CN106694018A - Cobalt-nitrogen co-doped carbon oxygen reduction catalyst with gradient pore structure, and preparation method and application thereof - Google Patents
Cobalt-nitrogen co-doped carbon oxygen reduction catalyst with gradient pore structure, and preparation method and application thereof Download PDFInfo
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- CN106694018A CN106694018A CN201611154359.XA CN201611154359A CN106694018A CN 106694018 A CN106694018 A CN 106694018A CN 201611154359 A CN201611154359 A CN 201611154359A CN 106694018 A CN106694018 A CN 106694018A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000011148 porous material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000009467 reduction Effects 0.000 title claims abstract description 18
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 title abstract 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 title abstract 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 33
- 239000011258 core-shell material Substances 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 15
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 13
- 239000003610 charcoal Substances 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000006911 nucleation Effects 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 241001104043 Syringa Species 0.000 claims description 2
- 235000004338 Syringa vulgaris Nutrition 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 210000000481 breast Anatomy 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 208000021251 Methanol poisoning Diseases 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000036228 toxication Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 1
- ISDKBADJUSXAFO-UHFFFAOYSA-L CO.[Co](Cl)Cl Chemical compound CO.[Co](Cl)Cl ISDKBADJUSXAFO-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- -1 however Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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Abstract
The invention relates to a cobalt-nitrogen co-doped carbon oxygen reduction catalyst with a gradient pore structure, and a preparation method and application thereof. The catalyst adopts a ZIF-8@ZIF-67 core-shell structure, formed by adopting zeolite-like imidazate ZIF-8 as a core and ZIF-67 as a shell, as a precursor, and is obtained by virtue of high temperature carbonization in an inert atmosphere. Compared with the prior art, the catalyst has the advantages of high catalytic activity, high stability, methanol poisoning resisting capacity, simple and controllable preparation method, low price of raw materials, environment-friendliness in a preparation process, and wide application to the fields such as alkaline fuel cells, chloro-alkaline industry and the like.
Description
Technical field
The present invention relates to a kind of cobalt with graded pore structure, the agent of nitrogen co-doped charcoal oxygen reduction catalyst and its preparation side
Method, and the application in alkaline fuel cell and chlorine industry.
Background technology
Redox reactions（Oxygen reduction reaction, ORR）It is alkaline fuel cell and chlorine industry
Cathode electrode reacts, and the reaction activity is high, overpotential big, it is necessary to efficient catalyst degradation reaction activity, improves reaction
Speed, so as to save energy consumption.At present, Pt bases catalyst is most efficient class ORR catalyst, however, precious metals pt reserves have
Limit, expensive, stability is relatively low and easy methanol poisoning, limits its extensive use in fields such as fuel cells.Therefore, grind
The base metal oxygen reduction catalyst agent for studying carefully developing low-cost, high activity, high stability and anti methanol toxication has important meaning
Justice.
At present, it is transition metal, nitrogen co-doped charcoal to be studied in non-precious metal catalyst more（TM-N-C, TM: Fe、
Co、Mn、Ni）Catalyst.Because TM-N-C catalyst has active, cheap preparation cost higher, high stability and excellent
Different anti methanol toxication ability, it is considered to be most hopeful to replace a class non-precious metal catalyst of Pt base catalyst.However, phase
Than in Pt base catalyst, such catalyst activity is still relatively low, the practical application that can not still meet fuel cell and chlorine industry will
Ask.Research shows, avtive spot latent active, quantity and pore passage structure are to determine three of oxygen reduction catalyst catalysis activity most
Key influence factor.It is mesoporous to be conducive to the mass transfer, micropore then with a large amount of avtive spots of grappling and its to be promoted uniform in pore passage structure
Distribution.MOFs materials are transition metal and the three-dimensional porous crystal formed containing N or organoligand coordination containing O, with specific surface area
Greatly, the diversified advantage of particle diameter controllable, part, is a kind of preferable presoma for preparing TM-N-C.Using single MOFs as
TM-N-C catalyst prepared by presoma carbonization, due to its pore passage structure not easy-regulating, often catalysis activity is relatively low.Design and develop
Core shell structure MOFs presomas are carbonized, and prepared shell is that a large amount of mesoporous, kernels are the TM-N-C of the graded pore structure of micropore
Catalyst, is the effective means for further improving oxygen reduction performance.
The content of the invention
In order to solve problems of the prior art, it is an object of the invention to provide a kind of simple effective method system
Standby cobalt, nitrogen co-doped charcoal oxygen reduction catalyst agent with graded pore structure.The preparation method that the catalyst is used is simple, former
Material abundance, cheap, achievable large-scale production, and the catalyst has excellent redox property ability.
