CN111437845A - Co9S8Oxygen evolution catalyst of/CoP nano rod-porous hollow carbon nano fiber and preparation method thereof - Google Patents
Co9S8Oxygen evolution catalyst of/CoP nano rod-porous hollow carbon nano fiber and preparation method thereof Download PDFInfo
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- CN111437845A CN111437845A CN202010364526.3A CN202010364526A CN111437845A CN 111437845 A CN111437845 A CN 111437845A CN 202010364526 A CN202010364526 A CN 202010364526A CN 111437845 A CN111437845 A CN 111437845A
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 239000002073 nanorod Substances 0.000 claims abstract description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 15
- 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 abstract description 11
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000008247 solid mixture Substances 0.000 claims description 2
- 238000010041 electrostatic spinning Methods 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 239000012265 solid product Substances 0.000 claims 2
- 238000009987 spinning Methods 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012792 core layer Substances 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 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 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- 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
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- Materials Engineering (AREA)
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of oxygen evolution reaction catalysts, and discloses Co9S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst comprises the following formula raw materials and components: sodium hypophosphite, Co9S8Nanorods, polymethyl methacrylate, polyacrylonitrile copolymer, and polyvinylpyrrolidone. Such a Co9S8CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst, Co9S8The nano rod has larger specific surface area, polymethyl methacrylate is used as an inner core layer, polyacrylonitrile copolymer is used as an outer shell layer, polyvinylpyrrolidone is used as a pore-foaming agent, and hydrogen is used asPotassium oxide as activator to obtain Co9S8The nano-rod-porous hollow carbon nanofiber has excellent conductivity, rich pore structure, full contact and infiltration with electrolyte and provides a transmission channel for electrons, and sodium hypophosphite and part of Co under the action of high temperature9S8Formation of CoP, Co9S8And CoP as a synergistic electrocatalytic active center, showing excellent oxygen evolution activity.
Description
Technical Field
The invention relates to the technical field of oxygen evolution reaction catalysts, in particular to Co9S8A/CoP nano rod-porous hollow carbon nano fiber oxygen evolution catalyst and a preparation method thereof.
Background
The hydrogen energy is a clean energy with high heat value, cleanness and reproducibility, and the hydrogen production by electrolyzing water is green, environment-friendly and efficientThe method is characterized in that the anode oxygen evolution reaction for hydrogen production by water electrolysis is a kinetic slow reaction, the oxygen evolution overpotential is large, an oxygen evolution catalyst with low anode overpotential and high electrochemical stability needs to be added to improve the efficiency of electrochemical oxygen evolution and hydrogen production, and the existing oxygen evolution catalyst mainly comprises RuO2And IrO2And the like, and therefore, development of an oxygen evolution catalyst with low cost and high electrochemical activity becomes a research hotspot.
Transition metal oxides such as Co3O4、MnO2(ii) a Transition metal sulfide MoS2、Co9S8Etc.; the transition metal phosphide such as CoP, NiP and the like has good electrochemical oxygen evolution activity by the front surface, but Co9S8CoP and NiP have poor electronic conductivity and poor conductivity, and Co9S8The specific surface area of the catalyst is not high, the electrochemical active center is insufficient, and Co is limited9S8And (3) practical application of the oxygen evolution catalyst.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a Co9S8/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst and a preparation method thereof, and solves the problem of Co9S8The oxygen evolution catalyst has the problems of low specific surface area, poor conductivity and the like.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: co9S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst comprises the following raw materials and components: sodium hypophosphite and Co with the mass ratio of 5-15:2-5:25-40:1009S8Nanorods, polymethyl methacrylate, polyacrylonitrile copolymer, and polyvinylpyrrolidone.
Preferably, said Co9S8The preparation method of the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst comprises the following steps:
(1) adding N, N-dimethylformamide solvent, cobalt chloride and cysteine at a mass ratio of 1:1.2-1.5 into a reaction bottle, stirring at 30-40 deg.C for 10-15 hr to form sol, and dissolvingFully drying the colloidal product, placing the colloidal product in an atmosphere tube type resistance furnace, heating the colloidal product to 580-8 ℃/min and 620 ℃, and performing heat preservation and calcination for 30-60min to obtain Co9S8And (4) nanorods.
