CN111450830B - Nano CoFe2O4Oxygen reduction catalyst loaded with nitrogen-doped porous carbon and preparation method thereof - Google Patents
Nano CoFe2O4Oxygen reduction catalyst loaded with nitrogen-doped porous carbon 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 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 22
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 239000001301 oxygen Substances 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910003321 CoFe Inorganic materials 0.000 claims description 8
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- 239000003999 initiator Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 7
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- 239000011148 porous material Substances 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 abstract description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- 230000018109 developmental process Effects 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
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- 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
- 230000007547 defect Effects 0.000 description 1
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000926 separation method Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
The invention relates to the technical field of oxygen reduction catalysts, and discloses an oxygen reduction catalyst of nitrogen-doped porous carbon loaded with nano CoFe2O4, which comprises the following formula raw materials and components: chitosan, carboxylated polystyrene microsphere, CoFe2O4Porous nanowires. The nanometer CoFe2O4An oxygen reduction catalyst loaded with nitrogen-doped porous carbon, which takes glucose as a soft template, urotropine as a precipitator and CoFe2O4The porous nano-wire has rich electrochemical active centers, and the polystyrene microspheres are uniformly modified among the chitosan to form an interpenetrating network and then are mixed with the CoFe2O4The porous nanowires are compounded, and the nitrogen-doped porous carbon is prepared by high-temperature thermal cracking, has rich porous structure and large specific surface area, the graphite nitrogen is favorable for enhancing the conductivity of the porous carbon, and the pyridine nitrogen can be used as an active site for oxygen reduction catalysis, namely CoFe2O4The porous nanowires are uniformly dispersed in a matrix and a pore structure of the porous carbon material, and show excellent oxygen reduction catalytic performance.
Description
Technical Field
The invention relates to the technical field of oxygen reduction catalysts, in particular to nano CoFe2O4An oxygen reduction catalyst loaded with nitrogen-doped porous carbon and a preparation method thereof.
Background
In recent years, the environmental pollution problem is becoming more severe, the energy crisis problem is also becoming more severe, and the development of new and efficient energy storage and conversion devices, such as fuel cells, lithium ion batteries, supercapacitors, etc., is required, from the viewpoint of energy conservation and ecological environment protection, fuel cells are the most promising power generation technology, and whether the Oxygen Reduction Reaction (ORR) of the cathode can be performed efficiently determines the conversion efficiency of the fuel cells.
The prior oxygen reduction catalyst mainly comprises a platinum-based noble metal catalyst, a Fe-N-C catalyst, a carbon-based non-metal catalyst and the like. Wherein the transition metal oxide is, for example, MnO2、Co3O4、NiCo2O4、CoFe2O4Etc. has good catalytic activity, is cheap and easy to obtain,is an oxygen reduction catalyst with great development potential, but CoFe2O4The poor conductivity and insufficient electrochemical active center lead to insufficient utilization of electrochemical performance, and limit CoFe2O4Development of oxygen reduction catalysts.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides nano CoFe2O4The oxygen reduction catalyst of the loaded nitrogen-doped porous carbon and the preparation method thereof solve the problem of CoFe2O4Poor conductivity and electrochemically active center problems of oxygen reduction catalysts.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: nano CoFe2O4The oxygen reduction catalyst loaded with nitrogen-doped porous carbon comprises the following raw materials and components: chitosan, carboxylated polystyrene microsphere, CoFe2O4The mass ratio of the porous nano-wire is 10:3-6: 20-45.
Preferably, the nano CoFe2O4The preparation method of the oxygen reduction catalyst loaded with nitrogen-doped porous carbon comprises the following steps:
(1) adding a mixed solvent of distilled water and glycol, ferric chloride, cobalt chloride, urotropine and glucose into a reaction bottle, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a reaction kettle heating box, heating to 180 ℃ for reaction for 10-18h, centrifugally separating to remove the solvent, washing a solid precursor product by using distilled water and ethanol in sequence, drying, placing the solid precursor product in a muffle furnace, heating to 350 ℃ at the rate of 2-5 ℃/min, carrying out heat preservation treatment for 1-2h, heating to 550 ℃ at the rate of 500 ℃ for heat preservation and calcining for 2-4h, and preparing the CoFe2O4Porous nanowires.
