CN113522368A - Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and preparation method thereof - Google Patents
Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst 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 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 25
- 241000257465 Echinoidea Species 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004793 Polystyrene Substances 0.000 claims abstract description 24
- 229920002223 polystyrene Polymers 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229920000767 polyaniline Polymers 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000004005 microsphere Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910017061 Fe Co Inorganic materials 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002041 carbon nanotube Substances 0.000 abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- -1 supercapacitors Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- 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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- 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
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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
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y02E60/30—Hydrogen technology
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and a preparation method thereof3·6H2O construction of oxidation system for in-situ growth of polyaniline and adsorption of Co2+Then mixing melamine, in the high-temperature carbonization process, using high temperature to etch off the polystyrene template and carbonize the polystyrene layer, at the same time, using adsorbed metal to guide growth of carbon nano tube and reducing metal element to form nano alloy so as to prepare Fe and Co codoped carbon-based catalystThe sea urchin-like structure with high specific surface area is formed. The preparation method has the advantages of simplicity, low cost, ingenious catalyst morphology construction method, large specific surface area, high catalytic performance and good chemical stability of the catalyst; in addition, the method is green and environment-friendly, non-noble metals are used for replacing noble metals to be applied to production, and the method has important application value in the field of new energy.
Description
Technical Field
The invention belongs to the technical field of energy, and particularly relates to a Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and a preparation method thereof.
Background
The large-scale application of traditional fossil energy causes great resistance to the development of human society, the problem of environmental pollution caused by the traditional fossil energy, and the energy crisis caused by the non-renewable property of the traditional fossil energy form serious threats, so that the search of novel green, clean and renewable energy to replace the traditional fossil energy becomes one of the current popular research directions. The metal-air battery is a novel energy carrier, and has been widely noticed because of its advantages of environmental protection, high energy density, low cost, good safety, etc., and the reason for restricting its development is that the oxygen reduction reaction rate of its cathode is low, so that the reaction rate is accelerated by using an electro-catalyst, thereby improving the battery performance. The electrocatalysts currently in common use are noble metal based catalysts, such as Pt-C catalysts. The high cost of the noble metal-based catalyst and the scarcity of the noble metal resources are unfavorable for the development and large-scale commercial application of the noble metal-based catalyst, so that the search for a high-efficiency non-noble metal-based catalyst to replace the noble metal-based catalyst is one of the future development directions.
The hydrogen energy is an ideal sustainable substitute for energy substances in various energy systems, and has the remarkable advantages of greenness, safety, high energy density, centralized energy, wide application range and the like. However, the traditional preparation methods such as methane steam reforming and the like rely heavily on fossil energy, and the problems caused by the fossil energy cannot be solved well. The driving energy of the electrochemical water splitting hydrogen production technology can be electric energy generated by sustainable renewable energy sources such as solar energy, water energy and the like, the raw material for preparing the hydrogen is water, and the combustion product is water, so that the problems caused by fossil energy are well solved. The restriction factor is the slow hydrogen evolution reaction rate on the cathode, and in order to solve the problem, the catalyst commonly used at present is a noble metal-based catalyst, and the problems of high cost and resource shortage are not favorable for future development and large-scale commercial application, so that the search of a high-efficiency non-noble metal-based catalyst to replace the noble metal-based catalyst is one of the future research directions.
The hollow core-shell sphere has been widely studied due to its advantages of large specific surface area, small density, controllable morphology and size, high loading of doping elements, and the like. The unique structural characteristic of the hollow core-shell ball also enables the hollow core-shell ball to be widely applied to the fields of pollution treatment, photocatalysis, biological medicine, supercapacitors, fuel cells, electromagnetic shielding and the like. The hollow core-shell sphere structure has various preparation methods including a hard template method, a soft template method, a template-free method and the like, wherein the hard template method is most widely applied and the process is most mature. The specific surface area of the material can be further improved by further modifying the hollow core-shell spheres, so that the catalyst has more catalytic sites, and in the catalysis process, the modification enables more catalytic sites to be exposed in a solution environment, so that the catalysis efficiency is improved.
