CN109192996A - A kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst and its preparation method and application - Google Patents
A kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst and its preparation method and application Download PDFInfo
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- CN109192996A CN109192996A CN201810907493.5A CN201810907493A CN109192996A CN 109192996 A CN109192996 A CN 109192996A CN 201810907493 A CN201810907493 A CN 201810907493A CN 109192996 A CN109192996 A CN 109192996A
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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
- H01M4/9041—Metals or alloys
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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
Abstract
The present invention provides a kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, it is by prepared by following preparation method: first passing through guanidine nitrate synthesis 3, 6- bis- (3, 5- dimethyl pyrazole) -1, 2, 4, 5- tetrazine (BT), again 3, 6- bis- (3, 5- dimethyl pyrazole) -1, 2, 4, imidazoles synthesis 3 is added in 5- tetrazine (BT), 6- bis- (imidazole radicals) -1, 2, 4, 5- tetrazine (DT) ligand, then make 3, 6- bis- (imidazole radicals) -1, 2, 4, 5- tetrazine (DT) and transition metals cobalt ion coordination form cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF), again by high temperature pyrolysis cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) be prepared spherical nitrogen-doped carbon-supported cobalt-based ( Co-N/C) oxygen reduction catalyst.The method for preparing catalyst is simple, and cost is relatively low, and has active site extremely abundant, is conducive to push fuel cell practical application.
Description
Technical field
The present invention relates to a kind of oxygen reduction catalysts, and in particular to a kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst
And its preparation method and application, belong to fuel cell science and technology field.
Background technique
Fossil energy if being widely used for petroleum, natural gas and coal has pushed the fast development of human society, but is changed
The non-renewable and use process bring environmental problem of the stone energy is two hang-ups of facing mankind.Develop environment friend
Good, reproducible new energy and new energy technology have become the mostly important research hotspot in the world today.
Fuel cell is that a kind of redox reaction by between fuel and oxidant is direct by the chemical energy in fuel
It is converted into the power generator of electric energy, is the generation technology of a new generation.Fuel cell is directly to convert chemical energy without burning
For the novel energy converting system of electric energy.Fuel cell (Fuell Cell, FC) by Carnot cycle because do not limited, energy turns
Change high-efficient (up to 40%-60%) and environmental-friendly, is concerned in recent years.
But its service life is low, low efficiency and defect at high cost limit its large-scale commercial application.Main cause
It is that platinum based catalyst is at high cost and low to the catalytic performance of methanol oxidation.Therefore, low cost, high activity, high stability are developed
ORR non-precious metal catalyst to push fuel cell large-scale commercial application value it is great.A series of carbon of Dai equivalence
Carrier (RGO and CNT etc.) load C oOx nanoparticle catalyst.Due to the carbon carrier of CoOx nano particle and high graphitization degree
Between extensive chemical coupling effect, these catalyst all show excellent ORR electrocatalysis characteristic.(Nature Materials,
2011,10:780-786) Feng etc. is with Co (ac)2And CS2For raw material, pass through regulation Co2+Molar concentration is through a step hydro-thermal value
CoS with variable grain size2Nanocrystalline elctro-catalyst.The result shows that Co2+Molar concentration is bigger, CoS2Nano particle is got over
Small, electrocatalysis characteristic is more excellent.(Journal of Materials Chemistry A,2013,1(18):5741-5746).
Summary of the invention
For in the prior art to the demand of fuel cell oxygen reduction catalyst, inventor has synthesized cobalt-based zeolite imidazole ester
Frame coordination polymer (CoDT-ZIF) is as the catalysis of spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) hydrogen reduction derived from presoma
Agent.The method for preparing catalyst is simple, and cost is relatively low, and has active site extremely abundant, is conducive to push fuel cell
Practical application.
The main object of the present invention is to prepare one kind with cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) to be
The fuel cell ORR catalyst of presoma is mainly characterized by first synthesizing ligand 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazines
(DT), then by solvent-thermal method by DT and transition metals cobalt ion coordination, cobalt-based zeolite imidazole ester frame coordination polymerization is prepared
Object (CoDT-ZIF).Further the high temperature pyrolysis coordination polymer obtains spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) hydrogen reduction
Catalyst.
The first embodiment provided according to the present invention provides a kind of spherical nitrogen-doped carbon-supported cobalt-based hydrogen reduction catalysis
Agent.
A kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, it is by prepared by following preparation method: first being led to
Pernitric acid guanidine synthesis 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT), then in (3, the 5- dimethyl pyrazoles of 3,6- bis-
Azoles) -1,2,4,5- tetrazines (BT) are middle to be added imidazoles synthesis 3,6- bis- (imidazole radicals) -1, then 2,4,5- tetrazines (DT) ligand makes
(the imidazole radicals) -1,2,4,5- tetrazine of 3,6- bis- (DT) and transition metals cobalt ion coordination form the coordination of cobalt-based zeolite imidazole ester frame
Polymer (CoDT-ZIF), then be prepared by high temperature pyrolysis cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)
Spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst.
In the present invention, the transition metal cobalt ions comes from Cobalt salts.