(2) Adding distilled water solvent, acrylonitrile, methyl acrylate and itaconic acid into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 40-60 ℃, slowly adding initiator azobisisobutyronitrile, stirring at a constant speed for reaction for 1-3h, centrifugally separating the solution by using distilled water and ethanol, and washing to prepare the polyacrylonitrile copolymer.
(3) Adding N, N-dimethylformamide solvent and Co into a reaction bottle9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring at a constant speed for 12-18h to form a spinning solution, carrying out an electrostatic spinning process on the spinning solution by an electrostatic spinning method at a spinning flow rate of 5-8m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 300-350 ℃ at a heating rate of 2-8 ℃/min in an air atmosphere, carrying out heat preservation treatment for 2-3h, introducing argon gas at a heating rate of 5-10 ℃/min, heating to 950-1000 ℃ and carrying out heat preservation calcination for 1-1.5h, thus obtaining the hollow carbon nanofiber-coated Co-coated hollow carbon nanofiber9S8And (4) nanorods.
(4) Adding distilled water solvent and hollow carbon nanofiber-coated Co into a reaction bottle9S8Stirring the nano-rod and the potassium hydroxide at a constant speed for 12-24h, drying the solution in vacuum to remove the solvent, placing the solid mixed product in an atmosphere tubular resistance furnace, heating to 750-850 ℃ at a heating rate of 5-10 ℃/min in an argon atmosphere, carrying out heat preservation and calcination for 30-60min, washing the solid product with distilled water until the solid product is neutral, and preparing to obtain Co9S8Nanorod-porous hollow carbon nanofibers.
(5) Adding distilled water solvent and Co into a reaction bottle9S8Uniformly dispersing nano rod-porous hollow carbon nano fiber and sodium hypophosphite by ultrasonic, uniformly stirring for 12-24h at a constant speed, fully drying the solution, placing the solid mixture in an atmosphere tube type resistance furnace, heating to 600-700 ℃ at the heating rate of 5-10 ℃/min in the argon atmosphere, and carrying out heat preservation and calcination for 2-3h to prepare the Co-based composite material9S8the/CoP nano rod-porous hollow carbon nano fiber oxygen evolution catalyst.
Preferably, the atmosphere tube resistance furnace in the step (1) comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the surface in the calcining furnace, a rotating ball is movably connected to the supporting block, the rotating ball is movably connected to a rotating air tube, an air tube hole is formed in the surface of the rotating air tube, an air channel is formed in the rotating air tube, and an air vent is formed in the surface of the air channel.
Preferably, the acrylonitrile, the methyl acrylate, the itaconic acid and the azobisisobutyronitrile in the step (2) are 100:5-10:1-3: 0.5-0.8.
Preferably, the hollow carbon nanofibers in step (4) are Co-coated9S8The mass ratio of the nano rod to the potassium hydroxide is 1: 3-5.
Preferably, Co is used in said step (5)9S8The mass ratio of the nanorod-porous hollow carbon nanofiber to the sodium hypophosphite is 10: 1-3.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
such a Co9S8CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst, Co9S8The nano-rod has larger specific surface area, a large number of electrochemical active sites can be exposed, polymethyl methacrylate is used as an inner core layer, polyacrylonitrile copolymer is used as an outer shell layer, carbon-oxygen single bonds in polyacrylonitrile copolymer molecular chains are oxidized into carbonyl and ester bonds with higher thermal stability under the chemical action of oxygen in the high-temperature activation process, the polyacrylonitrile copolymer of the outer shell layer forms a carbon layer in the high-temperature calcination process, the polymethyl methacrylate of the inner core layer has poorer thermal stability, high-temperature cracking escapes from the carbon layer, a large number of hollow structures are formed in the carbon layer, polyvinylpyrrolidone is used as a pore-forming agent, and potassium hydroxide is used as an activating agent to prepare Co9S8The nano rod-porous hollow carbon nano fiber has excellent conductive performance and rich poresThe gap structure and the huge specific surface area not only fully contact and infiltrate the electrolyte, but also provide a transmission channel for electrons, and sodium hypophosphite is used as a phosphorus source to react with part of Co under the action of high temperature9S8Formation of CoP to form Co9S8CoP nanorod-porous hollow carbon nanofiber, Co9S8And the CoP nano rod is used as a synergistic electrocatalytic active center, and shows lower oxygen evolution overpotential and excellent oxygen evolution activity.
