CN103170334B - Carbon-supported cobalt oxide catalyst and preparation and application thereof - Google Patents

Carbon-supported cobalt oxide catalyst and preparation and application thereof Download PDF

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CN103170334B
CN103170334B CN201110436256.3A CN201110436256A CN103170334B CN 103170334 B CN103170334 B CN 103170334B CN 201110436256 A CN201110436256 A CN 201110436256A CN 103170334 B CN103170334 B CN 103170334B
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cobalt oxide
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oxide catalyst
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CN103170334A (en
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孙公权
刘静
姜鲁华
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Dalian Institute of Chemical Physics of CAS
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to a carbon-supported cobalt oxide catalyst. The carbon-supported cobalt oxide catalyst is characterized in that the cobalt oxide is one or more than two of Co3O4, CoO (OH) and Co2O3. Compared with the prior art, the preparation of the carbon-supported cobalt oxide catalyst, provided by the invention, has the advantages that the high-heat treatment preparation route is abandoned, the surface of a carbon support is modified through solvothermal reaction at extremely low temperature, a transition metallic oxide is supported at room temperature, and the oxygen reduction reaction close to the 4e-process can be realized on the surface of the prepared catalyst; and the catalyst improves the oxygen reduction reaction, simplifies the catalyst preparation process, decreases the catalyst cost, and plays an important role in the commercialized development of fuel cells.