Disclosure of Invention
In order to solve the problems in the technology, the invention provides a Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and a preparation method thereof. In particular, polystyrene microspheres are used as templates and FeCl is used for preparing the porous material3·6H2And O builds an oxidation system, and achieves the purpose of doping Fe element while growing a polyaniline layer on the surface of the polystyrene microsphere in situ. After adsorbing Co element and mixing melamine, etching the polystyrene microspheres by a certain carbonization process to form a hollow structure and forming holes on the carbon layer; in addition, melamine is decomposed at high temperature, and is guided by Fe and Co adsorbed by polyaniline, so that carbon nano tubes grow on the surface of the carbon layer, and Fe and Co form nano alloy in the carbonization process, thereby preparing the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
The technical scheme adopted by the invention is as follows:
(1) dissolving styrene and polyvinylpyrrolidone in deionized water, pouring into a three-neck flask, mechanically stirring, continuously introducing high-purity nitrogen to remove air, adding potassium persulfate aqueous solution, heating, and refluxing. The resulting emulsion was centrifuged and the emulsion was collected.
(2) Ultrasonically dispersing the polystyrene microspheres obtained in the step (1) in deionized water, adding aniline for magnetic stirring, and then adding FeCl dissolved in the aniline3·6H2O in water, and reacting at room temperature. After the reaction is completed, washing is performed.
(3) Ultrasonically dispersing the powder obtained in the step (2) in absolute ethyl alcohol, and adding Co (NO)3)2·6H2And continuously carrying out ultrasonic treatment until the mixture is uniform, and then placing the mixture in a vacuum oven for drying. And fully grinding and mixing the collected powder and melamine, putting the mixture into a porcelain boat, putting the porcelain boat into a tube furnace, vacuumizing the porcelain boat, introducing inert gas into the porcelain boat, repeating the steps for three times, then preserving the heat at a low temperature for a period of time, carbonizing the mixture at a high temperature, and collecting the powder after complete carbonization to obtain the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
Further, the mass ratio of the styrene to the polyvinylpyrrolidone to the potassium persulfate in the step (1) is (6-20): (1-5): (0.2-2).
Further, the heating reflux time in the step (1) is 10-24 h.
Further, the rotation speed of the mechanical stirring in the step (1) is maintained at 500rpm and 300-.
Further, the polystyrene microspheres, polyaniline and FeCl used in the step (2)3·6H2The mass ratio of O is (0.1-0.5): (0.1-0.5): (1-10).
Further, the magnetic stirring after the aniline is added in the step (2) is kept for 0.5-4h, and the rotating speed is kept at 200-500 rpm.
Further, the polymerization reaction time in the step (2) is 6-24 h.
Further, the solution obtained after the reaction in the step (2) is centrifugally washed by deionized water and ethanol, and the centrifugal rotation speed is 7000-10000 rpm.
Further, the powder, Co (NO) in the step (3)3)2·6H2The mass ratio of O to melamine is (0.2-1): (0.05-0.5): (2-20).
Further, the inert atmosphere in the step (3) adopts N2Atmosphere or Ar atmosphere.
Further, the low-temperature heat preservation in the step (3) is carried out at the temperature of 340-.
Further, the carbonization temperature in the step (3) is selected from 600 ℃ and 1100 ℃, and is kept for 0.5-4 h.
On the other hand, the invention provides the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst prepared by the preparation method of the first aspect of the invention, which is used for fuel cells, metal-air cells and electrochemical water cracking electrocatalysts, and compared with the prior art, the invention has the following advantages:
(1) the catalyst has the characteristics of controllable appearance, low cost, simple process, good catalytic performance, good chemical stability and the like.
(2) The invention utilizes the polystyrene as a template, not only realizes the aim of preparing the hollow core-shell carbon sphere, but also causes a multi-stage porous structure and defect sites on the carbon shell due to the characteristic of decomposing the polystyrene at high temperature. The structure is beneficial to improving the mass transfer efficiency and the electron transmission efficiency while increasing the specific surface area and improving the load of the active sites, thereby improving the oxygen reduction reaction rate.
(3) The invention utilizes FeCl3·6H2And the characteristic of O is that an oxidation system is constructed, so that the effect of an initiator is achieved, the effect of a dopant is also achieved, and the growth of the carbon nano tube is guided in the carbonization process by cooperating with Co metal elements.
(4) The metal element introduced by the invention and the N element carried by the carbonized polyaniline mutually play a synergistic role, so that the catalyst has multiple catalytic functions, and high-efficiency catalytic performance and good chemical stability are achieved.