Preferably, Cobalt salts are cabaltous nitrate hexahydrate, basic cobaltous carbonate, Cobalt monosulfate heptahydrate, cobalt chloride, bromination
One of cobalt, cobaltous iodide are a variety of.
Second of the embodiment provided according to the present invention provides a kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst
Preparation method.
A kind of preparation method of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst prepares institute in the first embodiment
The method for stating spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, method includes the following steps:
(1) 3,6- the preparation of (3,5- the dimethyl pyrazole) -1,2,4,5- tetrazine of 3,6- bis- (BT): is synthesized by guanidine nitrate
Two (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT)；
(2) preparation of (the imidazole radicals) -1,2,4,5- of 3,6- bis- tetrazine (DT) ligand: by (the 3,5- dimethyl pyrazole of 3,6- bis-
Azoles) -1,2,4,5- tetrazines (BT) are fitted into reactor, and imidazoles is added, and it is heating reaction a period of time, cooling, it filters, it is dry, i.e.,
Obtain 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand；
(3) preparation of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF): taking 3,6- bis- (imidazole radicals) -1,2,
4,5- tetrazines (DT) ligand is dissolved in organic solvent, and Cobalt salts are added, and after dispersion, heating reaction a period of time, is taken out after cooling
Filter, washing, obtains brown solid, as cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)；
(4) preparation of spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst: the cobalt-based that step (3) is obtained boils
Stone imidazate frame coordination polymer (CoDT-ZIF) is by high-temperature heat treatment to get spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C)
Oxygen reduction catalyst.
Preferably, step (1) specifically: guanidine nitrate is dissolved in organic solvent (preferably dioxane solution), is added
Enter hydrazine hydrate, heat (being preferably heated to 80-140 DEG C, preferably 90-130 DEG C, more preferably 100-120 DEG C) and flows back anti-
(preferably back flow reaction 1-6h, preferably 2-5.5h, more preferably 3-5h) is answered, white solid is obtained after filtering, then will be white
Solid is dissolved in water, and acetylacetone,2,4-pentanedione is added wherein, and heating (is preferably heated to 50-90 DEG C, preferably 55-85 DEG C, more preferably
60-80 DEG C) under reaction (preferably reaction 1-6h, preferably 2-5.5h, more preferably 3-5h), filtering, solid is washed with water simultaneously
3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazine (BT) is obtained after drying.
Preferably, step (2) specifically: by 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT) are packed into
In the reactor for filling organic solvent (preferably acetonitrile), it is stirring evenly and then adding into the organic solution of imidazoles at normal temperature (preferably
For the acetonitrile solution dissolved with imidazoles), heating (is preferably heated to 65-100 DEG C, preferably 68-95 DEG C, more preferably 70-
90 DEG C) back flow reaction (preferably back flow reaction 0.2-6h, preferably 0.5-4h, more preferably 1-2h) is carried out, it is cooled to room temperature,
Filtering, washing (are preferably washed using acetonitrile and/or methylene chloride), dry (being preferably dried under vacuum to constant weight) to get to 3,
6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand.
Preferably, step (3) specifically: take 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazines (DT) ligand is dissolved in organic
In solvent (preferably DMF), after ultrasound is evenly dispersed, Cobalt salts are added under agitation, after dispersion, heating is (preferably
It is heated to 100-180 DEG C, preferably 120-160 DEG C, more preferably 130-150 DEG C) and reaction (preferably reaction 1-12h, preferably
2-8h, more preferably 2.5-6h), it filters after natural cooling and (is preferably filtered using PTFE organic film), obtained solid is by washing
It washs and (is preferably washed using DMF), it is dry (preferably dry for 50-120 DEG C of dry 6-24h, preferably 60- in a vacuum drying oven
100 DEG C of dry 8-18h), obtain brown solid, as cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF).
Preferably, step (4) specifically: the cobalt-based zeolite imidazole ester frame coordination polymer for obtaining step (3)
(CoDT-ZIF) it is placed in the high temperature process furnances of inert gas or nitrogen, (preferably, is heat-treated by high-temperature heat treatment
Temperature be 500-1500 DEG C, preferably 600-1200 DEG C, more preferably 700-900 DEG C；The time of heat treatment is 0.5-6h, excellent
It is selected as 1-4h, more preferably 2-3h), the carbon material using CoDT-ZIF as presoma is obtained, CoDT-ZIF-T is labeled as；It will
After CoDT-ZIF-T carbon material is fully ground, dilute acid solution is added and stirs 12- under 50-100 DEG C (preferably 60-90 DEG C)
96h (preferably 18-72h), is filtered and (is preferably filtered using PTFE moisture film), is washed (preferably adopt and be washed with deionized), dry
(preferably in a vacuum drying oven 40-80 DEG C dry 2-24h, preferably 50-70 DEG C dry 4-12h) is to get spherical N doping
Carbon carries cobalt-based (Co-N/C) oxygen reduction catalyst.