Drawings
FIG. 1 is a schematic front view of a calciner;
FIG. 2 is an enlarged schematic view of the airway;
FIG. 3 is a schematic view of rotational airway adjustment;
FIG. 4 is a schematic top view of the rotating trachea;
FIG. 5 is Co9S8Scanning electron microscope SEM image of the nano rod;
FIG. 6 is Co9S8TEM image of transmission electron microscope of/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst.
1-a calciner; 2-calcining the crucible; 3-a support block; 4-rotating the ball; 5-rotating the air pipe; 6-trachea holes; 7-air passage; 8-trachea holes.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: co9S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst comprises the following raw materials and components: sodium hypophosphite and Co with the mass ratio of 5-15:2-5:25-40:1009S8Nanorods, polymethyl methacrylate, polyacrylonitrile copolymer, and polyvinylpyrrolidone.
Co9S8The preparation method of the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst comprises the following steps:
(1) adding N, N-dimethylformamide solvent, cobalt chloride and cysteine at a mass ratio of 1:1.2-1.5 into a reaction bottle, stirring at 30-40 deg.C for 10-15 hr to form sol, drying the sol product, placing in an atmosphere tubular resistance furnace, and performing atmosphere tubular electric heatingThe blocking furnace comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the surface in the calcining furnace, a rotating ball is movably connected to the supporting block, a rotating air pipe is movably connected to the rotating ball, an air pipe hole is formed in the surface of the rotating air pipe, an air channel is arranged in the rotating air pipe, an air hole is formed in the surface of the air channel, the heating rate is 2-8 ℃/min, the temperature is raised to 580-620 ℃, the temperature is kept for calcining for 30-60min, and the prepared Co is9S8And (4) nanorods.
(2) Adding distilled water solvent, acrylonitrile, methyl acrylate and itaconic acid into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating the reaction bottle to 40-60 ℃, slowly adding an initiator azobisisobutyronitrile with the mass ratio of 100:5-10:1-3:0.5-0.8, stirring the mixture at a constant speed for reaction for 1-3h, centrifugally separating and washing the solution by using distilled water and ethanol, and preparing the polyacrylonitrile copolymer.
(3) Adding N, N-dimethylformamide solvent and Co into a reaction bottle9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring at a constant speed for 12-18h to form a spinning solution, carrying out an electrostatic spinning process on the spinning solution by an electrostatic spinning method at a spinning flow rate of 5-8m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 300-350 ℃ at a heating rate of 2-8 ℃/min in an air atmosphere, carrying out heat preservation treatment for 2-3h, introducing argon gas at a heating rate of 5-10 ℃/min, heating to 950-1000 ℃ and carrying out heat preservation calcination for 1-1.5h, thus obtaining the hollow carbon nanofiber-coated Co-coated hollow carbon nanofiber9S8And (4) nanorods.
(4) Adding distilled water solvent and hollow carbon nanofiber-coated Co into a reaction bottle9S8The mass ratio of the nanorod to the potassium hydroxide is 1:3-5, the solution is stirred at a constant speed for 12-24h, the solvent is removed by vacuum drying, the solid mixed product is placed in an atmosphere tube type resistance furnace, the temperature rise rate is 5-10 ℃/min in the argon atmosphere, the temperature rises to 750 ℃ and 850 ℃, the heat preservation and calcination are carried out for 30-60min, the solid product is washed by distilled water until the solid product is neutral, and the Co is prepared9S8Nanorod-porous hollow carbon nanofibers.
(5) Adding distilled water into a reaction bottleAgent, Co9S8The mass ratio of the nano rod to the porous hollow carbon nano fiber to the sodium hypophosphite is 10:1-3, the mixture is uniformly dispersed by ultrasonic, stirred at a constant speed for 12-24h, the solution is fully dried, the solid mixture is placed in an atmosphere tube type resistance furnace, the temperature rise rate is 5-10 ℃/min in the argon atmosphere, the temperature rises to 600 ℃ and 700 ℃, and the heat preservation and calcination are carried out for 2-3h, so that the Co-doped carbon nano fiber/sodium hypophosphite is prepared9S8the/CoP nano rod-porous hollow carbon nano fiber oxygen evolution catalyst.