Detailed Description
The following description of the present invention is provided as illustrative of various embodiments thereof and is not to be construed as limiting the invention but rather as providing a detailed description of certain features and specific operations thereof, embodiments of the invention being limited to the exemplary embodiments set forth below. Structural modifications and content optimizations of the embodiments of the present invention without departing from the scope of the present invention should be understood to be within the scope of the present invention.
Example 1
Step one, taking styrene: the polyvinylpyrrolidone with the mass ratio of 10:1 is dissolved in 80ml of deionized water, and the mixture is poured into a three-neck flask and mechanically stirred for 30min at 300rpm, and high-purity nitrogen is continuously introduced during the stirring process to remove air. Then 0.35g of potassium persulfate dissolved in 20ml of deionized water was added and the temperature was raised to 70 ℃ and heated under reflux for 24 h. After the reaction was complete, the emulsion was collected.
Step two, taking 0.2g of the polystyrene microspheres obtained in the step one, ultrasonically dispersing the polystyrene microspheres in 30ml of deionized water, adding 0.2g of aniline, keeping the stirring speed at 300rpm for 1 hour, and then adding 20ml of FeCl dissolved with 2.16g of FeCl3·6H2O aqueous solution, and magnetic stirring was maintained at room temperature. After 8h, the mixture was washed with deionized water and ethanol, and the powder was collected by centrifugation at 9000rpm and dried.
Step three, taking 0.2g of the powder obtained in the step two, ultrasonically dispersing the powder in 20ml of absolute ethyl alcohol, and adding 0.145g of Co (NO)3)2·6H2And continuing to perform ultrasonic treatment until the mixture is uniform, and then placing the mixture in a vacuum oven for drying. After the powder is dried, fully grinding and mixing the powder with 2g of melamine, putting the mixture into a ceramic boat, putting the ceramic boat into a tube furnace, vacuumizing the ceramic boat, and introducing N2And (3) repeating the reaction for three times, keeping the reaction at 400 ℃ for 1h, then raising the temperature to 900 ℃ for carbonization for 2h, and collecting powder after complete carbonization to obtain the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
Example 2
Step one, taking styrene: the polyvinylpyrrolidone with the mass ratio of 6:1 is dissolved in 80ml of deionized water, and the mixture is poured into a three-neck flask and mechanically stirred at 350rpm for 30min, and high-purity nitrogen is continuously introduced during the stirring to remove air. Then 0.23g of potassium persulfate dissolved in 20ml of deionized water was added and the temperature was raised to 75 ℃ and heated under reflux for 24 h. After the reaction was complete, the emulsion was collected.
Step two, taking 0.2g of the polystyrene microspheres obtained in the step one, ultrasonically dispersing the polystyrene microspheres in 30ml of deionized water, adding 0.2g of aniline, and keeping the magnetic force at 300rpmStirring for 1h, then adding 20ml FeCl dissolved with 2.16g3·6H2O aqueous solution, and magnetic stirring was maintained at room temperature. After 8h, the mixture was washed with deionized water and ethanol, and the powder was collected by centrifugation at 9000rpm and dried.
Step three, taking 0.2g of the powder obtained in the step two, ultrasonically dispersing the powder in 20ml of absolute ethyl alcohol, and adding 0.145g of Co (NO)3)2·6H2And continuing to perform ultrasonic treatment until the mixture is uniform, and then placing the mixture in a vacuum oven for drying. After the powder is dried, fully grinding and mixing the powder with 2g of melamine, putting the mixture into a ceramic boat, putting the ceramic boat into a tube furnace, vacuumizing the ceramic boat, and introducing N2And (3) repeating the reaction for three times, keeping the reaction at 400 ℃ for 1h, then raising the temperature to 900 ℃ for carbonization for 2h, and collecting powder after complete carbonization to obtain the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
Example 3
Step one, taking styrene: the polyvinylpyrrolidone with the mass ratio of 10:1 is dissolved in 80ml of deionized water, and the mixture is poured into a three-neck flask and mechanically stirred for 30min at 300rpm, and high-purity nitrogen is continuously introduced during the stirring process to remove air. Then 0.35g of potassium persulfate dissolved in 20ml of deionized water was added and the temperature was raised to 70 ℃ and heated under reflux for 24 h. After the reaction was complete, the emulsion was collected.
