CN111437846B - Porous CoO/CoP nanotube and preparation method and application thereof - Google Patents
Porous CoO/CoP nanotube and preparation method and application thereof Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 37
- LOCYLIRBVCIGNR-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;cobalt Chemical compound [Co].OC(=O)[C@@H](N)CC(O)=O LOCYLIRBVCIGNR-DKWTVANSSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 19
- 235000003704 aspartic acid Nutrition 0.000 claims description 18
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 14
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 36
- 239000000919 ceramic Substances 0.000 description 20
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- -1 Platinum Group Metals Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a porous CoO/CoP nanotube, a preparation method thereof and application thereof as a hydrogen evolution reaction catalyst. The invention provides a novel preparation method of a porous CoO/CoP nanotube, the porous CoO/CoP nanotube is prepared by a self-sacrifice template method which is simple and convenient and can realize large-scale production, and the method has the advantages of simple and easy process, simple operation and realization of large-scale production.
Description
Technical Field
The invention relates to a porous CoO/CoP nanotube, a preparation method thereof and application thereof as a hydrogen evolution reaction catalyst, belonging to the technical field of Co-based nanotube materials.
Background
Energy crisis and environmental pollution are two major problems that human beings must face at present, and the development of new technology and new energy is the key to solve the two problems, and is also a research focus in the scientific research field, and a series of new energy such as solar energy, wind energy, biomass energy and the like are generated at the same time, wherein hydrogen energy is regarded as a high-efficient clean renewable energy source and is regarded as a novel energy carrier with the most development prospect in the future. Among the various hydrogen production methods, the hydrogen production by water electrolysis is unique due to the advantages of high efficiency, green, environmental protection, rich raw materials and the like, and the electric energy required by electrolysis can be supplied by solar energy, wind energy and the like, so the hydrogen production by water electrolysis is also an important energy conversion and storage means. Although the noble metals Platinum Group Metals (PGMs) are the most advanced electrocatalysts, their scarcity and high cost severely hamper their widespread commercial use. At present, the development of non-noble metal catalysts is one of the important scientific problems today. Including heteroatom-doped nanocarbons, transition metal chalcogenides, carbides, nitrides, oxides, phosphates, and the like. Among them, Transition Metal Phosphides (TMPs) are typical representatives of high-activity, low-cost catalysts, and are expected to replace noble metals for electrolyzing water. However, these materials have low conductivity, low intrinsic activity and poor performance. Strategies to further improve their catalytic performance, including hybrid compounding, electronic regulation, and design of nanostructures, are needed. The development of efficient, low cost electrocatalysts is central to the electrolysis of water.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention aims to provide a porous CoO/CoP nanotube, a preparation method thereof and application of an electrode material prepared by the method in hydrogen evolution reaction. According to the invention, a cobalt-aspartic acid complex precursor is prepared by a simple and universal self-sacrifice template method, and is oxidized and then phosphorized to generate the porous CoO/CoP nanotube, which shows excellent HER performance and stability.
The technical scheme is as follows: in order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a porous CoO/CoP nanotube comprises the steps of using cobalt salt as a metal source and aspartic acid as a coordination agent, preparing a cobalt-aspartic acid complex in advance through a solvothermal reaction, calcining and oxidizing the cobalt-aspartic acid complex, and carrying out phosphating treatment to obtain the porous CoO/CoP nanotube.
Preferably, the method comprises the following steps:
the cobalt salt is selected from Co (NO)3)2And CoCl2One or two of them.
The solvothermal reaction is to add aspartic acid, cobalt salt and sodium hydroxide into a mixed solution of water and ethylene glycol, uniformly mix, and perform solvothermal reaction at 140-200 ℃ for 4-10 h.
More preferably, in the mixed solution of water and ethylene glycol, the volume ratio of water to ethylene glycol is (0.1-99): 1; the molar ratio of the aspartic acid to the cobalt salt to the sodium hydroxide is (0.01-1): (0.01-1): (0.01-1).
The calcining oxidation is to heat the linear cobalt-aspartic acid complex to 300-400 ℃ in an oxygen atmosphere in a temperature programming manner, and keep the temperature for 3-8h, and preferably 300 ℃.
Further preferably, the temperature programming rate is 0.5-10 ℃/min.