Example 1
(1) Adding N, N-dimethylformamide solvent, cobalt chloride and cysteine with the mass ratio of 1:1.2 into a reaction bottle, stirring at 30 ℃ for 10h at constant speed to form a sol, fully drying the sol product, placing the dried sol product into an atmosphere tubular resistance furnace, wherein the atmosphere tubular resistance furnace comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the inner surface of the calcining furnace, a rotating ball is movably connected to the supporting block, a rotating air pipe is movably connected to the rotating ball, an air pipe hole is arranged on the surface of the rotating air pipe, an air channel is arranged in the rotating air pipe, an air vent is arranged on the surface of the air channel, the heating rate is 2 ℃/min, heating is carried out to 580 ℃, keeping the temperature and calcining for 309S8And (4) nanorods.
(2) Adding distilled water solvent, acrylonitrile, methyl acrylate and itaconic acid into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating the reaction bottle to 40 ℃, slowly adding an initiator azobisisobutyronitrile with the mass ratio of 100:5:1:0.5, stirring at a constant speed for reaction for 1 hour, centrifugally separating and washing the solution by using distilled water and ethanol, and preparing the polyacrylonitrile copolymer.
(3) Adding an N, N-dimethylformamide solvent and Co with the mass ratio of 5:2:25:100 into a reaction bottle9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring at a constant speed for 12 hours to form a spinning solution, carrying out an electrostatic spinning process on the spinning solution by an electrostatic spinning method, wherein the spinning flow rate is 5m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 300 ℃ at the heating rate of 2 ℃/min in an air atmosphere, carrying out heat preservation treatment for 2 hours, then introducing argon gas, and the heating rate is 5Heating to 950 ℃ for 1h at a temperature of 950 ℃ per min, and calcining at the temperature to obtain the hollow carbon nanofiber-coated Co9S8And (4) nanorods.
(4) Adding distilled water solvent and hollow carbon nanofiber-coated Co into a reaction bottle9S8The mass ratio of the nanorod to the potassium hydroxide is 1:3, the solution is stirred at a constant speed for 12 hours, the solvent is removed by vacuum drying, the solid mixed product is placed in an atmosphere tubular resistance furnace, the temperature rise rate is 5 ℃/min in the argon atmosphere, the temperature is raised to 750 ℃, the heat preservation and calcination are carried out for 30 minutes, the solid product is washed by distilled water until the solid product is neutral, and the Co is prepared9S8Nanorod-porous hollow carbon nanofibers.
(5) Adding distilled water solvent and Co into a reaction bottle9S8The mass ratio of the nano rod to the porous hollow carbon nano fiber to the sodium hypophosphite is 10:1, the mixture is uniformly dispersed by ultrasonic, stirred at a constant speed for 12 hours, the solution is fully dried, the solid mixture is placed in an atmosphere tube type resistance furnace, the temperature is raised to 600 ℃ in the argon atmosphere at the temperature raising rate of 5 ℃/min, and the mixture is subjected to heat preservation and calcination for 2 hours to prepare the Co-containing material9S8a/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst material 1.
Example 2
(1) Adding N, N-dimethylformamide solvent and cobalt chloride and cysteine with the mass ratio of 1:1.3 into a reaction bottle, stirring at a constant speed for 15 hours at 30 ℃ to form a sol, fully drying the sol product, placing the dried sol product into an atmosphere tubular resistance furnace, wherein the atmosphere tubular resistance furnace comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the inner surface of the calcining furnace, a rotating ball is movably connected to the supporting block, a rotating air pipe is movably connected to the rotating ball, an air pipe hole is arranged on the surface of the rotating air pipe, an air channel is arranged in the rotating air pipe, an air vent is arranged on the surface of the air channel, the heating rate is 8 ℃/min, heating is carried out to 620 ℃, keeping the temperature and calcining for9S8And (4) nanorods.
(2) Adding distilled water solvent, acrylonitrile, methyl acrylate and itaconic acid into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating the reaction bottle to 50 ℃, slowly adding an initiator azobisisobutyronitrile with the mass ratio of 100:6:1.5:0.6, stirring at a constant speed for reaction for 3 hours, centrifugally separating and washing the solution by using distilled water and ethanol to prepare the polyacrylonitrile copolymer.