To achieve the above object, the present invention is adopted the following technical scheme that：It is a kind of cobalt with graded pore structure, nitrogen co-doped
Charcoal oxygen reduction catalyst agent, with the three-dimensional porous structure that mesoporous, micropore gradient is distributed, shell is predominantly mesoporous, pore size
2-6nm is distributed as, kernel is micropore, and size distribution is 0.5-2nm.
The present invention also protects cobalt, the preparation side of nitrogen co-doped charcoal oxygen reduction catalyst agent with graded pore structure
Method, the ZIF-8@ZIF-67 nucleocapsids that the catalyst is formed as core, ZIF-67 using class zeolite imidazole ester ZIF-8 as shell
Structure is obtained as presoma by high temperature cabonization under an inert atmosphere.
It is of the invention preferred embodiment in, ZIF-8@ZIF-67 sequentially add cobalt salt and 2- with ZIF-8 as core
Methylimidazole, one layer of ZIF-67 is grown by heterogeneous nucleation process in ZIF-8 appearances, forms core shell structure；Core ZIF-8
Footpath is 0.4-1 μm, and shell ZIF-67 is 30-100nm.
ZIF-8 be Zn ions and 2-methylimidazole be coordinated to be formed microcellular structure, three-dimensional order, with dodecahedron shape
The crystal of looks.During high temperature pyrolysis, wherein Zn ions are reduced into metal Zn and are volatilized by carbon, and micropore canals are left in material internal,
Nitrating Carbon Materials that carbonizing production is mainly microcellular structure and that nitrogen content is higher.Co ions are coordinated what is formed with 2-methylimidazole
ZIF-67, has identical structure with ZIF-8.During high temperature pyrolysis, Co ions are reduced into Co simple substance, and agglomeration forms Co
Nano-particle, while the carbon atom around Co nano particle catalysis forms the carbon-coating of high graphitization degree, above two mechanism is total to
With cause ZIF-67 to be pyrolyzed to be formed it is a large amount of it is mesoporous, while there are the Carbon Materials of small part micropore.As described above, existing when in solution
During ZIF-8 cores, Co ions preferentially can be coordinated with 2-methylimidazole in ZIF-8 appearances, by heterogeneous nucleation, be formed
ZIF-8@ZIF-67 core shell structures；During ZIF-8@ZIF-67 high temperature pyrolysis, that is, form shell most of for mesoporous, core is micropore
Graded pore structure Co-N-C catalyst.Wherein, the mesoporous mass transport process for being conducive to reactant and product, micropore is conducive to
Grappling Co-NXAvtive spot, and the reunion of Co nano-particles is inhibited to a certain extent, promote uniform point of avtive spot
Cloth, so as to improve catalysis activity.
It is of the invention preferred embodiment in, the preparation method specifically includes following steps：
（1）Zinc nitrate and 2-methylimidazole are dissolved in organic solvent respectively, and are mixed, stirred, stood, obtain breast
White opacity liquid, then suction filtration, drying, obtains white powder ZIF-8；Wherein, drying temperature is 60-100oC, when drying
Between be 6-10h；
（2）ZIF-8 and cobalt chloride are dissolved in organic solvent respectively, by-the 60min of ZIF-8 solution ultrasound 30 after, be added dropwise respectively
Cobalt chloride solution and 2-methylimidazole solution, suction filtration obtain lilac powder ZIF-8@ZIF-67 after drying；Wherein, cobalt chloride
Concentration is 0.075-0.3 mol L-1, 2-methylimidazole concentration is 1.2-4.8 mol L-1；Drying temperature is 60-100oC, does
The dry time is 6-10h；
（3）By above-mentioned ZIF-8@ZIF-67 under an inert atmosphere with 1-10oCmin-1 is warming up to 900-1000oC, is incubated 1-3
H, is cooled to room temperature, and the cobalt of graded pore structure, nitrogen co-doped charcoal oxygen reduction catalyst agent are obtained after grinding.
It is of the invention preferred embodiment in, step（1）In, zinc nitrate is 1 with the mol ratio of 2-methylimidazole:
2.35-1:4；The order of the mixing pours into zinc nitrate solution for 2-methylimidazole solution；Dwell temperature is 30oC,
It is of the invention preferred embodiment in, the organic solvent is preferably methyl alcohol or ethanol.
By changing the addition of cobalt chloride solution and 2-methylimidazole solution, different shell thicknesses can be prepared
Core shell structure ZIF-8 ZIF-67 presomas, the presoma of the different shell thicknesses that are carbonized is to be capable of achieving pore structure and specific surface area
Regulation and control.