In the present invention, the molar ratio of guanidine nitrate and hydrazine hydrate is 1:2.0-5.0, preferably 1:2.5- in step (1)
4.5, further preferred 1:3.0-4.0.The molar ratio of acetylacetone,2,4-pentanedione and guanidine nitrate be 1:1.0-4.0, preferably 1:1.5-3.5,
Further preferred 1:2.0-3.0.
In the present invention, in step (2), 3,6- bis- (3,5- dimethyl pyrazoles) -1,2,4,5- tetrazines (BT) and imidazoles
Molar ratio is 1:0.5-5, preferably 1:1-4, more preferably 1:2-3.5.
In the present invention, bis- (imidazole radicals) -1 3,6- bis- (imidazole radicals) -1 in step (3), 2,4,5- tetrazines (DT) 3,6-,
The molar ratio of 2,4,5- tetrazines (DT) and Cobalt salts is 1:0.06-1, preferably 1:0.08-0.9, further preferably 1:0.15-
0.7, more preferable 1:0.2-0.5.
Preferably, the Cobalt salts are cabaltous nitrate hexahydrate, basic cobaltous carbonate, Cobalt monosulfate heptahydrate, cobalt chloride, bromine
Change one of cobalt, cobaltous iodide or a variety of.
Preferably, the acid solution is one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or a variety of；Preferably, acid is molten
The concentration of liquid is 0.05-5mol/L, preferably 0.1-3mol/L, more preferably 0.2-2mol/L.
Preferably, the inert gas is Ar or He.
The third embodiment provided according to the present invention provides a kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst
Purposes.
In fact according to spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst described in the first embodiment or according to second
The spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst for applying the preparation of any one of scheme the method, is used for oxygen also for the catalyst
Original reaction.
It is preferred that the catalyst to be used for the hydrogen reduction catalysis reaction of fuel cell.
In the present invention, in the heat treatment process in step (4), heating speed and cooling velocity are not required.Generally
, heat treatment heating (or heating) rate is 1-10 DEG C of min-1, preferably 2-8 DEG C of min-1, more preferably 3-6 DEG C of min-1.Rate of temperature fall when cooling is 1-10 DEG C of min-1, preferably 2-8 DEG C of min-1, more preferably 3-6 DEG C of min-1。
In the present invention, triamido guanidine nitrate is generated by guanidine nitrate and hydration hydrazine reaction first；Triamido guanidine nitrate with
Acetylacetone,2,4-pentanedione reaction obtains 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines using oxidation (or heat treatment)
(BT).Then synthetic ligands 3,6- bis- is reacted with imidazoles by (3,5- the dimethyl pyrazole) -1,2,4,5- tetrazine of 3,6- bis- (BT)
(imidazole radicals) -1,2,4,5- tetrazine (DT)；Cobalt salts are added in ligand again, to synthesize presoma cobalt-based zeolite imidazole
Ester frame coordination polymer (CoDT-ZIF).Spherical nitrogen-doped carbon-supported cobalt-based can be obtained by being heat-treated presoma CoDT-ZIF
(Co-N/C) oxygen reduction catalyst.Spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst that the present invention obtains is spherical
Structure, it is more stable to change catalyst, reacts applied to fuel cell oxygen reduction catalysis, battery passes through 20000 charge and discharges
After electricity, battery performance can be good at keeping.The catalyst is in methanol tolerance and 10000s stability test, Co-N/ of the present invention
C-800 catalyst current density does not change, and the current density of Pt/C catalyst die-offs to 70% or so of initial value.Make
To be preferred, spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst of the invention under alkaline condition particularly suitable for making
With.
Ligand used in cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) is 3,6- bis- (imidazole radicals) -1,2,
4,5- tetrazines (DT), coordinating metal salt be cabaltous nitrate hexahydrate, basic cobaltous carbonate, Cobalt monosulfate heptahydrate, cobalt chloride, cobaltous bromide,
One of cobaltous iodide.Forming solvent selected by a kind of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) is N,
Dinethylformamide (DMF).Cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) is before a kind of high nitrogen content
Drive body.
Spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst provided by the invention has the advantage that the present invention
Preparation method relative to other catalyst is different, we are for the first time with 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazines (DT) conduct
Ligand successfully synthesizes a kind of new cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF), has preparation method letter
It is single, low in cost, the short advantage of synthesis cycle.It is urged by being pyrolyzed obtained spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) hydrogen reduction
Agent, which contains, enriches efficient fuel cell ORR active site, and has biggish specific surface area, higher graphitization journey
Degree.In addition, gained catalyst not only has good ORR catalytic activity, also have excellent stability and methanol tolerance performance.
Electro-chemical test is mainly to be to electrode, the diameter coated with catalyst using Ag/AgCl as reference electrode, Pt
The glass-carbon electrode of 3mm is that working electrode forms three electrode test systems, with O2The 0.1mol/L KOH solution of saturation is electrolyte
A series of electro-chemical tests are carried out, using linear voltammetric scan method, cyclic voltammetry, electrochemical AC impedance method, chrono-amperometric
Method investigates catalyst ORR catalytic activity under alkaline condition.The result shows that ORR catalyst of the invention is in alkaline medium
There are good take-off potential, half wave potential and limiting current density, take-off potential (Eo) 25mV high compared with Pt/C catalyst, half-wave electricity
Position (E1/2) 40mV, limiting current density (J high compared with Pt/C catalystl) 0.15mA cm high compared with Pt/C catalyst-2.In acid medium
Middle take-off potential (Eo) it is lower than Pt/C catalyst 50mV, the catalyst of the business that can match in excellence or beauty Pt/C.