(2) Introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid, uniformly stirring, introducing nitrogen into a reaction bottle B, adding the ethanol solvent, styrene with the mass ratio of 10:2-2.5:0.6-1:0.25-0.4, polyvinylpyrrolidone serving as a stabilizer, triton X-100 serving as a surfactant and azodiisovaleronitrile serving as an initiator, placing the mixture into a water bath kettle, heating the mixture to 50-70 ℃, uniformly stirring the mixture for reaction for 1-1.5h, slowly dropwise adding the solution of the reaction bottle A into the reaction bottle B, controlling the total mass fraction of the solution to be 10-30%, reacting for 20-30h, distilling the solution under reduced pressure to remove the solvent, washing a solid product by using distilled water and ethanol, and drying to prepare the carboxylated polystyrene microsphere.
(3) Adding 2-4% acetic acid solution, chitosan, carboxylated polystyrene microsphere and CoFe2O4Stirring the porous nano-wire at a constant speed for 10-20h, standing and aging for 72-96 h, washing the solid mixed product to be neutral, placing the solid mixed product in an atmosphere resistance furnace, heating to 820-880 ℃ at a heating rate of 3-10 ℃/min in an argon atmosphere, and carrying out heat preservation and calcination for 2-3h to prepare the nano-CoFe2O4An oxygen reduction catalyst supporting nitrogen-doped porous carbon.
Preferably, the reation kettle heating cabinet includes heating device, the inside top fixedly connected with circulator of reation kettle heating cabinet, circulator and rotation axis swing joint, and rotation axis swing joint has the regulating ball, regulating ball and regulating spindle swing joint, regulating spindle and connector swing joint, and connector swing joint has the gag lever post, gag lever post and connection ball swing joint, connects ball swing joint and has the bracing piece, is provided with hydrothermal reaction kettle above the bracing piece.
Preferably, the mass ratio of the ferric chloride to the cobalt chloride to the urotropine to the glucose is 1:2:1-1.5: 15-30.
Preferably, the mass ratio of the styrene to the acrylic acid in the reaction bottle A is 10-15:1, and the mass ratio of the styrene to the reaction bottle A is 1: 1-1.5.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the nanometer CoFe2O4The oxygen reduction catalyst of the loaded nitrogen-doped porous carbon is prepared by taking glucose as a soft template and urotropine as a precipitator to obtain CoFe2O4The porous nano-wire has a large amount of mesoporous structures and can increase the electrochemical activityIonization of carboxyl group of core and carboxylated polystyrene microsphere to generate hydrogen ion to form COO-The negative ions and the hydrogen ions are combined with the amino group of the chitosan to generate NH3 +Positive ions improve the mutual attraction of the positive ions and the negative ions, so that the polystyrene microspheres are uniformly modified among the chitosan to form an interpenetrating network, and then the interpenetrating network is mixed with the CoFe2O4The porous nanowires are compounded, chitosan serves as a carbon source, carboxylated polystyrene microspheres serve as a pore-foaming agent, nitrogen-doped porous carbon is prepared through high-temperature thermal cracking, the porous carbon has rich pore structures and large specific surface area, the nitrogen is doped in the porous carbon material to form graphite nitrogen and pyridine nitrogen structures, the graphite nitrogen is favorable for enhancing the conductivity of the porous carbon, the pyridine nitrogen can serve as an active site for oxygen reduction catalysis, and CoFe2O4The porous nanowires are uniformly dispersed in the matrix and the pore structure of the porous carbon material, so that CoFe is reduced2O4The porous nanowires are agglomerated, and the pore structure promotes the wetting action of the catalyst and the electrolyte, so that the catalyst has excellent oxygen reduction catalytic performance under the synergistic action.
Drawings
FIG. 1 is a schematic front view of a reactor heating box;
FIG. 2 is an enlarged schematic view of the adjustment axis;
fig. 3 is a schematic view of adjustment of the adjustment shaft.
1. A reaction kettle heating box; 2. a heating device; 3. a rotator; 4. a rotating shaft; 5. adjusting the ball; 6. An adjustment shaft; 7. a connector; 8. a limiting rod; 9. a connecting ball; 10. a support bar; 11, a reaction kettle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: nano CoFe2O4The oxygen reduction catalyst loaded with nitrogen-doped porous carbon comprises the following raw materials and components: chitosan, carboxylated polystyrene microsphere, CoFe2O4The mass ratio of the porous nano-wire is 10:3-6: 20-45.
