CN111992238A - Nano cobaltosic oxide loaded nitrogen-doped ultra-short carbon nanotube oxygen evolution catalyst and preparation method thereof - Google Patents
Nano cobaltosic oxide loaded nitrogen-doped ultra-short carbon nanotube oxygen evolution catalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 97
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 97
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000001301 oxygen Substances 0.000 title claims abstract description 35
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 16
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
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- 239000010410 layer Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention relates to the technical field of electrocatalysis, and discloses a nanometer cobaltosic oxide loaded nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst, wherein the length of an obtained oxidized ultrashort carbon nanotube is greatly reduced to form a large number of edge defects after acidification of a concentrated sulfuric acid/concentrated nitric acid mixed acid system, the nitrogen-doped ultrashort carbon nanotube is obtained by high-temperature heat treatment by taking urea as a nitrogen source, the shape of the edge defect of a surface interface of the nitrogen-doped ultrashort carbon nanotube is partially curled after being doped with nitrogen atoms, an oxygen evolution catalytic active site is fully exposed, the nitrogen-doped ultrashort carbon nanotube is taken as a carrier to obtain a cobalt oxalate intermediate, and the nanometer cobaltosic oxide loaded nitrogen-doped carbon nanotube is obtained by high-temperature calcination, has good electrical property and chemical property, accelerates electron transfer, and solves the problem of low conductivity of the nanometer cobaltosic oxide catalyst, and the nanometer cobaltosic oxide loaded ultrashort carbon nanotube with higher nitrogen exhibits low oxygen evolution overpotential and excellent oxygen evolution Catalytic performance.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst and a preparation method thereof.
Background
The fuel cell is a new energy conversion device which converts chemical energy in fuel and oxidant into electric energy efficiently and pollution-free through electrochemical reaction, and is an important component in a future energy system, however, the slow kinetics of the important anode oxygen evolution reaction in the fuel cell seriously reduces the working efficiency of the whole electrochemical system, and the current commercial oxygen evolution reaction catalyst is mainly Ir-based and Ru-based materials, but the price is high, and the large-scale application of the catalyst in industrial production is seriously restricted.
At present, the development of a non-noble metal catalyst with rich raw material sources and excellent catalytic performance and stability is the key for solving the bottleneck of the cost and the service life of a fuel cell, and among various non-noble metal catalysts, cobaltosic oxide with a nano structure draws wide attention due to low price, rich reserves, high activity and durability in alkaline electrolyte, but the conductivity of the cobaltosic oxide is low, so that the excellent electrocatalytic performance of the cobaltosic oxide is seriously restricted, and in order to solve the problem, an effective method is to combine the cobaltosic oxide with a material with high conductivity.
The carbon nano tube as a two-dimensional tubular material formed by curling single-layer or multi-layer graphite has good electrical property and chemical property, and shows good application prospect in the field of oxygen precipitation, but the defects of surface inertia, poor hydrophilicity, small real specific surface area and the like seriously restrict the practical application of the carbon nano tube, so that the functionalization of the carbon nano tube is an effective mode.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nanometer cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst and a preparation method thereof, and solves the problems of poor conductivity and low oxygen evolution catalytic activity of the cobaltosic oxide oxygen evolution catalyst.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a nanometer cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst is prepared by the following steps:
(1) slowly adding concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 into a beaker, adding carbon nano tubes and potassium permanganate in an ice bath, treating for 6-18h in a water bath ultrasonic device, adding deionized water for dilution, then adding hydrogen peroxide, fully stirring for 1-3h to obtain a suspension, filtering, washing with deionized water and absolute ethyl alcohol, and drying to obtain oxidized ultrashort carbon nano tubes;
(2) mixing the oxidized ultra-short carbon nano tube with urea, and carrying out heat treatment at the temperature of 700-;
(3) adding deionized water into a beaker, adding a nitrogen-doped ultra-short carbon nano tube, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, reacting for 2-4h, centrifugally collecting, washing with deionized water and absolute ethyl alcohol, drying, placing a mixed product in a tubular furnace, and performing heat treatment at 320-380 ℃ for 2-4h in an air atmosphere to obtain the cobaltosic oxide nanorod loaded nitrogen-doped ultra-short carbon nano tube.