Step two, taking 0.1g of the polystyrene microspheres obtained in the step one, ultrasonically dispersing the polystyrene microspheres in 30ml of deionized water, adding 0.1g of aniline, keeping 440rpm for magnetic stirring for 0.5h, and then adding 20ml of FeCl dissolved with 1g of the aniline into the mixture3·6H2O aqueous solution, and magnetic stirring was maintained at room temperature. After 12h, the powder was collected by centrifugation at 8000rpm and dried by washing with deionized water and ethanol.
Step three, taking 0.2g of the powder obtained in the step two, ultrasonically dispersing the powder in 20ml of absolute ethyl alcohol, and adding 0.145g of Co (NO)3)2·6H2And continuing to perform ultrasonic treatment until the mixture is uniform, and then placing the mixture in a vacuum oven for drying. After the powder is dried, fully grinding and mixing the powder with 2g of melamine, putting the mixture into a ceramic boat, putting the ceramic boat into a tube furnace, vacuumizing the ceramic boat, and introducing N2Repeating the steps for three times, keeping the temperature at 400 ℃ for 1h, then raising the temperature to 900 ℃ for carbonization for 2h, and collecting powder after complete carbonization to obtain Fe and CoThe hollow carbon sphere electrocatalyst with a doped sea urchin structure.
Example 4
Step one, taking styrene: the polyvinylpyrrolidone with the mass ratio of 10:1 is dissolved in 80ml of deionized water, and the mixture is poured into a three-neck flask and mechanically stirred for 30min at 300rpm, and high-purity nitrogen is continuously introduced during the stirring process to remove air. Then, 0.35g of potassium persulfate dissolved in 20ml of deionized water was added, and the temperature was raised to 70 ℃ and heated under reflux for 24 hours. After the reaction was complete, the emulsion was collected.
Step two, taking 0.2g of the polystyrene microspheres obtained in the step one, ultrasonically dispersing the polystyrene microspheres in 30ml of deionized water, adding 0.2g of aniline, keeping the stirring speed at 300rpm for 1 hour, and then adding 20ml of FeCl dissolved with 2.16g of FeCl3·6H2O aqueous solution, and magnetic stirring was maintained at room temperature. After 8h, the mixture was washed with deionized water and ethanol, and the powder was collected by centrifugation at 9000rpm and dried.
Step three, taking 0.4g of the powder obtained in the step two, ultrasonically dispersing the powder in 20ml of absolute ethyl alcohol, and adding 0.25g of Co (NO)3)2·6H2And continuing to perform ultrasonic treatment until the mixture is uniform, and then placing the mixture in a vacuum oven for drying. After the powder is dried, fully grinding and mixing the powder with 5g of melamine, putting the mixture into a ceramic boat, putting the ceramic boat into a tube furnace, vacuumizing the ceramic boat, and introducing N2And (3) repeating the reaction for three times, keeping the reaction at 400 ℃ for 1h, then raising the temperature to 900 ℃ for carbonization for 2h, and collecting powder after complete carbonization to obtain the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
Example 5
Step one, taking styrene: the polyvinylpyrrolidone with the mass ratio of 10:1 is dissolved in 80ml of deionized water, and the mixture is poured into a three-neck flask and mechanically stirred for 30min at 300rpm, and high-purity nitrogen is continuously introduced during the stirring process to remove air. Then, 0.35g of potassium persulfate dissolved in 20ml of deionized water was added, and the temperature was raised to 70 ℃ and heated under reflux for 24 hours. After the reaction was complete, the emulsion was collected.
Step two, taking 0.2g of the polystyrene microspheres obtained in the step one, ultrasonically dispersing the polystyrene microspheres in 30ml of deionized water, adding 0.2g of aniline, keeping the stirring speed at 300rpm for 1 hour, and then adding 20ml of FeCl dissolved with 2.16g of FeCl3·6H2O aqueous solution andmagnetic stirring was carried out at room temperature. After 8h, the mixture was washed with deionized water and ethanol, and the powder was collected by centrifugation at 9000rpm and dried.