Nano CoFe2O4The preparation method of the oxygen reduction catalyst loaded with nitrogen-doped porous carbon comprises the following steps:
(1) adding a mixed solvent of distilled water and ethylene glycol, namely ferric chloride, cobalt chloride, urotropine and glucose in a mass ratio of 1:2:1-1.5:15-30 into a reaction bottle, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, wherein the reaction kettle heating box comprises a heating device, a rotator is fixedly connected above the interior of the reaction kettle heating box and movably connected with a rotating shaft, an adjusting ball is movably connected with the rotating shaft, the adjusting ball is movably connected with an adjusting shaft, the adjusting shaft is movably connected with a connector, a limiting rod is movably connected with a connecting ball, the connecting ball is movably connected with a supporting rod, the hydrothermal reaction kettle is arranged above the supporting rod, heating is carried out to 180 ℃, reacting for 10-18h, centrifugally separating the solvent, washing the solid precursor with distilled water and ethanol in sequence and drying the solid precursor, placing the solid precursor product in a muffle furnace, heating to 300-350 ℃ at the heating rate of 2-5 ℃/min, carrying out heat preservation treatment for 1-2h, heating to 500-550 ℃, carrying out heat preservation calcination for 2-4h, and preparing to obtain CoFe2O4Porous nanowires.
(2) Introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid in a mass ratio of 10-15:1, uniformly stirring, introducing nitrogen into a reaction bottle B, adding an ethanol solvent, styrene in a mass ratio of 10:2-2.5:0.6-1:0.25-0.4, a stabilizer polyvinylpyrrolidone, a surfactant Triton X-100 and an initiator azobisisovaleronitrile, wherein the mass ratio of the styrene in the reaction bottle A to the styrene in the reaction bottle B is 1:1-1.5, placing the mixture in a water bath kettle, heating to 50-70 ℃, uniformly stirring for reaction for 1-1.5h, slowly dropwise adding the solution in the reaction bottle B, controlling the total mass fraction of the solution to be 10-30%, reacting for 20-30h, removing the solvent by reduced pressure distillation, washing a solid product with distilled water and ethanol, drying, preparing the carboxylated polystyrene microspheres.
(3) Adding 2-4% acetic acid solution, chitosan, carboxylated polystyrene microsphere and CoFe2O4Stirring the porous nano-wire at a constant speed for 10-20h, standing and aging for 72-96 h, washing the solid mixed product to be neutral, placing the solid mixed product in an atmosphere resistance furnace, and heating at a rate of 3-10Heating to 820-880 ℃ in argon atmosphere at a temperature of between 2 and 3 hours, and calcining at the temperature to obtain the nano CoFe2O4An oxygen reduction catalyst supporting nitrogen-doped porous carbon.
Example 1
(1) Preparation of CoFe2O4Porous nanowire component 1: adding a mixed solvent of distilled water and ethylene glycol, namely ferric chloride, cobalt chloride, urotropine and glucose in a mass ratio of 1:2:1:15 into a reaction bottle, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a reaction kettle heating box, wherein the reaction kettle heating box comprises a heating device, a rotator is fixedly connected above the interior of the reaction kettle heating box and movably connected with a rotating shaft, an adjusting ball is movably connected with the rotating shaft, the adjusting ball is movably connected with an adjusting shaft, the adjusting shaft is movably connected with a connector, the connector is movably connected with a limiting rod, the limiting rod is movably connected with a connecting ball, a supporting rod is movably connected with the connecting ball, the hydrothermal reaction kettle is arranged above the supporting rod, heating is carried out to 150 ℃, reacting for 10 hours, centrifugally separating and removing the solvent, washing and drying the solid precursor product by using distilled water and ethanol in sequence, placing the solid precursor product into a muffle furnace, heating to 300 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 1h, heating to 500 ℃, carrying out heat preservation calcination for 2h, and preparing the CoFe2O4Porous nanowire component 1.
(2) Preparing a carboxylated polystyrene microsphere component 1: introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid in a mass ratio of 10:1, uniformly stirring, introducing nitrogen into a reaction bottle B, adding the ethanol solvent, styrene in a mass ratio of 10:2:0.6:0.25, polyvinylpyrrolidone serving as a stabilizer, triton X-100 serving as a surfactant and azodiisovaleronitrile serving as an initiator, placing the reaction bottle A and the reaction bottle B in a water bath kettle, heating to 50 ℃, uniformly stirring for reaction for 1h, slowly dropwise adding the solution of the reaction bottle A into the reaction bottle B, controlling the total mass fraction of the solution to be 10%, reacting for 20h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare a carboxylated polystyrene microsphere component 1.