And the phosphorization treatment is to heat the calcined and oxidized product and sodium hypophosphite to 300-350 ℃ in an inert atmosphere in a temperature programming manner, and keep the temperature for 20-80min for phosphorization.
Further preferably, the inert atmosphere comprises Ar, Ar/H2、N2At least one of; the temperature programming rate is 1-20 ℃/min.
The invention also provides the porous CoO/CoP nanotube prepared by the method.
And the application of the porous CoO/CoP nanotube as a hydrogen evolution reaction catalyst.
In the process of the invention, Co (NO) is used3)2Or CoCl2Aspartic acid (C) as a source of metal4H7NO4) As a coordination agent, a pink cobalt-aspartic acid complex is prepared in advance, and a porous CoO/CoP nanotube is obtained through oxidation and then phosphorization by a self-sacrifice template method. The material has a hollow tubular structure, the rough surface of the pipeline has rich pore channels, and the CoO and CoP heterostructure interfaces are mutually permeated.
The porous CoO/CoP nanotube prepared by the invention has the following advantages: the hollow tubular structure has abundant exposed and accessible active sites, and can promote mass transfer in a plane. Secondly, the organic components are effectively introduced into the pore channels during cracking, the unique appearance of the organic components is kept, a large specific surface area and rich active sites are exposed, and the organic components are beneficial to the transmission and diffusion of gas and electrolyte. And the interfaces of the heterogeneous structures with uniform CoO and CoP distribution are mutually permeated, so that the strong synergistic effect is achieved, the electric conductivity and the electron transfer are enhanced, and the hydrogen evolution reaction is promoted.
Has the advantages that: compared with the prior art, the invention has the advantages that:
the invention is a novel preparation method of porous CoO/CoP nanotube, the porous CoO/CoP nanotube is prepared by a self-sacrifice template method which is simple and convenient and can realize large-scale production, and the method has simple and easy process and simple operation and can realize large-scale production; the prepared product has the characteristics of regular appearance, rich pore channels, more active sites, good circulation stability, flower-shaped structure and the like. Compared with the conventional CoP material, the prepared CoO/CoP nanotube has strong synergistic effect, has more excellent structural characteristics and component advantages, is an electrolytic water catalytic material with extremely high potential, and has wide application prospect in the future energy industry.
Drawings
FIG. 1 is a TEM image of a linear cobalt-aspartic acid complex precursor prepared according to the method of the present invention;
FIG. 2 is an SEM image of a linear cobalt-aspartic acid complex precursor prepared according to the method of the present invention;
FIG. 3 is porous Co prepared according to the method of the present invention3O4TEM and SEM spectra of the nanotubes;
FIG. 4 is a porous Co prepared according to the method of the present invention3O4XRD pattern of nanotubes;
FIG. 5 is a TEM image of porous CoO/CoP nanotubes prepared according to the method of the present invention;
FIG. 6 is an XRD pattern of porous CoO/CoP nanotubes prepared according to the method of the present invention;
FIG. 7 is an LSV profile of HER of porous CoO/CoP nanotubes prepared according to the method of the invention;
FIG. 8 is a comparative HER plot before and after 1000 cycles of porous CoO/CoP nanotubes prepared according to the method of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail by the following specific examples.
Example 1
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthetic thread formCobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3O420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 2
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 6mmol NaOH are added to be dissolved in 36mL of mixed solution, stirred to pink, transferred to a reaction kettle, and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours.
3) Step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3O420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 3
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 1mmol NaOH is added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3O420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 4
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 140 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 5
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 12 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 6
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 2:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 7
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 2:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 8
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ by a program of 5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of the original ceramic boat) is arranged at the two ends of the porcelain boat at a distance of 5cm, the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, the temperature is kept for 30min, and then cooling is carried out, thus obtaining the ceramic boatAnd (4) obtaining a final product.
Example 9
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 300 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 30min, and then the final product is obtained after cooling.
Example 10
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of) is placed at the two ends of the porcelain boat at the distance of 5cm and in Ar/H2Heating to 350 deg.C at 5 deg.C/min under atmosphereTreating, keeping at the temperature for 30min, and cooling to obtain the final product.
Example 11
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of the original ceramic boat) are arranged at the two ends of the ceramic boat at a distance of 5cm, and the temperature is raised to 350 ℃ by a program of 5 ℃/min under Ar atmosphere for heat treatment, and the temperature is kept for 120min, and then the final product is obtained by cooling.