Preferably, the mass ratio of the carbon nanotubes, the potassium permanganate and the hydrogen peroxide in the step (1) is 100:200-400: 600-800.
Preferably, the mass ratio of the oxidized ultra-short carbon nanotubes to the urea in the step (2) is 100: 400-600.
Preferably, the mass ratio of the nitrogen-doped ultra-short carbon nanotube, the cobalt nitrate and the oxalic acid in the step (3) is 15-20:100: 360-400.
Preferably, the water bath ultrasonic device in step (1) includes the main part, the left side swing joint of main part has control module, the bottom swing joint of main part has the motor, the bottom swing joint of main part has two stoppers of symmetry, the centre swing joint of stopper has the roller bearing, the bottom swing joint of main part has the pivot, the top swing joint of pivot has the gear, the centre swing joint of main part has the resistance wire, the right side swing joint of main part has the display, the right side swing joint of main part has temperature regulation apparatus, the right side swing joint of main part has rotational speed adjusting device, the right side swing joint of main part has ultrasonic probe.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the nanometer cobaltosic oxide loaded nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst is acidified by a concentrated sulfuric acid/concentrated nitric acid mixed acid system, the length of the obtained oxidized ultrashort carbon nanotube is greatly reduced, a large number of edge defects are formed, the specific surface area of the carbon nanotube is increased, the subsequent nitrogen doping modification is facilitated, the urea is used as a nitrogen source, the nitrogen-doped ultrashort carbon nanotube is obtained through high-temperature heat treatment, after a large number of edge defects on the surface interface of the carbon nanotube are doped with nitrogen atoms, the appearance of the carbon nanotube is partially curled, the oxygen-doped ultrashort carbon nanotube is beneficial to fully exposing oxygen evolution catalytic active sites, and therefore the oxygen evolution catalytic activity of the carbon nanotube is obviously improved.
According to the nanometer cobaltosic oxide loaded nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst, a nitrogen-doped ultrashort carbon nanotube is used as a carrier to obtain a cobalt oxalate intermediate, the cobalt oxalate intermediate is calcined at a high temperature to obtain the nanometer cobaltosic oxide loaded nitrogen-doped ultrashort carbon nanotube, the cobaltosic oxide nanorod is shorter and has a random stacking structure, has a larger specific surface area than the nanotube and a nanosheet, exposes more oxygen evolution catalytic active sites, and is loaded on the nitrogen-doped ultrashort carbon nanotube with good electrical property and chemical property, so that the transfer of electrons is accelerated, the problem of low conductivity of the nanometer cobaltosic oxide catalyst is solved, and the nanometer cobaltosic oxide loaded nitrogen-doped ultrashort carbon nanotube shows lower oxygen evolution overpotential and excellent oxygen evolution catalytic property.
Drawings
FIG. 1 is a schematic front cross-sectional view of a magnetic stirring apparatus;
FIG. 2 is a schematic top cross-sectional view of a magnetic stirring apparatus;
FIG. 3 is a schematic front view of a magnetic stirring apparatus.
1. A main body; 2. a control module; 3. a motor; 4. a limiting block; 5. a roller; 6. a rotating shaft; 7. a gear; 8. a resistance wire; 9. a display; 10. a temperature adjustment device; 11. a rotational speed adjusting device; 12. an ultrasonic probe;
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a nanometer cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst is prepared by the following steps:
(1) slowly adding concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 into a beaker, adding carbon nano tubes and potassium permanganate into the beaker in an ice bath, and treating the mixture for 6 to 18 hours in a water bath ultrasonic device, wherein the water bath ultrasonic device comprises a main body, the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a motor, the bottom of the main body is movably connected with two symmetrical limiting blocks, the middle of each limiting block is movably connected with a roller, the bottom of the main body is movably connected with a rotating shaft, the top of the rotating shaft is movably connected with a gear, the middle of the main body is movably connected with a resistance wire, the right side of the main body is movably connected with a display, the right side of the main body is movably connected with a temperature regulating device, the right side of the main body, The mass ratio of potassium permanganate to hydrogen peroxide is 100: 200-;
(2) mixing the oxidized ultrashort carbon nanotube with urea, wherein the mass ratio of the oxidized ultrashort carbon nanotube to the urea is 100:400-600, and performing heat treatment at the temperature of 700-1100 ℃ for 1-3h in the argon atmosphere to obtain the nitrogen-doped ultrashort carbon nanotube;
(3) adding deionized water into a beaker, adding a nitrogen-doped ultrashort carbon nanotube, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, wherein the mass ratio of the nitrogen-doped ultrashort carbon nanotube to the cobalt nitrate to the oxalic acid is 15-20:100: 360-.