Detailed description of the invention
Fig. 1 is the synthetic route that embodiment 3 prepares 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand.
Fig. 2 is 3 monomer 3,6- of embodiment, bis- (imidazole radicals) -1,2,4,5- tetrazine (DT)1H NMR figure.
Fig. 3 is the synthetic route of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) prepared by embodiment 4.
Fig. 4 is the infrared spectrogram of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) prepared by embodiment 4.
Fig. 5 is the XRD spectra of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) prepared by embodiment 4.
Fig. 6 is the nitrogen adsorption desorption isotherm figure of catalyst prepared by the embodiment of the present invention 4.
Fig. 7 is the pore size distribution figure of catalyst prepared by the embodiment of the present invention 4.
Fig. 8 is that cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) prepared by embodiment 4 is that presoma ORR is urged
LSV curve of the agent under different pyrolysis temperatures.
Fig. 9 is that cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) prepared by embodiment 4 is that presoma ORR is urged
Agent is in 0.5M H2SO4Under LSV curve.
Figure 10 is that the scanning electron of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) prepared by embodiment 4 is aobvious
Micro mirror (SEM) picture.
Figure 11 is that cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) prepared by embodiment 4 is presoma ORR
Catalyst scanning electron microscope (SEM) picture.
Specific embodiment
The first embodiment provided according to the present invention provides a kind of spherical nitrogen-doped carbon-supported cobalt-based hydrogen reduction catalysis
Agent.
A kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, it is by prepared by following preparation method: first being led to
Pernitric acid guanidine synthesis 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT), then in (3, the 5- dimethyl pyrazoles of 3,6- bis-
Azoles) -1,2,4,5- tetrazines (BT) are middle to be added imidazoles synthesis 3,6- bis- (imidazole radicals) -1, then 2,4,5- tetrazines (DT) ligand makes
(the imidazole radicals) -1,2,4,5- tetrazine of 3,6- bis- (DT) and transition metals cobalt ion coordination form the coordination of cobalt-based zeolite imidazole ester frame
Polymer (CoDT-ZIF), then be prepared by high temperature pyrolysis cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)
Spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst.
In the present invention, the transition metal cobalt ions comes from Cobalt salts.
Preferably, Cobalt salts are cabaltous nitrate hexahydrate, basic cobaltous carbonate, Cobalt monosulfate heptahydrate, cobalt chloride, bromination
One of cobalt, cobaltous iodide are a variety of.
Second of the embodiment provided according to the present invention provides a kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst
Preparation method.
A kind of preparation method of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst prepares institute in the first embodiment
The method for stating spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, method includes the following steps:
(1) 3,6- the preparation of (3,5- the dimethyl pyrazole) -1,2,4,5- tetrazine of 3,6- bis- (BT): is synthesized by guanidine nitrate
Two (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT)；
(2) preparation of (the imidazole radicals) -1,2,4,5- of 3,6- bis- tetrazine (DT) ligand: by (the 3,5- dimethyl pyrazole of 3,6- bis-
Azoles) -1,2,4,5- tetrazines (BT) are fitted into reactor, and imidazoles is added, and it is heating reaction a period of time, cooling, it filters, it is dry, i.e.,
Obtain 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand；
(3) preparation of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF): taking 3,6- bis- (imidazole radicals) -1,2,
4,5- tetrazines (DT) ligand is dissolved in organic solvent, and Cobalt salts are added, and after dispersion, heating reaction a period of time, is taken out after cooling
Filter, washing, obtains brown solid, as cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)；
(4) preparation of spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst: the cobalt-based that step (3) is obtained boils
Stone imidazate frame coordination polymer (CoDT-ZIF) is by high-temperature heat treatment to get spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C)
Oxygen reduction catalyst.
Preferably, step (1) specifically: guanidine nitrate is dissolved in organic solvent (preferably dioxane solution), is added
Enter hydrazine hydrate, heat (being preferably heated to 80-140 DEG C, preferably 90-130 DEG C, more preferably 100-120 DEG C) and flows back anti-
(preferably back flow reaction 1-6h, preferably 2-5.5h, more preferably 3-5h) is answered, white solid is obtained after filtering, then will be white
Solid is dissolved in water, and acetylacetone,2,4-pentanedione is added wherein, and heating (is preferably heated to 50-90 DEG C, preferably 55-85 DEG C, more preferably
60-80 DEG C) under reaction (preferably reaction 1-6h, preferably 2-5.5h, more preferably 3-5h), filtering, solid is washed with water simultaneously
3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazine (BT) is obtained after drying.