It is of the invention preferred embodiment in, step（2）In, the order of dropwise addition is to be first added dropwise cobalt chloride solution, again
2-methylimidazole solution is added dropwise, cobalt chloride is 1 with the mol ratio of 2-methylimidazole:16, cobalt chloride is with the mass ratio of ZIF-8
0.45:1-2.2:1, core shell structure shell ZIF-67 thickness are 30-100 nm.
It is of the invention preferred embodiment in, the inert atmosphere be argon gas or nitrogen, heating rate is 5oC
min-1, soaking time is 2h.
The present invention also protects the cobalt with graded pore structure, the agent of nitrogen co-doped charcoal oxygen reduction catalyst to be fired for alkalescence
The redox reactions of material battery and chlorine industry.
Compared with prior art, the present invention has advantages below：
（1）Excellent oxygen reduction catalyst activity and high stability.Present invention design is prepared for the ZIF-8@with core shell structure
ZIF-67 presomas, are obtained the graded pore structure Co-N-C that shell is predominantly mesoporous, kernel is micropore and are catalyzed by high temperature pyrolysis
Agent.Wherein, the micropore of kernel can anchoring activity site, the reunion of suppression Co nano particles, so as to realize the uniform of avtive spot
Distribution.
（2）Excellent mass-transfer performance.The catalyst prepared using the method for the invention, shell is predominantly mesoporous, kernel
It is microcellular structure, is capable of achieving the rapid mass transfer of reactant and product, so as to realize being fully contacted for avtive spot and reactant,
Improve catalysis activity.
（3）Excellent anti methanol toxication ability.It is prepared by the chrono-amperometric test after adding methyl alcohol, the embodiment of the present invention
Catalyst there is excellent methanol tolerance performance.
（4）Preparation method is simple, easy to operate, low in raw material price and preparation process is environment-friendly, and repeatability is good, it is easy to
Batch production, can be widely applied to the fields such as alkaline fuel cell, chlorine industry.
Brief description of the drawings
Below in conjunction with accompanying drawing, the invention will be further described：
Fig. 1 is the scanning electron microscope (SEM) photograph of ZIF-8@ZIF-67 core shell structure presomas；
Fig. 2 is that the transmission electron microscope picture and element line of ZIF-8@ZIF-67 core shell structure presomas sweep distribution map；
Fig. 3 is the scanning electron microscope (SEM) photograph of the Co-N-C catalyst with graded pore structure；
Fig. 4 is the nitrogen adsorption desorption curve of the Co-N-C catalyst with graded pore structure；
Fig. 5 is the polarization curve of Co-N-C catalyst with graded pore structure and business 20%Pt/C catalyst.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only used to explain the present invention, without structure
Into limitation of the present invention.
Embodiment 1
（1）The preparation of ZIF-8
1.62g zinc nitrates are dissolved in 80mL methyl alcohol at room temperature, 1.052g2- methylimidazoles are dissolved in 80mL methyl alcohol, fully after dissolving,
2-methylimidazole solution is quickly poured into zinc nitrate solution, 2min, 30 is stirredoC stands 12h, rear suction filtration, methyl alcohol washing, 80oC dries 8h, obtains white ZIF-8 powder.
（2）The preparation of ZIF-8@ZIF-67 core shell structures
Take 160mgZIF-8 and be dissolved in 40mL methyl alcohol, ultrasonic 30min is dropwise added dropwise cobalt chloride methanol solution while stirring（0.075
mol L-1）, 2-methylimidazole methanol solution is then dropwise added dropwise（1.2mol L-1）, after continuing to stir 2min, 30oC stands
12h.Then suction filtration, methyl alcohol washing, 80oC dries 8h, obtains purple ZIF-8@ZIF-67 powder, and shell thickness is 30nm.
The ESEM of ZIF-8@ZIF-67 core shell structure presomas, transmission electron microscope picture and Elemental redistribution are as shown in Fig. 1-2.
（3）The preparation of the Co-N-C catalyst of graded pore structure
The above-mentioned core shell structure sample powders of 200 mg are taken in corundum crucible, in tube furnace under argon gas atmosphere protection with
5oCmin-1Heating rate be warming up to 950 oC, natural cooling after 2h is incubated, obtain the Co-N-C catalysis with graded pore structure
Agent.
Its stereoscan photograph is shown in Fig. 3.Its pattern keeps dodecahedron substantially, and structure has negligible parts against wear
With cave in；Specific surface area reaches 632.4 m2 g-1, mesoporous to be distributed in 2-6 nm, micropore is distributed in 0.5-2 nm；Oxygen reduction
Can be suitable with 20% Pt/C of business（See Fig. 5）, it is significantly better than TM-N-C catalyst of the prior art.