Example 1
(1) Slowly adding concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 into a beaker, adding carbon nano tubes and potassium permanganate into the beaker in an ice bath, and treating the mixture for 6 hours in a water bath ultrasonic device, wherein the water bath ultrasonic device comprises a main body, the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a motor, the bottom of the main body is movably connected with two symmetrical limiting blocks, the middle of each limiting block is movably connected with a roller, the bottom of the main body is movably connected with a rotating shaft, the top of the rotating shaft is movably connected with a gear, the middle of the main body is movably connected with a resistance wire, the right side of the main body is movably connected with a display, the right side of the main body is movably connected with a temperature regulating device, the right side of the main body is movably connected, The mass ratio of hydrogen peroxide is 100:200:600, fully stirring for 1h to obtain a suspension, filtering, washing with deionized water and absolute ethyl alcohol, and drying to obtain the oxidized ultrashort carbon nanotube;
(2) mixing the oxidized ultrashort carbon nanotube and urea, wherein the mass ratio of the oxidized ultrashort carbon nanotube to the urea is 100:400, and performing heat treatment at 700 ℃ for 1h in an argon atmosphere to obtain a nitrogen-doped ultrashort carbon nanotube;
(3) adding deionized water into a beaker, adding a nitrogen-doped ultrashort carbon nanotube, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, wherein the mass ratio of the nitrogen-doped ultrashort carbon nanotube to the cobalt nitrate to the oxalic acid is 15:100:360, reacting for 2 hours, centrifugally collecting, washing with deionized water and absolute ethyl alcohol, drying, placing a mixed product in a tubular furnace, and performing heat treatment at 320 ℃ for 2 hours in an air atmosphere to obtain the nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst.
Example 2
(1) Slowly adding concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 into a beaker, adding carbon nano tubes and potassium permanganate into the beaker in an ice bath, and treating the mixture in a water bath ultrasonic device for 12 hours, wherein the water bath ultrasonic device comprises a main body, the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a motor, the bottom of the main body is movably connected with two symmetrical limiting blocks, the middle of each limiting block is movably connected with a rolling shaft, the bottom of the main body is movably connected with a rotating shaft, the top of the rotating shaft is movably connected with a gear, the middle of the main body is movably connected with a resistance wire, the right side of the main body is movably connected with a display, the right side of the main body is movably connected with a temperature regulating device, the right side of the main body is movably, The mass ratio of hydrogen peroxide is 100:300:700, fully stirring for 2h to obtain a suspension, filtering, washing with deionized water and absolute ethyl alcohol, and drying to obtain the oxidized ultrashort carbon nanotube;
(2) mixing the oxidized ultrashort carbon nanotube with urea, wherein the mass ratio of the oxidized ultrashort carbon nanotube to the urea is 100: 400-;
(3) adding deionized water into a beaker, adding a nitrogen-doped ultrashort carbon nanotube, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, wherein the mass ratio of the nitrogen-doped ultrashort carbon nanotube to the cobalt nitrate to the oxalic acid is 17:100:380, reacting for 3 hours, centrifugally collecting, washing with deionized water and absolute ethyl alcohol, drying, placing a mixed product in a tubular furnace, and performing heat treatment at 350 ℃ for 3 hours in an air atmosphere to obtain the nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst.