(3) Preparation of Nano CoFe2O4Nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 1: adding 2 percent of acetic acid solution by mass into a reaction bottle, and adding chitosan, a carboxylated polystyrene microsphere component 1 and CoFe2O4The porous nanowire component 1 is prepared by uniformly stirring for 10h at a constant speed according to the mass ratio of 10:3:20, standing and aging for 72h, washing a solid mixed product to be neutral, placing the solid mixed product in an atmosphere resistance furnace, raising the temperature to 820-2O4A nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 1.
Example 2
(1) Preparation of CoFe2O4Porous nanowire component 2: adding a mixed solvent of distilled water and ethylene glycol, namely ferric chloride, cobalt chloride, urotropine and glucose in a mass ratio of 1:2:1.1:18 into a reaction bottle, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, wherein the reaction kettle heating box comprises a heating device, a rotator is fixedly connected above the interior of the reaction kettle heating box and movably connected with a rotating shaft, an adjusting ball is movably connected with the rotating shaft, the adjusting ball is movably connected with an adjusting shaft, the adjusting shaft is movably connected with a connector, the connector is movably connected with a limiting rod, the limiting rod is movably connected with a connecting ball, a supporting rod is movably connected with the connecting ball, the hydrothermal reaction kettle is arranged above the supporting rod, heating is carried out to 160 ℃, reacting for 18h, centrifugally separating and removing the solvent, washing and drying the solid precursor product by using distilled water and ethanol in sequence, placing the solid precursor product into a muffle furnace, the heating rate is 5 ℃/min, the temperature is raised to 350 ℃, the heat preservation treatment is carried out for 2h, the temperature is raised to 550 ℃, the heat preservation calcination is carried out for 2h, and the CoFe is prepared2O4Porous nanowire component 2.
(2) Preparation of carboxylated polystyrene microsphere component 2: introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid in a mass ratio of 11:1, uniformly stirring, introducing nitrogen into a reaction bottle B, adding the ethanol solvent, styrene in a mass ratio of 10:2.1:0.7:0.28, polyvinylpyrrolidone serving as a stabilizer, triton X-100 serving as a surfactant and azodiisovaleronitrile serving as an initiator, heating the mixture in a water bath kettle to 70 ℃, stirring and reacting for 1.5h, slowly dropwise adding the solution of the reaction bottle A into the reaction bottle B, controlling the total mass fraction of the solution to be 15%, reacting for 30h, distilling the solution under reduced pressure to remove the solvent, washing a solid product with distilled water and ethanol, and drying to prepare a carboxylated polystyrene microsphere component 2.
(3) Preparation of Nano CoFe2O4Nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 2: adding 3 percent of acetic acid solution by mass into a reaction bottle, and adding chitosan, a carboxylated polystyrene microsphere component 2 and CoFe2O4Stirring the porous nanowire component 2 at a constant speed for 10h, standing and aging for 96h, washing the solid mixed product to be neutral, placing the solid mixed product in an atmosphere resistance furnace at a heating rate of 10 ℃/min, heating to 880 ℃ in an argon atmosphere, and carrying out heat preservation and calcination for 3h to obtain the nano CoFe2O4A nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 2.
Example 3
(1) Preparation of CoFe2O4Porous nanowire component 3: adding a mixed solvent of distilled water and ethylene glycol, namely ferric chloride, cobalt chloride, urotropine and glucose in a mass ratio of 1:2:1.3:22 into a reaction bottle, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, wherein the reaction kettle heating box comprises a heating device, a rotator is fixedly connected above the interior of the reaction kettle heating box and movably connected with a rotating shaft, an adjusting ball is movably connected with the rotating shaft, the adjusting ball is movably connected with an adjusting shaft, the adjusting shaft is movably connected with a connector, the connector is movably connected with a limiting rod, the limiting rod is movably connected with a connecting ball, a supporting rod is movably connected with the connecting ball, the hydrothermal reaction kettle is arranged above the supporting rod, heating is carried out to 165 ℃ for 14 h, centrifugally separating and removing the solvent, washing and drying the solid precursor product by using distilled water and ethanol in sequence, placing the solid precursor product into a muffle furnace, the heating rate is 4 ℃/min, the temperature is raised to 320 ℃, the heat preservation treatment is carried out for 1.5h, the temperature is raised to 520 ℃, the heat preservation calcination is carried out for 3h, and the CoFe is prepared2O4Porous nanowire setAnd 3, dividing.
