),
(200), (220) crystal face), Fe3O4(PDF#75-0033,35.48 ° (3 1 1), 30.12 ° (2 2 0), 62.63 (440)), phase
The peak position answered and intensity such as figure mark.In addition, 2 θ=26 ° or so are the characteristic diffraction peak of graphene (002) crystal face, show
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 2
Sample obtained is that " Bamboo-shaped " carbon nano tube structure coats FeNi nano particle structure.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 range.
This clad structure can avoid metallic and contact with the direct of 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 163m2 g-1.Sample aperture made from embodiment 2 known to Fig. 4 (b) pore size distribution curve be distributed in 3.5nm and 20~
50nm.Meso-hole structure abundant facilitates the mass transfer of oxygen, to be conducive to the progress of ORR/OER reaction.
Fig. 5 (a) is the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electricity
The ORR polarization curve in liquid is solved, test voltage range is -0.8~0.2V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.Fig. 5 (b)
It is the sample according to made from embodiment 1-3 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1The pole OER in KOH electrolyte
Change curve, test voltage range is 0~1V, sweeps speed: 10mV s-1, revolving speed: 1600rpm.By Fig. 5 (a) and Fig. 5 (b) it is found that lemon
Lemon acid iron ammonium and NiCl2·6H2The feed ratio of O is affected to the ORR of catalyst.When ferric citrate and feed ratio are 1:1,
ORR limiting current density is larger, and value when take-off potential and feed ratio are 3:1 is close;OER performance connects when 1:3 with feed ratio
Closely.Consider from the difunctional angle of ORR and OER, when ferric citrate and feed ratio are 1:1, overpotential minimum (△ E=E
(jOER=10mA cm -2)-E(jORR=-3mA cm -2)=0.85V), ORR and OER best performance.
Fig. 6 (a) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH
ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.Fig. 6
It (b) is the sample according to made from embodiment 2,4,5 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1In KOH electrolyte
OER polarization curve, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.It will be appreciated from fig. 6 that calcination temperature
Be affected to ORR and OER performance, calcine preparation temperature be 800 DEG C when ORR performance half wave potential (- 0.176V) and
Limiting current density is maximum, ORR best performance;jOER=10mA cm-2It is maximum to locate voltage, OER best performance.
Fig. 7 (a) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH
ORR polarization curve in electrolyte, test voltage range are -0.8~0.2V, sweep speed: 10mV s-1, revolving speed: 1600rpm.Fig. 7
It (b) is the sample according to made from embodiment 2,6,7 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1In KOH electrolyte
OER polarization curve, test voltage range are 0~1V, sweep speed: 10mV s-1, revolving speed: 1600rpm.By Fig. 7 (a) it is found that embodiment
The half wave potential (- 0.176V) of 2 obtained catalyst, close to commercialization 20wt.%Pt/C catalyst half wave potential (-
0.126V), illustrating the catalyst under alkaline condition has good ORR catalytic performance;By Fig. 7 (b) it is found that embodiment 2 is made
Obtain its OER current potential of catalyst (Ej OER=10mA cm -2=0.686V) it is better than 20wt.%Pt/C catalyst, show that the catalyst also has
There is good OER catalytic performance.
Fig. 8 is the sample according to 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 is the peak ORR to go out for -0.18V or so in current potential in KOH electrolyte
It is existing.
Fig. 9 is the sample according to made from embodiment 2 in room temperature, O2The 0.1mol L of saturation-1Linearly sweeping in KOH electrolyte
Volt-ampere (LSV) curve is retouched, sweeps speed: 10mV s-1, revolving speed: 400rpm, 900rpm, 1600rpm, 2500rpm.As shown in Figure 9, with
Revolving speed increase, ORR take-off potential remains unchanged, and Limited diffusion current density constantly increases.
Figure 10 is Koutecky-Levich (K-L) song obtained according to the LSV curve (Fig. 9) that sample is made in embodiment 2
Line.It is 4 or so according to the electron transfer number that K-L equation calculates 2 surface catalysis ORR of embodiment, shows the catalysis obtained of embodiment 2
Agent is catalyzed ORR with 4 electronic processes.