Description

A kind of carbon carries cobalt oxide catalyst and Synthesis and applications thereof
Technical field
The present invention relates to a kind of novel non-platinum catalyst, relate to oxygen reduction catalyst under a kind of metal air fuel cell oxygen reduction catalyst, alkaline anion-exchange membrane fuel cell oxygen reduction catalyst or other alkali conditions specifically.
The invention still further relates to the preparation method of above-mentioned catalyst.
The invention still further relates to the application of above-mentioned catalyst.
Background technology
Oxygen reduction reaction is all very important process in fuel cell, metal-air battery and even chlorine industry.Research shows that mechanism of oxygen reduction is relevant with electrode material and reaction medium.Pt sill is widely used for as fuel battery negative pole oxygen reduction catalyst, but the price of its costliness and rare source limit commercializing fuel cells process.In recent years, due to the development of anion-exchange membrane, anion-exchange membrane fuel cells is more and more paid close attention to.Reduction kinetics of oxygen is faster than acid medium in alkaline medium, and the selection therefore for electrode material is more extensive.The non-Platinum Noble Metal Catalysts such as the catalyst based and Ag base of Pd are all used to alternative Pt sill, although comparatively Pt price is slightly low for these Pd, Ag noble metals, DEVELOPMENT PROSPECT is still limited.Exploitation base metal eelctro-catalyst, makes anion-exchange membrane fuel cells on cost, have more commercialization attraction.As far back as the sixties in 20th century, the transition metal macrocyclic compound that the reported first such as Jasinski have Metal-N4 structure has catalytic activity to ORR.But find in research subsequently, this type of transition metal macrocyclic compound is unstable in acid medium, can not practical application in a fuel cell.20 century 70s, researcher finds, to the heat treatment of transition metal macrocyclic compound under inert atmosphere, can significantly improve its ORR activity and stability.The eighties in 20th century, Gupta etc. are first with non-N 4the macrocyclic compound of structure is that N precursor prepares ORR catalyst.Henceforth, researcher adopts similar method, with the cheaper and common inorganic salts of price, material with carbon element and containing the compound of N for precursor, prepare other ORR catalyst a lot.Although although traditional M/N/C System Catalyst shows certain potentiality in activity and stability, its preparation all relates to high-temperature heat treatment process, is huge waste to energy consumption, loaded down with trivial details preparation technology is unfavorable for batch preparation simultaneously.
Carbon carrier has certain activity to ORR in alkaline medium, is 2e-process, and metal oxide such as Co 3o 4, MnO 2, Fe 2o 3deng to O 2there is good catalytic reduction ability, therefore utilize the metal oxide catalyst that carbon carries to be conducive to ORR process continuously with 2e -process is carried out, by carrying out carrier surface effectively modifying to strengthen the synergy between carrier and metal oxide.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to provide a kind of oxygen reduction catalyst and the Synthesis and applications thereof that are applied to Proton Exchange Membrane Fuel Cells.
For achieving the above object, the present invention adopts following concrete scheme to realize:
Compared with prior art, carbon-carried transition metal oxide catalyst of the present invention has the following advantages:
Compared with the method prepares non-precious metal catalyst with conventional method, abandon the route of high-temperature heat treatment, at a lower temperature, by solvent thermal reaction, carbon support has been modified, transition metal oxide carried under room temperature, can realize close to 4e at obtained catalyst surface -the oxygen reduction reaction of process, this catalyst improves oxygen reduction reaction efficiency, simplifies catalyst preparation process, reduces catalyst cost, is extremely important to the commercialized development of fuel cell.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the sample prepared according to embodiment one to embodiment five;
Fig. 2 is the ORR expression activitiy of sample in the saturated 0.1M NaOH electrolyte of oxygen of sample and the comparative example one prepared according to embodiment one to embodiment five;
Fig. 3 is the ORR expression activitiy of sample in the saturated 0.1M NaOH electrolyte of oxygen of sample and the comparative example one prepared according to embodiment two, six, seven, eight;
The ORR expression activitiy that Fig. 4 is the sample for preparing according to embodiment two, nine, ten in the saturated 0.1M NaOH electrolyte of oxygen;
The ORR expression activitiy that Fig. 5 is the sample for preparing according to embodiment two, 11,12 in the saturated 0.1MNaOH electrolyte of oxygen;
Fig. 6 is the sample different rotating speeds RDE test result prepared according to embodiment two.
Fig. 7 is rotating ring disk electrode (r.r.d.e) (RRDE) test result of embodiment two and comparative example two, three.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is explained in detail.Certain the present invention is not limited in these specific embodiments.
Embodiment 1:
First, in 600mL 5M HNO 310000mgXC-72R carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the carbon dust 500mg after above-mentioned process, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the XC-72R carbon carrier after process.
Get the XC-72R carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
XRD spectra as shown in Figure 1 can be found out, this catalyst may by Co 3o 4form with CoO (OH).
Embodiment 2:
First, in 600mL 5M HNO 310000mgXC-72R carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the carbon dust 500mg after above-mentioned process, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the XC-72R carbon carrier after process.
Get the XC-72R carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
Embodiment 3:
First, in 600mL 5M HNO 310000mgXC-72R carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the carbon dust 500mg after above-mentioned process, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the XC-72R carbon carrier after process.
Get the XC-72R carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 2mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
Embodiment 4:
First, in 600mL 5M HNO 310000mgXC-72R carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the carbon dust 500mg after above-mentioned process, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the XC-72R carbon carrier after process.
Get the XC-72R carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 4mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
Embodiment 5:
First, in 600mL 5M HNO 310000mgXC-72R carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the carbon dust 500mg after above-mentioned process, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the XC-72R carbon carrier after process.
Get the XC-72R carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 8mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
Embodiment 6:
First, in 600mL 5M HNO 38000mg BP-2000 carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the carbon dust 500mg after above-mentioned process, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the BP-2000 carbon carrier after process.
Get the BP-2000 carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of BP-2000 carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that BP-2000 supports.
Embodiment 7:
First, in 600mL 5M HNO 38000mg BP-2000 carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the CNT 500mg after above-mentioned process, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the BP-2000 carbon carrier after process.
Get the MWCNT carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of MWCNT carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that BP-2000 supports.
Embodiment 8:
Take graphene oxide 500mg, and be scattered in 200mL ethanol, add the NH that 1mL mass concentration is 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the Graphene carrier after process.
Get the Graphene carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of graphene carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that Graphene supports.
As seen from Figure 3, the better catalytic activity of catalyst towards oxygen reduction on BP-2000 and XC-72 of finishing.
Embodiment 9:
Take XC-72R 500mg, and be scattered in 200mL ethanol, add the whole mass concentration of 1mL is the NH of 25% simultaneously 3h 2o, proceeds to mixture in 2L reactor after stirring, and reacts 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the XC-72R carrier after process.
Get the XC-72R carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports
Embodiment 10:
First, in 600mL 5M HNO 310000mgXC-72R carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Take the carbon dust 500mg after above-mentioned process, and be scattered in stir in 200mL ethanol after mixture is proceeded in 2L reactor, react 3h under 160 DEG C of conditions.Revolve to steam and in convection oven, dry 12h under 80 DEG C of conditions except after desolventizing, obtain the XC-72R carbon carrier after process.
Get the XC-72R carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
As shown in Figure 4, the adding of ammoniacal liquor in the oxidation processes of carbon support and solvent heat process is all necessary to the higher oxygen reduction catalytic activity of generation.
Embodiment 11:
XC-72R carbon carrier 80mg adds in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
Embodiment 12:
First, in 600mL 5M HNO 310000mgXC-72R carbon dust is added in solution, after ultrasonic disperse 30min, reflux under 110 DEG C of conditions 6h, except deashing and increasing Surface oxygen-containing groups, adopt the washing of a large amount of deionized water after filtering to suspension in neutral, after again filtering in convection oven under 120 DEG C of conditions dry 12h.
Get the XC-72R carbon carrier 80mg after above-mentioned process to add in 20mL ethanol, and by even for its ultrasonic disperse.Meanwhile, 0.5g cobalt acetate is added and fills in the 250mL three-neck flask of 25mL absolute ethyl alcohol, after ultrasonic disperse is even, add the NH of 2.5mL mass concentration 25% 3h 2o, reflux 3.5h under 100 DEG C of conditions, obtains the brown colloid of cobalt/cobalt oxide.
To pipette above-mentioned colloid 1mL, and be joined and be above-mentionedly dispersed with in the ethanol of XC-72R carbon carrier, solvent evaporated after magnetic agitation 4h, in convection oven, 80 degree of dry 12h, obtain the cobalt oxide catalyst that XC-72R supports.
As shown in Figure 5, XC-72R is not treated, and only through nitric acid oxidation process, all can not obtain highly reactive form of oxygen reducing catalyst.
Fig. 6 and Fig. 7 all shows that in embodiment two, gained catalyst towards oxygen reduction has higher catalytic activity, is nearly 4e-process.
Comparative example one: 20%Pt/C-Etek
Comparative example two: the XC-72R of the finishing of gained in embodiment two
Comparative example three: the cobalt oxide colloidal solution of gained in embodiment two.