Example 3
(1) Slowly adding concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 into a beaker, adding carbon nano tubes and potassium permanganate into the beaker in an ice bath, and treating the mixture in a water bath ultrasonic device for 10 hours, wherein the water bath ultrasonic device comprises a main body, the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a motor, the bottom of the main body is movably connected with two symmetrical limiting blocks, the middle of each limiting block is movably connected with a rolling shaft, the bottom of the main body is movably connected with a rotating shaft, the top of the rotating shaft is movably connected with a gear, the middle of the main body is movably connected with a resistance wire, the right side of the main body is movably connected with a display, the right side of the main body is movably connected with a temperature regulating device, the right side of the main body is movably, The mass ratio of hydrogen peroxide is 100:400:600, fully stirring for 2h to obtain a suspension, filtering, washing with deionized water and absolute ethyl alcohol, and drying to obtain the oxidized ultrashort carbon nanotube;
(2) mixing the oxidized ultrashort carbon nanotube with urea, wherein the mass ratio of the oxidized ultrashort carbon nanotube to the urea is 100:600, and performing heat treatment at 1100 ℃ for 2h in an argon atmosphere to obtain a nitrogen-doped ultrashort carbon nanotube;
(3) adding deionized water into a beaker, adding a nitrogen-doped ultrashort carbon nanotube, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, wherein the mass ratio of the nitrogen-doped ultrashort carbon nanotube to the cobalt nitrate to the oxalic acid is 18:100:380, reacting for 3 hours, centrifugally collecting, washing with deionized water and absolute ethyl alcohol, drying, placing a mixed product in a tubular furnace, and performing heat treatment at 380 ℃ for 2 hours in an air atmosphere to obtain the nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst.
Example 4
(1) Slowly adding concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 into a beaker, adding carbon nano tubes and potassium permanganate into the beaker in an ice bath, and treating the mixture for 18 hours in a water bath ultrasonic device, wherein the water bath ultrasonic device comprises a main body, the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a motor, the bottom of the main body is movably connected with two symmetrical limiting blocks, the middle of each limiting block is movably connected with a rolling shaft, the bottom of the main body is movably connected with a rotating shaft, the top of the rotating shaft is movably connected with a gear, the middle of the main body is movably connected with a resistance wire, the right side of the main body is movably connected with a display, the right side of the main body is movably connected with a temperature regulating device, the right side of the main body is movably, The mass ratio of hydrogen peroxide is 100:400:800, fully stirring for 1h to obtain a suspension, filtering, washing with deionized water and absolute ethyl alcohol, and drying to obtain the oxidized ultrashort carbon nanotube;
(2) mixing the oxidized ultrashort carbon nanotube with urea, wherein the mass ratio of the oxidized ultrashort carbon nanotube to the urea is 100:600, and performing heat treatment at 1100 ℃ for 1h in an argon atmosphere to obtain a nitrogen-doped ultrashort carbon nanotube;
(3) adding deionized water into a beaker, adding a nitrogen-doped ultrashort carbon nanotube, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, wherein the mass ratio of the nitrogen-doped ultrashort carbon nanotube to the cobalt nitrate to the oxalic acid is 15:100:360, reacting for 2 hours, centrifugally collecting, washing with deionized water and absolute ethyl alcohol, drying, placing a mixed product in a tubular furnace, and performing heat treatment at 320 ℃ for 4 hours in an air atmosphere to obtain the nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst.