Figure 11 is the sample according to made from embodiment 2 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte
In chronoamperogram, revolving speed: 1600rpm, voltage are constant in -0.4V.By comparison it is found that in the timing electricity by 1800s
After flowing stability test, catalyst activity made from embodiment 2 decays to 98.16%;Under the same terms, 20wt.% is commercialized
Pt/C catalyst activity decays to 85.43%, illustrates catalyst stability made from embodiment 2 better than comparative example 1.
Figure 12 is the sample according to made from embodiment 2 in O2The 0.1moL L of saturation-1The circle of (a) 8000 follows in KOH electrolyte
ORR activity comparison diagram after ring, CV -0.4~0.1V of scanning range sweep speed: 10mV s-1, revolving speed: 1600rpm;(b) 2000 circle
OER activity comparison diagram after circulation, CV 0.2~0.7V of scanning range sweep speed: 10mV s-1, revolving speed: 1600rpm.By Figure 12 (a)
It is found that catalyst made from embodiment 2 is in O2The 0.1moL L of saturation-1In KOH electrolyte solution, after 8000 circle circulations,
CV curve shows that catalyst ORR stability made from embodiment 2 is preferable without significant change.By Figure 12 (b) it is found that embodiment 2 is made
The catalyst obtained is in O2The 0.1moL L of saturation-1In KOH electrolyte solution, after 2000 circle circulations, CV curve becomes without obvious
Change, 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 figure in KOH electrolyte, sweeps speed: 10mV s-1.As shown in Figure 13, embodiment 2 is made
Catalyst in the electrolyte solution whether there is or not methanol, CV curve without significant change, show catalyst made from embodiment 2 by
Methanol fuel influence is 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 figure in KOH electrolyte, sweeps 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, firing vulnerable to methanol influences.
Claims (4)
1. a kind of preparation method of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, which is characterized in that institute
The catalyst stated is unique " Bamboo-shaped " carbon nanotube, is tri- doped carbon nanometer pipe coated catalyst of Fe, Ni, N;Metal object
Phase FeNi alloy and Fe3O4It is coated in carbon nanotube NCNT, and is mainly dispersed in inside the tube wall of NCNT, part grain
Son is located at the tip inside pipe, can effectively avoid metallic in reaction process from contacting with the direct of electrolyte, improve catalysis
The stability of agent;Bimetallic combination is capable of providing variation of valence abundant, is catalyzed ORR and/or OER reaction;
The preparation method the following steps are included:
1) dissolving metal salts Yu Shuizhong is obtained into solution A, the mixed solution that dicyandiamide is dissolved in solution A and ethyl alcohol is obtained into solution
B;Wherein, the molar ratio of dicyandiamide and metal salt is 10:1-80:1, and iron nickel molar ratio is 1:0-1:10, the volume of water and ethyl alcohol
Than for 20:1-1:20;The metal salt includes ferric citrate and NiCl2·6H2O;
2) drying steps 1) resulting 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 to 400-600 DEG C of calcining 1-4h, then be warming up at 650-1200 DEG C of pyrolysis temperature and forge
After burning 1-10h, FeNi@NCNT catalyst is obtained after natural cooling.
2. the preparation of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 1
Method, which is characterized in that drying means described in step 2) is vacuum drying, air atmosphere is dry or inert atmosphere is dry, is done
Dry temperature is 0-150 DEG C, drying time 3-100h.
3. tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N according to claim 1 or 2
Preparation method, which is characterized in that the heating rate that 400-600 DEG C is warming up in step 3) is 1-20 DEG C of min-1;It is warming up to pyrolysis
650-1200 DEG C of temperature of heating rate is 3-10 DEG C of min-1。
4. the preparation method of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of a kind of Fe, Ni, N described in claim 1
Catalyst obtained is used as fuel cell, electrolysis water or metal-air battery cathode ORR and/or OER elctro-catalyst.
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