Step three, taking 0.3g of the powder obtained in the step two, ultrasonically dispersing the powder in 20ml of absolute ethyl alcohol, and adding 0.2g of Co (NO)3)2·6H2And continuing to perform ultrasonic treatment until the mixture is uniform, and then placing the mixture in a vacuum oven for drying. After the powder is dried, fully grinding and mixing the powder with 4g of melamine, putting the mixture into a ceramic boat, putting the ceramic boat into a tube furnace, vacuumizing the ceramic boat, and introducing N2And (3) repeating the reaction for three times, keeping the reaction at 340 ℃ for 5h, then raising the temperature to 900 ℃ for carbonization for 1h, and collecting powder after complete carbonization to obtain the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
Example 6
Step one, taking styrene: the polyvinylpyrrolidone with the mass ratio of 11:1.5 is dissolved in 100ml of deionized water, and the solution is poured into a three-neck flask to be mechanically stirred for 30min at 280rpm, and high-purity nitrogen is continuously introduced during the stirring to remove air. Then 0.38g of potassium persulfate dissolved in 20ml of deionized water was added and the temperature was raised to 70 ℃ and heated under reflux for 10 hours. After the reaction was complete, the emulsion was collected.
Step two, taking 0.3g of the polystyrene microspheres obtained in the step one, ultrasonically dispersing the polystyrene microspheres in 30ml of deionized water, adding 0.3g of aniline, keeping the magnetic stirring at 400rpm for 1h, and then adding 20ml of FeCl dissolved with 3.2g of FeCl3·6H2O aqueous solution, and magnetic stirring was maintained at room temperature. After 12h, the powder was collected by centrifugation at 8000rpm and dried by washing with deionized water and ethanol.
Step three, taking 0.3g of the powder obtained in the step two, ultrasonically dispersing the powder in 15ml of absolute ethyl alcohol, and adding 0.18g of Co (NO)3)2·6H2And continuing to perform ultrasonic treatment until the mixture is uniform, and then placing the mixture in a vacuum oven for drying. After the powder is dried, the powder is fully ground and mixed with 3.5g of melamine, the mixture is placed in a ceramic boat and is placed in a tube furnace, N is introduced after the vacuum pumping2And (3) repeating the reaction for three times, keeping the reaction at 400 ℃ for 1h, then raising the temperature to 800 ℃ for carbonization for 2h, and collecting powder after complete carbonization to obtain the Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
Claims (6)
1. A Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and a preparation method thereof are characterized by comprising the following steps:
(1) dissolving styrene and polyvinylpyrrolidone in deionized water, pouring into a three-neck flask for mechanical stirring, continuously introducing high-purity nitrogen to remove air during the mechanical stirring, adding a potassium persulfate aqueous solution, heating, refluxing, and collecting emulsion;
(2) ultrasonically dispersing the polystyrene microspheres obtained in the step (1) in deionized water, adding aniline for magnetic stirring, and then adding FeCl dissolved in the aniline3·6H2Reacting the water solution of O at room temperature, and washing after the reaction is finished;
(3) ultrasonically dispersing the powder obtained in the step (2) in absolute ethyl alcohol, and adding Co (NO)3)2·6H2And continuously carrying out ultrasonic treatment on the O to be uniform, then placing the O in a vacuum oven for drying, collecting the powder, fully grinding and mixing the powder and melamine, placing the mixture in a porcelain boat, placing the porcelain boat in a tube furnace, vacuumizing the porcelain boat, introducing inert gas, repeating the steps for three times, then carrying out high-temperature carbonization after keeping the temperature at a low temperature for a period of time, and collecting the powder after the carbonization is completed to obtain the Fe-Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst.
2. The Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and the preparation method thereof according to claim 1, wherein the polystyrene microspheres are prepared from styrene, polyvinylpyrrolidone and potassium persulfate according to the mass ratio of (6-20): (1-5): (0.2-2).
3. The Fe and Co Co-doped urchin-like structure hollow carbon sphere electrocatalyst and the preparation method thereof as claimed in claim 1, wherein the polystyrene microspheres, polyaniline, FeCl3·6H2The mass ratio of O is (0.1-0.5): (0.1-0.5): (1-10).
4. The Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and preparation thereof as claimed in claim 1The method is characterized in that the powder and Co (NO) are mixed3)2·6H2The mass ratio of O to melamine is (0.2-1): (0.05-0.5): (2-20).
5. The Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and the preparation method thereof as claimed in claim 1, wherein the carbonization process is performed at 600-.
6. The Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and the preparation method thereof are characterized in that the electrocatalyst is prepared by the preparation method of any one of claims 1-5, and the obtained material is applied to the energy fields of electrocatalysis, fuel cells, metal-air cells, electrocatalysis full-hydrolysis and the like.
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| CN116947640B (en) * | 2023-09-21 | 2023-12-15 | 深圳市普利凯新材料股份有限公司 | Purification method of acetoacetyl ethyl methacrylate |
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