Comparative example 1
(1) Slowly adding concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 into a beaker, adding carbon nano tubes and potassium permanganate into the beaker in an ice bath, and treating the mixture for 18 hours in a water bath ultrasonic device, wherein the water bath ultrasonic device comprises a main body, the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a motor, the bottom of the main body is movably connected with two symmetrical limiting blocks, the middle of each limiting block is movably connected with a rolling shaft, the bottom of the main body is movably connected with a rotating shaft, the top of the rotating shaft is movably connected with a gear, the middle of the main body is movably connected with a resistance wire, the right side of the main body is movably connected with a display, the right side of the main body is movably connected with a temperature regulating device, the right side of the main body is movably, The mass ratio of hydrogen peroxide is 100:150:500, fully stirring for 3h to obtain a suspension, filtering, washing with deionized water and absolute ethyl alcohol, and drying to obtain the oxidized ultrashort carbon nanotube;
(2) mixing the oxidized ultrashort carbon nanotube with urea, wherein the mass ratio of the oxidized ultrashort carbon nanotube to the urea is 100:300, and carrying out heat treatment at 1200 ℃ for 1h in an argon atmosphere to obtain a nitrogen-doped ultrashort carbon nanotube;
(3) adding deionized water into a beaker, adding a nitrogen-doped ultrashort carbon nanotube, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, wherein the mass ratio of the nitrogen-doped ultrashort carbon nanotube to the cobalt nitrate to the oxalic acid is 10:100:350, reacting for 2 hours, centrifugally collecting, washing with deionized water and absolute ethyl alcohol, drying, placing a mixed product in a tubular furnace, and performing heat treatment at 300 ℃ for 2 hours in an air atmosphere to obtain the nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst.
The nanometer cobaltosic oxide supported nitrogen-doped ultra-short carbon nanotube oxygen evolution catalyst obtained in the embodiment and the comparative example is respectively placed in an ethanol solvent, Nafion solution is added, ultrasonic treatment is carried out for 30min, catalyst slurry which is uniformly dispersed is obtained, the catalyst slurry is uniformly coated on the surface of a disc electrode which is polished and cleaned, air drying is carried out at room temperature, a catalyst thin layer with uniform thickness is formed, and then a film working electrode is obtained, and oxygen precipitation catalytic activity performance test is carried out in a CHI660D type electrochemical workstation by taking a platinum electrode as a counter electrode, a saturated silver chloride electrode as a reference electrode and an electrolyte as a KOH solution with 1 mol/L.
Claims (5)
1. A nanometer cobaltosic oxide loaded nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst is characterized in that: the preparation method of the nanometer cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst comprises the following steps:
(1) adding carbon nano tubes and potassium permanganate into concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1 in an ice bath, treating for 6-18h in a water bath ultrasonic device, diluting, then adding hydrogen peroxide, fully stirring for 1-3h to obtain a suspension, filtering, washing and drying to obtain oxidized ultrashort carbon nano tubes;
(2) mixing the oxidized ultra-short carbon nano tube with urea, and carrying out heat treatment at the temperature of 700-;
(3) adding the nitrogen-doped ultrashort carbon nanotube into deionized water, performing ultrasonic dispersion treatment, adding cobalt nitrate, then adding an oxalic acid solution while stirring, reacting for 2-4h, centrifugally collecting, washing and drying, placing a mixed product in a tube furnace, and performing heat treatment at 320-380 ℃ for 2-4h in the air atmosphere to obtain the cobaltosic oxide nanorod loaded nitrogen-doped ultrashort carbon nanotube.
2. The nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst as claimed in claim 1, wherein: the mass ratio of the carbon nano tube, the potassium permanganate and the hydrogen peroxide in the step (1) is 100:200-400: 600-800.
3. The nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst as claimed in claim 1, wherein: the mass ratio of the oxidized ultra-short carbon nano-tube to the urea in the step (2) is 100: 400-600.
4. The nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst as claimed in claim 1, wherein: the mass ratio of the nitrogen-doped ultra-short carbon nano tube, the cobalt nitrate and the oxalic acid in the step (3) is 15-20:100: 360-.
5. The nano cobaltosic oxide supported nitrogen-doped ultrashort carbon nanotube oxygen evolution catalyst as claimed in claim 1, wherein: the water bath ultrasonic device in step (1) includes the main part, the left side swing joint of main part has control module, the bottom swing joint of main part has the motor, the bottom swing joint of main part has two stoppers of symmetry, the middle swing joint of stopper has the roller bearing, the bottom swing joint of main part has the pivot, the top swing joint of pivot has the gear, the middle swing joint of main part has the resistance wire, the right side swing joint of main part has the display, the right side swing joint of main part has temperature regulation apparatus, the right side swing joint of main part has rotational speed adjusting device, the right side swing joint of main part has ultrasonic probe.
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