(3) Adding N, N-dimethylformamide solvent and Co with the mass ratio of 8:3:30:100 into a reaction bottle9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring at a constant speed for 18h to form a spinning solution, carrying out an electrostatic spinning process on the spinning solution by an electrostatic spinning method, wherein the spinning flow rate is 5m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 350 ℃ at the heating rate of 8 ℃/min in the air atmosphere, carrying out heat preservation treatment for 3h, then introducing argon, heating to 1000 ℃ at the heating rate of 10 ℃/min, carrying out heat preservation calcination for 1.5h, and preparing the hollow carbon nanofiber-coated Co-coated hollow carbon nanofiber9S8And (4) nanorods.
(4) Adding distilled water solvent and hollow carbon nanofiber-coated Co into a reaction bottle9S8The mass ratio of the nanorod to the potassium hydroxide is 1:4, stirring at a constant speed for 18h, vacuum-drying the solution to remove the solvent, placing the solid mixed product in an atmosphere tubular resistance furnace, heating to 850 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, carrying out heat preservation and calcination for 60min, washing the solid product with distilled water until the solid product is neutral, and preparing to obtain Co9S8Nanorod-porous hollow carbon nanofibers.
(5) Adding distilled water solvent and Co into a reaction bottle9S8The mass ratio of the nano rod to the porous hollow carbon nano fiber to the sodium hypophosphite is 10:1.5, the mixture is uniformly dispersed by ultrasonic, stirred at a constant speed for 15 hours, the solution is fully dried, the solid mixture is placed in an atmosphere tube type resistance furnace, the temperature rise rate is 10 ℃/min, the temperature is raised to 700 ℃ in the argon atmosphere, the heat preservation and calcination are carried out for 3 hours, and the Co is prepared9S8a/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst material 2.
Example 3
(1) Adding N, N-dimethylformamide solvent, cobalt chloride and cysteine at a mass ratio of 1:1.4 into a reaction bottle, stirring at 35 deg.C for 12 hr to obtain sol, and mixingFully drying the product, placing the product in an atmosphere tubular resistance furnace, wherein the atmosphere tubular resistance furnace comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the surface in the calcining furnace, a rotating ball is movably connected to the supporting block, the rotating ball is movably connected to a rotating air pipe, an air pipe hole is formed in the surface of the rotating air pipe, an air passage is formed in the rotating air pipe, an air hole is formed in the surface of the air passage, the heating rate is 5 ℃/min, the temperature is increased to 600 ℃, keeping the temperature and calcining for 45min9S8And (4) nanorods.
(2) Adding distilled water solvent, acrylonitrile, methyl acrylate and itaconic acid into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating the reaction bottle to 50 ℃, slowly adding an initiator azobisisobutyronitrile with the mass ratio of 100:8:2.5:0.7, stirring at a constant speed for reaction for 2 hours, centrifugally separating and washing the solution by using distilled water and ethanol to prepare the polyacrylonitrile copolymer.
(3) Adding an N, N-dimethylformamide solvent and Co with the mass ratio of 12:4:35:100 into a reaction bottle9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring at a constant speed for 18h to form a spinning solution, carrying out an electrostatic spinning process on the spinning solution by an electrostatic spinning method, wherein the spinning flow rate is 5m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 350 ℃ at the heating rate of 8 ℃/min in the air atmosphere, carrying out heat preservation treatment for 3h, then introducing argon, heating to 950 ℃ at the heating rate of 10 ℃/min, carrying out heat preservation calcination for 1h, and preparing the hollow carbon nanofiber-coated Co-coated hollow carbon nanofiber9S8And (4) nanorods.
(4) Adding distilled water solvent and hollow carbon nanofiber-coated Co into a reaction bottle9S8The mass ratio of the nanorod to the potassium hydroxide is 1:4.5, stirring at a constant speed for 18h, vacuum-drying the solution to remove the solvent, placing the solid mixed product in an atmosphere tubular resistance furnace, heating to 800 ℃ at a heating rate of 8 ℃/min in an argon atmosphere, keeping the temperature and calcining for 45min, washing the solid product with distilled water until the solid product is neutral, and preparing to obtain the Co/KOH/Al/Si/Al/9S8Nanorod-porous hollow carbon nanofibers.
(5) Adding distilled water solvent and Co into a reaction bottle9S8The mass ratio of the nano rod to the porous hollow carbon nano fiber to the sodium hypophosphite is 10:2.5, the mixture is uniformly dispersed by ultrasonic, stirred at a constant speed for 18 hours, the solution is fully dried, the solid mixture is placed in an atmosphere tube type resistance furnace, the temperature rise rate is 8 ℃/min in the argon atmosphere, the temperature is raised to 650 ℃, the heat preservation and the calcination are carried out for 2.5 hours, and the Co is prepared9S8a/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst material 3.