Preferably, step (2) specifically: by 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT) are packed into
In the reactor for filling organic solvent (preferably acetonitrile), it is stirring evenly and then adding into the organic solution of imidazoles at normal temperature (preferably
For the acetonitrile solution dissolved with imidazoles), heating (is preferably heated to 65-100 DEG C, preferably 68-95 DEG C, more preferably 70-
90 DEG C) back flow reaction (preferably back flow reaction 0.2-6h, preferably 0.5-4h, more preferably 1-2h) is carried out, it is cooled to room temperature,
Filtering, washing (are preferably washed using acetonitrile and/or methylene chloride), dry (being preferably dried under vacuum to constant weight) to get to 3,
6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand.
Preferably, step (3) specifically: take 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazines (DT) ligand is dissolved in organic
In solvent (preferably DMF), after ultrasound is evenly dispersed, Cobalt salts are added under agitation, after dispersion, heating is (preferably
It is heated to 100-180 DEG C, preferably 120-160 DEG C, more preferably 130-150 DEG C) and reaction (preferably reaction 1-12h, preferably
2-8h, more preferably 2.5-6h), it filters after natural cooling and (is preferably filtered using PTFE organic film), obtained solid is by washing
It washs and (is preferably washed using DMF), it is dry (preferably dry for 50-120 DEG C of dry 6-24h, preferably 60- in a vacuum drying oven
100 DEG C of dry 8-18h), obtain brown solid, as cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF).
Preferably, step (4) specifically: the cobalt-based zeolite imidazole ester frame coordination polymer for obtaining step (3)
(CoDT-ZIF) it is placed in the high temperature process furnances of inert gas or nitrogen, (preferably, is heat-treated by high-temperature heat treatment
Temperature be 500-1500 DEG C, preferably 600-1200 DEG C, more preferably 700-900 DEG C；The time of heat treatment is 0.5-6h, excellent
It is selected as 1-4h, more preferably 2-3h), the carbon material using CoDT-ZIF as presoma is obtained, CoDT-ZIF-T is labeled as；It will
After CoDT-ZIF-T carbon material is fully ground, dilute acid solution is added and stirs 12- under 50-100 DEG C (preferably 60-90 DEG C)
96h (preferably 18-72h), is filtered and (is preferably filtered using PTFE moisture film), is washed (preferably adopt and be washed with deionized), dry
(preferably in a vacuum drying oven 40-80 DEG C dry 2-24h, preferably 50-70 DEG C dry 4-12h) is to get spherical N doping
Carbon carries cobalt-based (Co-N/C) oxygen reduction catalyst.
In the present invention, the molar ratio of guanidine nitrate and hydrazine hydrate is 1:2.0-5.0, preferably 1:2.5- in step (1)
4.5, further preferred 1:3.0-4.0.The molar ratio of acetylacetone,2,4-pentanedione and guanidine nitrate be 1:1.0-4.0, preferably 1:1.5-3.5,
Further preferred 1:2.0-3.0.
In the present invention, in step (2), 3,6- bis- (3,5- dimethyl pyrazoles) -1,2,4,5- tetrazines (BT) and imidazoles
Molar ratio is 1:0.5-5, preferably 1:1-4, more preferably 1:2-3.5.
In the present invention, bis- (imidazole radicals) -1 3,6- bis- (imidazole radicals) -1 in step (3), 2,4,5- tetrazines (DT) 3,6-,
The molar ratio of 2,4,5- tetrazines (DT) and Cobalt salts is 1:0.06-1, preferably 1:0.08-0.9, further preferably 1:0.15-
0.7, more preferable 1:0.2-0.5.
Preferably, the Cobalt salts are cabaltous nitrate hexahydrate, basic cobaltous carbonate, Cobalt monosulfate heptahydrate, cobalt chloride, bromine
Change one of cobalt, cobaltous iodide or a variety of.
Preferably, the acid solution is one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or a variety of；Preferably, acid is molten
The concentration of liquid is 0.05-5mol/L, preferably 0.1-3mol/L, more preferably 0.2-2mol/L.
Preferably, the inert gas is Ar or He.
The third embodiment provided according to the present invention provides a kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst
Purposes.
In fact according to spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst described in the first embodiment or according to second
The spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst for applying the preparation of any one of scheme the method, is used for oxygen also for the catalyst
Original reaction.
It is preferred that the catalyst to be used for the hydrogen reduction catalysis reaction of fuel cell.
Embodiment 1
A kind of preparation method of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, method includes the following steps:
(1) 3,6- the preparation of (3,5- the dimethyl pyrazole) -1,2,4,5- tetrazine of 3,6- bis- (BT): is synthesized by guanidine nitrate
Two (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT)；
(2) preparation of (the imidazole radicals) -1,2,4,5- of 3,6- bis- tetrazine (DT) ligand: by (the 3,5- dimethyl pyrazole of 3,6- bis-
Azoles) -1,2,4,5- tetrazines (BT) are fitted into reactor, and imidazoles is added, and it is heating reaction a period of time, cooling, it filters, it is dry, i.e.,
Obtain 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand；
(3) preparation of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF): taking 3,6- bis- (imidazole radicals) -1,2,
4,5- tetrazines (DT) ligand is dissolved in organic solvent, and cabaltous nitrate hexahydrate is added, heating reaction a period of time, cooling after dispersion
After filter, wash, obtain brown solid, as cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)；
(4) preparation of spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst: the cobalt-based that step (3) is obtained boils
Stone imidazate frame coordination polymer (CoDT-ZIF) is by high-temperature heat treatment to get spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C)
Oxygen reduction catalyst.