Claims (8)

1. carbon carries a cobalt oxide catalyst, it is characterized in that: cobalt/cobalt oxide is Co 3o 4, CoO (OH), Co 2o 3in one or more, in catalyst, the load amount of cobalt/cobalt oxide is 1%-99%;
Comprise following preparation process,
(1) carbon support base group modification:
A. in strong oxidant solution, add carbon dust, ultrasonic disperse evenly after under 90-150 degrees celsius reflow treatment 6-24 hour, filter and adopt deionized water to wash to neutral, dryly under 80-120 degrees celsius processing 12-48 hour;
B. products therefrom in step a is scattered in alcohol solvent, after being uniformly mixed, adds the NH that mass concentration is 10%-30% 3h 2o, proceeds in reactor by mixture after being again uniformly mixed, under 100-200 degrees celsius, react 3-6 hour, processes 8-48 hour, obtain the carbon carrier after finishing except dry under 80 degrees celsius after desolventizing; Wherein add NH in every 100 milliliters of alcohol solvents 3h 2the volume of O is 0.1-10ml;
(2) carbon carries the preparation of cobalt oxide catalyst:
A. get the carbon carrier after the finishing of step (1) b gained, and be scattered in ethanol, ultrasonic disperse is even;
B. in ethanol, add cobalt acetate, after ultrasonic disperse is even, in every 100 milliliters of alcohol solvents, add the NH that mass concentration is 10%-30% 3h 2o 0.1-10ml, reflux 3.5-24 hour under 80-140 degrees celsius, obtains the brown colloid of cobalt/cobalt oxide;
C. removing step (2) b gained colloid, and added in step (2) a gained suspension, stir 4-24 hour, solvent evaporated, dry 8-48 hour under 80-120 degree condition, obtains carbon and carries cobalt oxide catalyst.
2. carbon carries cobalt oxide catalyst as claimed in claim 1, it is characterized in that: strong oxidizer described in step (1) a is one or more in nitric acid, sulfuric acid, potassium permanganate, and the concentration of described strong oxidizer is 3-6 mol/L.
3. carbon carries cobalt oxide catalyst as claimed in claim 1, it is characterized in that: described in step (1) a, carbon dust is Vulcan XC-72, BP, multi-walled carbon nano-tubes; The amount of substance of described carbon dust is 0.25:1-1:1 with the ratio of the amount of substance of strong oxidizer.
4. carbon carries cobalt oxide catalyst as claimed in claim 1, it is characterized in that: described in step (1) b, product is 20:1-1:1 with the ratio of the amount of substance of ethanol.
5. carbon carries cobalt oxide catalyst as claimed in claim 1, it is characterized in that: described in step (2) b, cobalt acetate is 40:1-4:1 with the ratio of the amount of substance of ethanol.
6. carbon carries cobalt oxide catalyst as claimed in claim 1, it is characterized in that: described in step (2) a, carbon carrier is 15:1-100:1 with the ratio of the amount of substance of ethanol.
7. carbon carries cobalt oxide catalyst as claimed in claim 1, it is characterized in that: described in step (2) c, the volume ratio of colloid and suspension is 0.05:1-0.5:1.
8. carbon according to claim 1 carries an application for cobalt oxide catalyst, it is characterized in that: can be used as oxygen reduction catalyst under metal air fuel cell oxygen reduction catalyst, alkaline anion-exchange membrane fuel cell oxygen reduction catalyst or other alkali conditions.
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