Example 4
(1) Adding N, N-dimethylformamide solvent, cobalt chloride and cysteine with the mass ratio of 1:1.5 into a reaction bottle, stirring at a constant speed for 15 hours at 40 ℃ to form a sol, fully drying the sol product, placing the dried sol product into an atmosphere tubular resistance furnace, wherein the atmosphere tubular resistance furnace comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the inner surface of the calcining furnace, a rotating ball is movably connected to the supporting block, a rotating air pipe is movably connected to the rotating ball, an air pipe hole is arranged on the surface of the rotating air pipe, an air channel is arranged in the rotating air pipe, an air vent is arranged on the surface of the air channel, the heating rate is 8 ℃/min, heating is carried out to 620 ℃, keeping the temperature and calcining for9S8And (4) nanorods.
(2) Adding distilled water solvent, acrylonitrile, methyl acrylate and itaconic acid into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating the reaction bottle to 60 ℃, slowly adding an initiator azobisisobutyronitrile with the mass ratio of 100:10:3:0.8, stirring at a constant speed for reaction for 3 hours, centrifugally separating and washing the solution by using distilled water and ethanol to prepare the polyacrylonitrile copolymer.
(3) Adding an N, N-dimethylformamide solvent and Co with the mass ratio of 15:5:40:100 into a reaction bottle9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring at a constant speed for 18h to form a spinning solution, carrying out an electrostatic spinning process on the spinning solution by an electrostatic spinning method at a spinning flow rate of 8m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 350 ℃ at a heating rate of 8 ℃/min in an air atmosphere, carrying out heat preservation treatment for 3h, and then carrying out heat preservation treatment on the obtained productThen introducing argon, raising the temperature to 1000 ℃ at the rate of 10 ℃/min, and carrying out heat preservation and calcination for 1.5h to obtain the hollow carbon nanofiber-coated Co9S8And (4) nanorods.
(4) Adding distilled water solvent and hollow carbon nanofiber-coated Co into a reaction bottle9S8The mass ratio of the nanorod to the potassium hydroxide is 1:5, stirring at a constant speed for 24h, vacuum-drying the solution to remove the solvent, placing the solid mixed product in an atmosphere tubular resistance furnace, heating to 850 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, carrying out heat preservation and calcination for 60min, washing the solid product with distilled water until the solid product is neutral, and preparing to obtain Co9S8Nanorod-porous hollow carbon nanofibers.
(5) Adding distilled water solvent and Co into a reaction bottle9S8The mass ratio of the nano rod to the porous hollow carbon nano fiber to the sodium hypophosphite is 10:3, the mixture is uniformly dispersed by ultrasonic and then stirred at a constant speed for 24 hours, the solution is fully dried, the solid mixture is placed in an atmosphere tube type resistance furnace, the temperature rise rate is 10 ℃/min in the argon atmosphere, the temperature is raised to 700 ℃, the heat preservation and calcination are carried out for 3 hours, and the Co is prepared9S8a/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst material 4.
Comparative example 1
(1) Adding N, N-dimethylformamide solvent and cobalt chloride and cysteine with the mass ratio of 1:1 into a reaction bottle, stirring at 30 ℃ for 15 hours at constant speed to form a sol, fully drying the sol product, placing the dried sol product into an atmosphere tubular resistance furnace, wherein the atmosphere tubular resistance furnace comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the inner surface of the calcining furnace, a rotating ball is movably connected to the supporting block, a rotating air pipe is movably connected to the rotating ball, an air pipe hole is arranged on the surface of the rotating air pipe, an air channel is arranged in the rotating air pipe, an air vent is arranged on the surface of the air channel, the heating rate is 8 ℃/min, heating is carried out to 600 ℃, keeping the temperature and calcining for 459S8And (4) nanorods.
(2) Adding distilled water solvent, acrylonitrile, methyl acrylate and itaconic acid into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating the reaction bottle to 40 ℃, slowly adding an initiator azobisisobutyronitrile with the mass ratio of 100:4:0.5:1, stirring at a constant speed for reaction for 3 hours, centrifugally separating and washing the solution by using distilled water and ethanol, and preparing the polyacrylonitrile copolymer.