(2) Preparation of carboxylated polystyrene microsphere component 3: introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid in a mass ratio of 13:1, uniformly stirring, introducing nitrogen into a reaction bottle B, adding the ethanol solvent, wherein the mass ratio of the styrene in the reaction bottle A to the styrene in the reaction bottle B is 1: 2.2:0.8:0.32, polyvinylpyrrolidone serving as a stabilizer, triton X-100 serving as a surfactant and azodiisovaleronitrile serving as an initiator, heating the mixture in a water bath kettle to 60 ℃, stirring and reacting for 1.5h, slowly dropwise adding the solution in the reaction bottle B, controlling the total mass fraction of the solution to be 20%, reacting for 26h, distilling the solution under reduced pressure to remove the solvent, washing a solid product with distilled water and ethanol, and drying to prepare a carboxylated polystyrene microsphere component 3.
(3) Preparation of Nano CoFe2O4Nitrogen-doped porous carbon-supported oxygen reduction catalyst material 3: adding 4 mass percent of acetic acid solution into a reaction bottle, and adding chitosan, a carboxylated polystyrene microsphere component 3 and CoFe2O4Stirring the porous nanowire component 3 at a constant speed for 15h, standing and aging for 85h, washing the solid mixed product to be neutral, placing the solid mixed product in an atmosphere resistance furnace at a heating rate of 6 ℃/min, heating to 850 ℃ in an argon atmosphere, and carrying out heat preservation and calcination for 2.5h to obtain the nano CoFe2O4A nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 3.
Example 4
(1) Preparation of CoFe2O4Porous nanowire component 4: adding a mixed solvent of distilled water and ethylene glycol, ferric chloride, cobalt chloride, urotropine and glucose with the mass ratio of 1:2:1.4:26 into a reaction bottle, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a reaction kettle heating box, wherein the reaction kettle heating box comprises a heating device, a rotator is fixedly connected above the inner part of the reaction kettle heating box and movably connected with a rotating shaft, an adjusting ball is movably connected with the rotating shaft, the adjusting ball is movably connected with an adjusting shaft, the adjusting shaft is movably connected with a connector, a limiting rod is movably connected with the connector, and the limiting rod is movably connected with a connecting ballConnecting, movably connecting the connecting ball with a support rod, arranging a hydrothermal reaction kettle above the support rod, heating to 180 ℃, reacting for 18h, centrifugally separating to remove the solvent, washing the solid precursor product with distilled water and ethanol in sequence, drying, placing the solid precursor product in a muffle furnace at a heating rate of 4 ℃/min, heating to 330 ℃, performing heat preservation treatment for 1.5h, heating to 500 ℃, performing heat preservation and calcining for 3h, and preparing the CoFe2O4A porous nanowire component 4.
(2) Preparation of carboxylated polystyrene microsphere component 4: introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid in a mass ratio of 14:1, uniformly stirring, introducing nitrogen into a reaction bottle B, adding the ethanol solvent, wherein the mass ratio of the styrene in the reaction bottle A to the styrene in the reaction bottle B is 1: 2.4:0.9:0.36, polyvinylpyrrolidone serving as a stabilizer, triton X-100 serving as a surfactant and azodiisovaleronitrile serving as an initiator, heating the mixture in a water bath kettle to 70 ℃, stirring for reaction for 1h, slowly dropwise adding the solution in the reaction bottle A into the reaction bottle B, controlling the total mass fraction of the solution to be 10%, reacting for 30h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare a carboxylated polystyrene microsphere component 4.
(3) Preparation of Nano CoFe2O4Nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 4: adding 4 mass percent of acetic acid solution into a reaction bottle, and adding chitosan, a carboxylated polystyrene microsphere component 4 and CoFe2O4Stirring the porous nanowire component 4 with the mass ratio of 10:5.5:40 at a constant speed for 20h, standing and aging for 96h, washing the solid mixed product to be neutral, placing the solid mixed product in an atmosphere resistance furnace, heating to 820 ℃ in an argon atmosphere at the heating rate of 5 ℃/min, and carrying out heat preservation and calcination for 3h to obtain the nano CoFe2O4A nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 4.