Example 12
A preparation method of a porous CoO/CoP nanotube comprises the following steps:
1) synthesizing a linear cobalt-aspartic acid complex: a mixed solution (water: ethylene glycol volume ratio 1:1) was prepared, 3mmol of aspartic acid and 3mmol of Co (NO)3)2And 3mmol of NaOH are added to be dissolved in 36mL of the mixed solution, the mixed solution is stirred to be pink, and the mixed solution is transferred to a reaction kettle and reacted for 5 hours at 180 ℃. Centrifuging and vacuum drying to obtain pink powder, namely the linear cobalt-aspartic acid complex;
2) preparing porous CoO/CoP nanotubes: heating the pink powder prepared in the step 1) to 300 ℃ at a program of 0.5 ℃/min in an oxygen atmosphere for heat treatment, and keeping the temperature for 4 hours;
3) step 2) obtaining black powder Co3O4With sodium hypophosphite (mass: Co)3 O 420 times of) is arranged at the two ends of the porcelain boat at a distance of 5cmHeating to 350 ℃ by a program of 2 ℃/min under Ar atmosphere, carrying out heat treatment, keeping the temperature for 30min, and then cooling to obtain the final product.
The porous CoO/CoP nanotubes prepared in the above examples were physically characterized by means of TEM, SEM, XRD and the like. The prepared precursor was observed in a TEM and SEM spectrum (fig. 1 and 2) to have a linear structure. FIG. 3, TEM and SEM images after oxidation, showing Co3O4The hollow tubular structure of (1). From FIG. 4, XRD spectrum shows that the diffraction peak of the catalyst can be associated with Co3O4The standard cards of (3) are matched. FIG. 5, TEM image, shows the hollow tubular structure of the catalyst after phosphorization, showing the homogeneous CoO and CoP distribution and the interface interpenetration of the heterostructure. From fig. 6, the XRD pattern shows that the diffraction peaks of the catalyst can be matched with the standard cards of CoO and CoP. Finally, the prepared flower porous CoO/CoP nanotubes were applied to the HER reaction using commercial 20% Pt/C as a reference catalyst. FIG. 7 is a comparison of HER performance at 10mA cm for two catalysts-2The overpotential of the porous CoO/CoP nanotube is 65mV, which is better than that of pure phase CoP, namely 92 mV. Fig. 8 shows that the overpotential changes only slightly after the 1000-cycle accelerated durability stability test.
Claims (3)
1. A preparation method of a porous CoO/CoP nanotube is characterized by comprising the steps of preparing a cobalt-aspartic acid complex in advance through solvothermal reaction by using cobalt salt as a metal source and aspartic acid as a coordination agent, calcining and oxidizing the cobalt-aspartic acid complex, and then carrying out phosphating treatment to obtain the porous CoO/CoP nanotube; the cobalt salt is selected from Co (NO)3)2And CoCl2One or two of them; the solvothermal reaction is carried out by adding aspartic acid, cobalt salt and sodium hydroxide into a mixed solution of water and ethylene glycol, uniformly mixing, and carrying out solvothermal reaction at 140-200 ℃ for 4-10 h; in the mixed solution of water and ethylene glycol, the volume ratio of water to ethylene glycol is (0.1-99): 1; the molar ratio of the aspartic acid to the cobalt salt to the sodium hydroxide is (0.01-1): (0.01-1): (0.01 to 1); the calcination oxidation is carried out by subjecting the linear cobalt-aspartic acid complex to an oxygen atmosphereHeating to 300-400 ℃ in a heating mode, keeping for 3-8h, and calcining and oxidizing; the rate of temperature programming during calcination and oxidation is 0.5-10 ℃/min; the phosphating treatment is to heat a calcined and oxidized product and sodium hypophosphite to 300-350 ℃ in an inert atmosphere in a temperature programming manner, and keep the temperature for 20-80min for phosphating; the inert atmosphere comprises Ar and Ar/H2、N2At least one of; and the rate of temperature programmed rise during the phosphating treatment is 1-20 ℃/min.
2. A porous CoO/CoP nanotube prepared by the process of claim 1.
3. Use of the porous CoO/CoP nanotubes of claim 2 as a catalyst for hydrogen evolution reactions.
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