(3) Adding an N, N-dimethylformamide solvent and Co with the mass ratio of 3:1.5:20:100 into a reaction bottle9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring at a constant speed for 12 hours to form a spinning solution, carrying out an electrostatic spinning process on the spinning solution by an electrostatic spinning method, wherein the spinning flow rate is 8m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 350 ℃ at the heating rate of 2 ℃/min in the air atmosphere, carrying out heat preservation treatment for 3 hours, then introducing argon, heating to 1000 ℃ at the heating rate of 10 ℃/min, carrying out heat preservation calcination for 1 hour, and preparing the hollow carbon nanofiber-coated Co-coated hollow carbon nanofiber9S8And (4) nanorods.
(4) Adding distilled water solvent and hollow carbon nanofiber-coated Co into a reaction bottle9S8The mass ratio of the nanorod to the potassium hydroxide is 1:6, stirring at a constant speed for 24h, vacuum-drying the solution to remove the solvent, placing the solid mixed product in an atmosphere tubular resistance furnace, heating to 750 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, calcining at a heat preservation time of 60min, washing the solid product with distilled water until the solid product is neutral, and preparing to obtain Co9S8Nanorod-porous hollow carbon nanofibers.
(5) Adding distilled water solvent and Co into a reaction bottle9S8The mass ratio of the nano rod to the porous hollow carbon nano fiber to the sodium hypophosphite is 10:4, the mixture is uniformly dispersed by ultrasonic, stirred at a constant speed for 20 hours, the solution is fully dried, the solid mixture is placed in an atmosphere tube type resistance furnace, the temperature is raised to 700 ℃ in the argon atmosphere at the temperature raising rate of 10 ℃/min, and is subjected to heat preservation and calcination for 3 hours to prepare the Co-containing material9S8Comparative material 1 of/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst.
Co in examples and comparative examples was used9S8Placing the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst in an ethanol solvent, adding Nafion solution respectively, and mixingAnd uniformly coating the slurry on the surface of a glassy carbon electrode and drying to prepare a working electrode, taking a platinum sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking a 1 mol/L potassium hydroxide solution as an electrolyte, and carrying out an electrochemical oxygen evolution performance test in a CHI760D electrochemical workstation by using a three-electrode system, wherein the test standard is GB/T26800-2011.
In summary, the one Co9S8CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst, Co9S8The nano-rod has larger specific surface area, a large number of electrochemical active sites can be exposed, polymethyl methacrylate is used as an inner core layer, polyacrylonitrile copolymer is used as an outer shell layer, carbon-oxygen single bonds in polyacrylonitrile copolymer molecular chains are oxidized into carbonyl and ester bonds with higher thermal stability under the chemical action of oxygen in the high-temperature activation process, the polyacrylonitrile copolymer of the outer shell layer forms a carbon layer in the high-temperature calcination process, the polymethyl methacrylate of the inner core layer has poorer thermal stability, high-temperature cracking escapes from the carbon layer, a large number of hollow structures are formed in the carbon layer, polyvinylpyrrolidone is used as a pore-forming agent, and potassium hydroxide is used as an activating agent to prepare Co9S8The nano rod-porous hollow carbon nano fiber has excellent conductivity, rich pore structure and huge specific surface area, is fully contacted and infiltrated with electrolyte, provides a transmission channel for electrons, takes sodium hypophosphite as a phosphorus source, and is partially contacted with Co under the action of high temperature9S8Formation of CoP to form Co9S8CoP nanorod-porous hollow carbon nanofiber, Co9S8And the CoP nano rod is used as a synergistic electrocatalytic active center, and shows lower oxygen evolution overpotential and excellent oxygen evolution activity.
Claims (6)
1. Co9S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst comprises the following raw materials and components, and is characterized in that: sodium hypophosphite and Co with the mass ratio of 5-15:2-5:25-40:1009S8Nanorods, polymethyl methacrylate, polyacrylonitrile copolymer, and polyvinylpyrrolidone.