Embodiment 2
The preparation of (3,5- the dimethyl pyrazole) -1,2,4,5- tetrazine of 3,6- bis- (BT):
6.11g guanidine nitrate is dissolved in 50ml dioxane solution, 6.26g hydrazine hydrate is added, is heated to 110 DEG C, and return
Stream reaction 4h, obtains white solid, then white solid is dissolved in water after filtering, 15.02g acetylacetone,2,4-pentanedione, heating are added wherein
4h is reacted to 70 DEG C, is filtered, solid obtains 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines after being washed with water and drying
(BT)。
Embodiment 3
3,6- bis- (imidazole radicals) -1, the synthesis of 2,4,5- tetrazines (DT) ligand, include the following steps:
4.05g BT is added in the two mouth flask equipped with reflux unit for filling 25ml acetonitrile, stirring is equal at normal temperature
The acetonitrile solution of 2.35g imidazoles is added after even, is warming up to 80 DEG C of back flow reaction 1h, is cooled to room temperature, filters, with acetonitrile, dichloro
Methane wash product is dried under vacuum to constant weight and obtains target product.
Fig. 1 is the synthetic route for preparing 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand；Fig. 2 is list obtained
(the imidazole radicals) -1,2,4,5- tetrazine of body 3,6- bis- (DT)1H NMR figure.
Embodiment 4
Cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) synthesis and spherical nitrogen-doped carbon-supported cobalt-based (Co-N/
C) the preparation of oxygen reduction catalyst, includes the following steps:
(1) 0.86g 3,6- bis- (imidazole radicals) -1 are taken, 2,4,5- tetrazines (DT) are placed in 30ml DMF, and ultrasound is evenly dispersed
Afterwards, 0.556g cabaltous nitrate hexahydrate is added under agitation, after being uniformly dispersed, pours the mixture into 50mL reaction kettle,
3h is reacted at 140 DEG C, is filtered after reaction kettle natural cooling using PTFE organic film, is washed with DMF, obtain brown solid, in
80 DEG C of dry 12h are to constant weight in vacuum oven；As cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)；
(2) preparation of spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst, includes the following steps: to take 300mg
Cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) be put into porcelain crucible and be placed in tube furnace, under nitrogen atmosphere
It is warming up to 800 DEG C, after constant temperature 2h, is cooled to room temperature, gained non-carbon material 0.5M H2SO4Sulfuric acid sufficiently washs, and uses after suction filtration
Deionized water is washed to neutrality, in a vacuum drying oven 80 DEG C of dry 12h, gained spherical nitrogen-doped carbon-supported cobalt-based ORR catalyst；
Label are as follows: CoDT-ZIF-800.
Fig. 3 is the synthetic route of the cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) of preparation.
Fig. 4 is the infrared spectrogram of the cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) of preparation.
Fig. 5 is the XRD spectra of the cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) of preparation.
Fig. 6 is the nitrogen adsorption desorption isotherm figure of the catalyst of preparation.It can be seen from the figure that CoDT-ZIF-800 has
There is higher specific surface area (223cm2/ g), be conducive to the exposure of active site
The pore size distribution figure for the catalyst that Fig. 7 is.It can be seen from the figure that CoDT-ZIF-800 major part hole is to be situated between
Hole macropore is conducive to the immersion of electrolyte.
Figure 10 is the scanning electron microscope of the cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) of preparation
(SEM) picture.
Figure 11 is that the cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) of preparation is that presoma ORR catalyst is swept
Retouch electron microscope (SEM) picture.
Embodiment 5
The preparation of (3,5- the dimethyl pyrazole) -1,2,4,5- tetrazine of 3,6- bis- (BT):
6.11g guanidine nitrate is dissolved in 50ml dioxane solution, 10.01g hydrazine hydrate is added, is heated to 130 DEG C, and return
Stream reaction 2h, obtains white solid, then white solid is dissolved in water after filtering, 20.02g acetylacetone,2,4-pentanedione, heating are added wherein
2h is reacted to 80 DEG C, is filtered, solid obtains 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines after being washed with water and drying
(BT)。
Embodiment 6
3,6- bis- (imidazole radicals) -1, the synthesis of 2,4,5- tetrazines (DT) ligand, include the following steps:
4.05g BT is added in the two mouth flask equipped with reflux unit for filling 25ml acetonitrile, stirring is equal at normal temperature
The acetonitrile solution of 3.01g imidazoles is added after even, is warming up to 90 DEG C of back flow reaction 2h, is cooled to room temperature, filters, with acetonitrile, dichloro
Methane wash product is dried under vacuum to constant weight and obtains target product.