Example 5
(1) Preparation of CoFe2O4Porous nanowire component 5: adding a mixed solvent of distilled water and ethylene glycol, ferric chloride, cobalt chloride and urotropine in a mass ratio of 1:2:1.5:30 into a reaction bottleThe product and glucose are evenly stirred, then the solution is poured into a hydrothermal reaction kettle and placed in a reaction kettle heating box, the reaction kettle heating box comprises a heating device, a rotator is fixedly connected to the upper part inside the reaction kettle heating box, the rotator is movably connected with a rotating shaft, the rotating shaft is movably connected with an adjusting ball, the adjusting ball is movably connected with an adjusting shaft, the adjusting shaft is movably connected with a connector, the connector is movably connected with a limiting rod, the limiting rod is movably connected with a connecting ball, the connecting ball is movably connected with a supporting rod, a hydrothermal reaction kettle is arranged above the supporting rod and heated to 180 ℃ for reaction for 18h, the solvent is removed by centrifugal separation, a solid precursor product is washed by distilled water and ethanol in sequence and dried, the solid precursor product is placed in a muffle furnace, the heating rate is 5 ℃/min, the temperature is raised to 350 ℃, the solution is subjected to heat preservation treatment for 2h, the temperature is raised to 550 ℃, the solution is subjected to heat preservation and calcined for 4h, preparation of CoFe2O4A porous nanowire component 5.
(2) Preparation of carboxylated polystyrene microsphere component 5: introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid in a mass ratio of 15:1, uniformly stirring, introducing nitrogen into a reaction bottle B, adding the ethanol solvent, styrene in a mass ratio of 10:2.5:1:0.4, polyvinylpyrrolidone serving as a stabilizer, triton X-100 serving as a surfactant and azodiisovaleronitrile serving as an initiator, heating the mixture in a water bath kettle to 70 ℃, uniformly stirring for reaction for 1.5h, slowly dropwise adding the solution in the reaction bottle A into the reaction bottle B, controlling the total mass fraction of the solution to be 30%, reacting for 30h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to obtain a carboxylated polystyrene microsphere component 5.
(3) Preparation of Nano CoFe2O4Nitrogen-doped porous carbon-supported oxygen reduction catalyst material 5: adding 4 mass percent of acetic acid solution into a reaction bottle, and adding chitosan, a carboxylated polystyrene microsphere component 5 and CoFe2O4The porous nanowire component 5 is stirred at a constant speed for 20 hours with the mass ratio of 10:6:45, then is kept stand and aged for 96 hours, the solid mixed product is washed to be neutral, and is placed in an atmosphere resistance furnace with the heating rate of 10 ℃/min in argon atmosphereHeating the enclosure to 880 ℃, and carrying out heat preservation and calcination for 3 hours to prepare the nano CoFe2O4A nitrogen-doped porous carbon-loaded oxygen reduction catalyst material 5.
Mixing nano CoFe2O4Respectively placing the nitrogen-doped porous carbon-loaded oxygen reduction catalyst materials 1-5 in an ethanol solvent, respectively adding a Nafion solution, uniformly dispersing, uniformly coating the slurry on a foamed nickel current collector, drying and tabletting to prepare a working electrode material, taking a Pt sheet as a working electrode, Hg/HgO as a reference electrode, and 1mol/L potassium hydroxide solution as an electrolyte, and performing electrochemical performance test and oxygen reduction performance test in a CHI660E electrochemical workstation.
In summary, the nanometer CoFe2O4The oxygen reduction catalyst of the loaded nitrogen-doped porous carbon is prepared by taking glucose as a soft template and urotropine as a precipitator to obtain CoFe2O4The porous nano-wire has a large amount of mesoporous structures, can increase electrochemical active centers, and the carboxyl of the carboxylated polystyrene microsphere is ionized to generate hydrogen ions to form COO-The negative ions and the hydrogen ions are combined with the amino group of the chitosan to generate NH3 +Positive ions improve the mutual attraction of the positive ions and the negative ions, so that the polystyrene microspheres are uniformly modified among the chitosan to form an interpenetrating network, and then the interpenetrating network is mixed with the CoFe2O4The porous nanowires are compounded, chitosan serves as a carbon source, carboxylated polystyrene microspheres serve as a pore-foaming agent, nitrogen-doped porous carbon is prepared through high-temperature thermal cracking, the porous carbon has rich pore structures and large specific surface area, the nitrogen is doped in the porous carbon material to form graphite nitrogen and pyridine nitrogen structures, the graphite nitrogen is favorable for enhancing the conductivity of the porous carbon, the pyridine nitrogen can serve as an active site for oxygen reduction catalysis, and CoFe2O4The porous nanowires are uniformly dispersed in the matrix and the pore structure of the porous carbon material, so that CoFe is reduced2O4Agglomeration of porous nanowires and void junctionsThe wetting effect of the catalyst and the electrolyte is promoted, and the excellent oxygen reduction catalytic performance is shown under the synergistic effect.