2. Co according to claim 19S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst is characterized in that: the Co9S8The preparation method of the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst comprises the following steps:
(1) adding cobalt chloride and cysteine with the mass ratio of 1:1.2-1.5 into N, N-dimethylformamide solvent, stirring at 30-40 ℃ for 10-15h to form sol, fully drying the sol product, placing the sol product into an atmosphere tubular resistance furnace, heating at the rate of 2-8 ℃/min to 580-620 ℃, and carrying out heat preservation and calcination for 30-60min to prepare Co9S8A nanorod;
(2) adding acrylonitrile, methyl acrylate and itaconic acid into a distilled water solvent, heating to 40-60 ℃, slowly adding an initiator azobisisobutyronitrile, reacting for 1-3h, centrifugally separating and washing to prepare a polyacrylonitrile copolymer;
(3) adding Co to N, N-dimethylformamide solvent9S8Carrying out ultrasonic dispersion treatment on nano rods, polymethyl methacrylate, polyacrylonitrile copolymer and polyvinylpyrrolidone, stirring for 12-18h to form a spinning solution, carrying out an electrostatic spinning process by an electrostatic spinning method, wherein the spinning flow rate is 5-8m L/h, placing an electrostatic spinning precursor in an atmosphere resistance furnace, heating to 350 ℃ at the heating rate of 2-8 ℃/min in the air atmosphere, carrying out heat preservation treatment for 2-3h, introducing argon gas at the heating rate of 5-10 ℃/min, heating to 1000 ℃ at the heating rate of 950-9S8A nanorod;
(4) adding hollow carbon nanofiber coated Co into distilled water solvent9S8Stirring the nano-rod and potassium hydroxide for 12-24h, drying in vacuum to remove the solvent, placing the solid mixed product in an atmosphere tubular resistance furnace, heating to 750-850 ℃ at the heating rate of 5-10 ℃/min in the argon atmosphere, carrying out heat preservation and calcination for 30-60min, washing the solid product with distilled water until the solid product is neutral, and preparing to obtain Co9S8Nanorod-porous hollow carbon nanofibers;
(5) adding Co to distilled water solvent9S8Uniformly dispersing the nano-rod-porous hollow carbon nano-fiber and sodium hypophosphite by ultrasonic, stirring for 12-24h, placing the solid mixture in an atmosphere tube type resistance furnace, heating to 600-700 ℃ at the heating rate of 5-10 ℃/min in the argon atmosphere, and carrying out heat preservation and calcination for 2-3h to obtain Co9S8the/CoP nano rod-porous hollow carbon nano fiber oxygen evolution catalyst.
3. Co according to claim 29S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst is characterized in that: the atmosphere tube type resistance furnace in the step (1) comprises a calcining furnace, a calcining crucible is arranged in the calcining chamber, a supporting block is fixedly connected to the surface in the calcining furnace, a rotating ball is movably connected to the supporting block, a rotating air pipe is movably connected to the rotating ball, an air pipe hole is formed in the surface of the rotating air pipe, an air passage is formed in the rotating air pipe, and an air vent is formed in the surface of the air passage.
4. Co according to claim 29S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst is characterized in that: the ratio of acrylonitrile to methyl acrylate to itaconic acid to azobisisobutyronitrile in the step (2) is 100:5-10:1-3: 0.5-0.8.
5. Co according to claim 29S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst is characterized in that: the hollow carbon nanofiber coated with Co in the step (4)9S8The mass ratio of the nano rod to the potassium hydroxide is 1: 3-5.
6. Co according to claim 29S8the/CoP nanorod-porous hollow carbon nanofiber oxygen evolution catalyst is characterized in that: co in the step (5)9S8The mass ratio of the nanorod-porous hollow carbon nanofiber to the sodium hypophosphite is 10: 1-3.
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| CN114481368A (en) * | 2022-02-14 | 2022-05-13 | 南方科技大学 | Hollow carbon nanofiber and preparation method thereof |
| CN117535677A (en) * | 2023-09-27 | 2024-02-09 | 暨南大学 | N, P Co-doped Co 9 S 8 Integrated water decomposition electrocatalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114481368A (en) * | 2022-02-14 | 2022-05-13 | 南方科技大学 | Hollow carbon nanofiber and preparation method thereof |
| CN114481368B (en) * | 2022-02-14 | 2023-11-28 | 南方科技大学 | Hollow carbon nanofiber and preparation method thereof |
| CN117535677A (en) * | 2023-09-27 | 2024-02-09 | 暨南大学 | N, P Co-doped Co 9 S 8 Integrated water decomposition electrocatalyst and preparation method and application thereof |
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