Embodiment 2
Using the preparation process of embodiment 1, it is that the concentration of cobalt chloride increases to 0.15 mol L to be different from part-1, 2- first
The concentration of base imidazoles increases to 2.4 mol L-1, shell thickness increases to 50 nm.Compared to catalyst prepared by embodiment 1, the catalysis
Agent Limited diffusion current density is smaller, and half wave potential is relatively born, and catalysis activity is suitable with the catalyst of embodiment 1.
The above, specific embodiment only of the invention, but protection scope of the present invention is not limited thereto, and it is any
The change or replacement expected without creative work, should all be included within the scope of the present invention.Therefore, it is of the invention
Protection domain should be determined by the scope of protection defined in the claims.
Claims (10)
1. a kind of cobalt with graded pore structure, nitrogen co-doped charcoal oxygen reduction catalyst agent, it is characterised in that with mesoporous, micro-
The three-dimensional porous structure of gradient pores distribution, shell is predominantly mesoporous, and size distribution is 2-6nm, and kernel is micropore, and aperture is big
It is small to be distributed as 0.5-2nm.
2. the cobalt with graded pore structure according to claim 1, the preparation side of nitrogen co-doped charcoal oxygen reduction catalyst agent
Method, it is characterised in that the ZIF- that the catalyst is formed as core, ZIF-67 using class zeolite imidazole ester ZIF-8 as shell
8@ZIF-67 core shell structures are obtained as presoma by high temperature cabonization under an inert atmosphere.
3. preparation method according to claim 2, it is characterised in that ZIF-8@ZIF-67 with ZIF-8 as core, successively plus
Enter cobalt salt and 2-methylimidazole, one layer of ZIF-67 is grown in ZIF-8 appearances by heterogeneous nucleation process, form core shell structure；
Core ZIF-8 particle diameters are 0.4-1 μm, and shell ZIF-67 is 30-100nm.
4. the preparation method according to Claims 2 or 3, it is characterised in that the preparation method specifically includes following steps：
（1）Zinc nitrate and 2-methylimidazole are dissolved in organic solvent respectively, and are mixed, stirred, stood, obtain breast
White opacity liquid, then suction filtration, drying, obtains white powder ZIF-8；Wherein, drying temperature is 60-100oC, when drying
Between be 6-10h；
（2）ZIF-8 and cobalt chloride are dissolved in organic solvent respectively, by-the 60min of ZIF-8 solution ultrasound 30 after, be added dropwise respectively
Cobalt chloride solution and 2-methylimidazole solution, suction filtration obtain lilac powder ZIF-8@ZIF-67 after drying；Wherein, cobalt chloride
Concentration is 0.075-0.3 mol L-1, 2-methylimidazole concentration is 1.2-4.8 mol L-1；Drying temperature is 60-100oC, does
The dry time is 6-10h；
（3）By above-mentioned ZIF-8@ZIF-67 under an inert atmosphere with 1-10oCmin-1 is warming up to 900-1000oC, is incubated 1-3 h,
Room temperature is cooled to, the cobalt of graded pore structure, nitrogen co-doped charcoal oxygen reduction catalyst agent are obtained after grinding.
5. preparation method according to claim 4, it is characterised in that step（1）In, zinc nitrate rubs with 2-methylimidazole
You are than being 1:2.35-1:4；The order of the mixing pours into zinc nitrate solution for 2-methylimidazole solution；Dwell temperature is 30oC。
6. preparation method according to claim 4, it is characterised in that the organic solvent is methyl alcohol or ethanol.
7. preparation method according to claim 4, it is characterised in that step（2）In, the order of dropwise addition is that chlorination is first added dropwise
Cobalt liquor, 2-methylimidazole solution is added dropwise again, cobalt chloride is 1 with the mol ratio of 2-methylimidazole:16, cobalt chloride is with ZIF-8's
Mass ratio is 0.45:1-2.2:1, core shell structure shell ZIF-67 thickness are 30-100 nm.
8. preparation method according to claim 4, it is characterised in that the inert atmosphere is argon gas or nitrogen, heat up speed
Rate is 5oC min-1, soaking time is 2h.
9. the cobalt with graded pore structure described in claim 1, the agent of nitrogen co-doped charcoal oxygen reduction catalyst are used for basic fuel
The redox reactions of battery and chlorine industry.
10. the catalyst that the preparation method any one of claim 2-8 is prepared is used for alkaline fuel cell and chlorine
The redox reactions of alkali industry.
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