Embodiment 7
Cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) synthesis and spherical nitrogen-doped carbon-supported cobalt-based (Co-N/
C) the preparation of oxygen reduction catalyst, includes the following steps:
(1) 0.86g 3,6- bis- (imidazole radicals) -1 are taken, 2,4,5- tetrazines (DT) are placed in 50ml DMF, and ultrasound is evenly dispersed
Afterwards, 0.712g cobalt chloride is added under agitation, after being uniformly dispersed, pours the mixture into 100mL reaction kettle, at 100 DEG C
Lower reaction 5h is filtered using PTFE organic film after reaction kettle natural cooling, is washed with DMF, obtain brown solid, dry in vacuum
60 DEG C of dry 18h are to constant weight in dry case；As cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)；
(2) preparation of spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst, includes the following steps: to take 300mg
Cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) be put into porcelain crucible and be placed in tube furnace, under argon atmosphere
It is warming up to 900 DEG C, after constant temperature 1h, is cooled to room temperature, gained non-carbon material is sufficiently washed with 0.2M HCl, and deionization is used after suction filtration
Water washing is to neutrality, 60 DEG C of dry 18h in a vacuum drying oven, gained spherical nitrogen-doped carbon-supported cobalt-based ORR catalyst；Label
Are as follows: CoDT-ZIF-900.
Embodiment 8
Embodiment 7 is repeated, only the heat treatment temperature in step (2) is 700 DEG C, gained spherical nitrogen-doped carbon-supported cobalt-based
ORR catalyst；Label are as follows: CoDT-ZIF-700.
Embodiment 9
Spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst prepared by embodiment 4 is used for the oxygen of fuel cell
Reduction catalysts reaction.
Fig. 8 is that the cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) of preparation is that presoma ORR catalyst exists
LSV curve under different pyrolysis temperatures.It can be seen from the figure that CoDT-ZIF-800 take-off potential (E prepared by the present inventiono) high
In Pt/C catalyst 25mV, half wave potential (E1/2) it is higher than Pt/C catalyst 40mV, limiting current density (Jl) it is higher than Pt/C catalysis
Agent 0.15mA cm-2。
Claims (10)
1. a kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, it is by prepared by following preparation method: being first passed through
Guanidine nitrate synthesis 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT), then in 3,6- bis- (3,5- dimethyl pyrazole) -
Imidazoles synthesis 3,6- bis- (imidazole radicals) -1 is added in 1,2,4,5- tetrazine (BT), then 2,4,5- tetrazines (DT) ligand makes 3,6-
Two (imidazole radicals) -1,2,4,5- tetrazines (DT) and transition metals cobalt ion coordination form cobalt-based zeolite imidazole ester frame coordination polymerization
Object (CoDT-ZIF), then by high temperature pyrolysis cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) be prepared it is spherical
Nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst.
2. spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst according to claim 1, it is characterised in that: the transition gold
Belong to cobalt ions and comes from Cobalt salts；Preferably, Cobalt salts be cabaltous nitrate hexahydrate, basic cobaltous carbonate, Cobalt monosulfate heptahydrate,
One of cobalt chloride, cobaltous bromide, cobaltous iodide are a variety of.
3. a kind of preparation method of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst is prepared as claimed in claim 1 or 2 spherical
The method of nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, method includes the following steps:
(1) 3,6- bis- preparation of (3,5- the dimethyl pyrazole) -1,2,4,5- tetrazine of 3,6- bis- (BT): is synthesized by guanidine nitrate
(3,5- dimethyl pyrazole) -1,2,4,5- tetrazine (BT)；
(2) preparation of (the imidazole radicals) -1,2,4,5- of 3,6- bis- tetrazine (DT) ligand: by 3,6- bis- (3,5- dimethyl pyrazole) -1,
2,4,5- tetrazines (BT) are fitted into reactor, are added imidazoles, heating reaction a period of time, cooling, filtering, dry to get to 3,
6- bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) ligand；
(3) preparation of cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF): 3,6- bis- (imidazole radicals) -1,2,4,5- is taken
Tetrazine (DT) ligand is dissolved in organic solvent, and Cobalt salts are added, and after dispersion, heating reaction a period of time, is filtered, is washed after cooling
It washs, obtains brown solid, as cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF)；
(4) preparation of spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst: the cobalt-based zeolite miaow that step (3) is obtained
Azoles ester frame coordination polymer (CoDT-ZIF) by high-temperature heat treatment to get spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen also
Raw catalyst.
4. according to the method described in claim 3, it is characterized by: step (1) specifically: guanidine nitrate is dissolved in organic solvent
In (preferably dioxane solution), hydrazine hydrate is added, heating (is preferably heated to 80-140 DEG C, preferably 90-130 DEG C, more
Preferably 100-120 DEG C) and back flow reaction (preferably back flow reaction 1-6h, preferably 2-5.5h, more preferably 3-5h), filtering
After obtain white solid, then white solid is dissolved in water, acetylacetone,2,4-pentanedione is added wherein, heating (is preferably heated to 50-90
DEG C, preferably 55-85 DEG C, more preferably 60-80 DEG C) under reaction (preferably reaction 1-6h, preferably 2-5.5h, more preferably
3-5h), it filters, solid obtains 3,6- bis- (3,5- dimethyl pyrazole) -1,2,4,5- tetrazines (BT) after being washed with water and drying.