Claims (4)
1. Nano CoFe2O4The oxygen reduction catalyst loaded with nitrogen-doped porous carbon is characterized in that: comprises the following raw materials and components of chitosan, carboxylated polystyrene microspheres and CoFe2O4The mass ratio of the porous nano-wire is 10:3-6: 20-45;
the nano CoFe2O4The preparation method of the oxygen reduction catalyst loaded with nitrogen-doped porous carbon comprises the following steps:
(1) adding a mixed solvent of distilled water and ethylene glycol, ferric chloride, cobalt chloride, urotropine and glucose into a hydrothermal reaction kettle, placing the mixture into a reaction kettle heating box, heating to 150-180 ℃, reacting for 10-18h, centrifugally separating, washing a solid precursor product, drying, placing the product into a muffle furnace at the temperature rise rate of 2-5 ℃/min, raising the temperature to 300-350 ℃, carrying out heat preservation treatment for 1-2h, raising the temperature to 500-550 ℃, and carrying out heat preservation calcination for 2-4h to obtain the CoFe2O4A porous nanowire;
(2) introducing nitrogen into a reaction bottle A, adding an ethanol solvent, styrene and acrylic acid, uniformly stirring, introducing nitrogen into a reaction bottle B, adding the ethanol solvent, styrene with the mass ratio of 10:2-2.5:0.6-1:0.25-0.4, polyvinylpyrrolidone serving as a stabilizer, triton X-100 serving as a surfactant and azodiisovaleronitrile serving as an initiator, heating to 50-70 ℃, reacting for 1-1.5h, slowly dropwise adding the solution of the reaction bottle A into the reaction bottle B, controlling the total mass fraction of the solution to be 10-30%, reacting for 20-30h, removing the solvent, washing and drying to prepare the carboxylated polystyrene microspheres;
(3) adding chitosan, carboxylated polystyrene microspheres and CoFe into acetic acid solution with the mass fraction of 2-4%2O4Stirring the porous nano-wire at a constant speed for 10-20h, standing and aging for 72-96 h, washing the solid mixed product to be neutral, placing the solid mixed product in an atmosphere resistance furnace, heating to 820-880 ℃ at a heating rate of 3-10 ℃/min in an argon atmosphere, and carrying out heat preservation and calcination for 2-3h to prepare the nano-CoFe2O4An oxygen reduction catalyst supporting nitrogen-doped porous carbon.
2. Nano CoFe according to claim 12O4The oxygen reduction catalyst loaded with nitrogen-doped porous carbon is characterized in that: the reaction kettle heating box comprises a heating device, a rotator and a rotating shaft movably connected to the upper portion inside the reaction kettle heating box, an adjusting ball is movably connected to the rotating shaft, the adjusting ball is movably connected to the adjusting shaft, the adjusting shaft is movably connected to the connector, a limiting rod is movably connected to the connector, the limiting rod is movably connected to the connecting ball, a supporting rod is movably connected to the connecting ball, and a hydrothermal reaction kettle is arranged above the supporting rod.
3. Nano CoFe according to claim 22O4The oxygen reduction catalyst loaded with nitrogen-doped porous carbon is characterized in that: the mass ratio of the ferric chloride to the cobalt chloride to the urotropine to the glucose is 1:2:1-1.5: 15-30.
4. Nano CoFe according to claim 22O4The oxygen reduction catalyst loaded with nitrogen-doped porous carbon is characterized in that: the mass ratio of the styrene to the acrylic acid in the reaction bottle A is 10-15:1, and the mass ratio of the styrene to the reaction bottle B is 1: 1-1.5.
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