5. the method according to claim 3 or 4, it is characterised in that: step (2) specifically: by (3, the 5- dimethyl of 3,6- bis-
Pyrazoles) -1,2,4,5- tetrazines (BT) are fitted into the reactor for filling organic solvent (preferably acetonitrile), are stirred evenly at normal temperature
The organic solution (preferably dissolved with the acetonitrile solution of imidazoles) of imidazoles is added afterwards, heat up (it is preferably heated to 65-100 DEG C,
Preferably 68-95 DEG C, more preferably 70-90 DEG C) progress back flow reaction (preferably back flow reaction 0.2-6h, preferably 0.5-4h,
More preferably 1-2h), it is cooled to room temperature, filters, washing (is preferably washed using acetonitrile and/or methylene chloride), and drying is (preferably
It is dried under vacuum to constant weight) to get to 3,6- bis- (imidazole radicals) -1,2,4,5- tetrazines (DT) ligand.
6. the method according to any one of claim 3-5, it is characterised in that: step (3) specifically: take 3,6-, bis- (miaow
Oxazolyl) -1,2,4,5- tetrazines (DT) ligand is dissolved in organic solvent (preferably DMF), after ultrasound is evenly dispersed, in stirring condition
Lower addition Cobalt salts, after dispersion, heating (is preferably heated to 100-180 DEG C, preferably 120-160 DEG C, more preferably 130-
150 DEG C) it reacts (preferably reaction 1-12h, preferably 2-8h, more preferably 2.5-6h), it filters and (preferably uses after natural cooling
PTFE organic film filters), obtained solid (is preferably washed using DMF) by washing, dry (preferably dry in vacuum drying
50-120 DEG C of dry 6-24h in case, preferably 60-100 DEG C dry 8-18h), obtain brown solid, as cobalt-based zeolite imidazole
Ester frame coordination polymer (CoDT-ZIF).
7. the method according to any one of claim 3-6, it is characterised in that: step (4) specifically: obtain step (3)
To cobalt-based zeolite imidazole ester frame coordination polymer (CoDT-ZIF) be placed in the high temperature process furnances of inert gas or nitrogen
In, by high-temperature heat treatment (preferably, the temperature of heat treatment be 500-1500 DEG C, preferably 600-1200 DEG C, more preferably
700-900℃；The time of heat treatment is 0.5-6h, preferably 1-4h, more preferably 2-3h), it obtains with CoDT-ZIF as forerunner
The carbon material of body is labeled as CoDT-ZIF-T；After CoDT-ZIF-T carbon material is fully ground, dilute acid solution is added in 50-
12-96h (preferably 18-72h) is stirred under 100 DEG C (preferably 60-90 DEG C), filters and (is preferably filtered using PTFE moisture film), is washed
It washs and (preferably adopts and be washed with deionized), dry (preferably in a vacuum drying oven 40-80 DEG C dry 2-24h, preferably 50-
70 DEG C of dry 4-12h) to get spherical nitrogen-doped carbon-supported cobalt-based (Co-N/C) oxygen reduction catalyst.
8. the method according to any one of claim 3-7, it is characterised in that: guanidine nitrate and hydrazine hydrate in step (1)
Molar ratio is 1:2.0-5.0, preferably 1:2.5-4.5, further preferred 1:3.0-4.0；Mole of acetylacetone,2,4-pentanedione and guanidine nitrate
Than for 1:1.0-4.0, preferably 1:1.5-3.5, further preferred 1:2.0-3.0；And/or
In step (2), 3,6- bis- (3,5- dimethyl pyrazoles) -1, the molar ratio of 2,4,5- tetrazines (BT) and imidazoles is 1:0.5-5,
Preferably 1:1-4, more preferably 1:2-3.5；And/or
In step (3) bis- (imidazole radicals) -1,2,4,5- tetrazine (DT) of (the imidazole radicals) -1,2,4,5- of 3,6- bis- tetrazine (DT) 3,6- with
The molar ratio of Cobalt salts is 1:0.06-1, preferably 1:0.08-0.9, further preferably 1:0.15-0.7, more preferable 1:0.2-
0.5。
9. the method according to any one of claim 3-8, it is characterised in that: the Cobalt salts are six nitric hydrates
One of cobalt, basic cobaltous carbonate, Cobalt monosulfate heptahydrate, cobalt chloride, cobaltous bromide, cobaltous iodide are a variety of；And/or
The acid solution is one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or a variety of；Preferably, the concentration of acid solution is
0.05-5mol/L, preferably 0.1-3mol/L, more preferably 0.2-2mol/L；And/or
The inert gas is Ar or He.
10. spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst according to claim 1 or 2 or according to claim 3-9
Any one of the method preparation spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst, it is anti-that which is used for hydrogen reduction
It answers, which is preferably used for the hydrogen reduction catalysis reaction of fuel cell.
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