CN112079346A - Metal organic framework in-situ activated hollow carbon sphere and preparation method and application thereof - Google Patents
Metal organic framework in-situ activated hollow carbon sphere and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 91
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 29
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 29
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 29
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 29
- 238000004140 cleaning Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000000919 ceramic Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 238000004729 solvothermal method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 9
- 150000001340 alkali metals Chemical class 0.000 abstract description 9
- 238000002791 soaking Methods 0.000 abstract description 9
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000003738 black carbon Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/51—
-
- B01J35/617—
-
- B01J35/618—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of inorganic non-metallic materials and electrochemistry, and discloses a metal organic framework in-situ activated hollow carbon sphere, and a preparation method and application thereof. The preparation method comprises the following steps: (1) adding zinc salt, ligand and polyvinylpyrrolidone into an organic solvent, stirring, putting into a reaction kettle, putting the reaction kettle into a drying oven at 110-200 ℃ for reaction, cooling, cleaning, and keeping the temperature at 60-120 ℃ to obtain hollow metal organic framework particles; (2) placing the dried metal organic frame particles in a hearth, raising the temperature to 550-750 ℃ at the rate of 5 ℃ per minute, preserving the heat for 1-10 hours, and naturally cooling to room temperature to obtain hollow carbon spheres; (3) and heating the hollow carbon spheres to 800-1400 ℃, preserving the heat for 1-10 hours, naturally cooling to room temperature, soaking, cleaning, and carrying out suction filtration/centrifugal drying to obtain the in-situ activated hollow carbon spheres. The method has the advantages of simple preparation, easy operation and low cost, and the obtained hollow carbon spheres have high application value in the fields of super capacitors and alkali metal batteries.
Description
Technical Field
The invention belongs to the field of inorganic non-metallic materials and electrochemistry, and particularly relates to a metal organic framework, a preparation method of an in-situ activated hollow carbon sphere of the metal organic framework, and application of the material in the fields of supercapacitors, lithium ion batteries or electrocatalysis.
Background
With the reduction of renewable energy sources in the world, research, development and utilization of renewable energy sources are more and more perfected. But the appearance of new materials can bring unexpected surprise to the field of new energy. Therefore, the exploration and research of new materials are very significant. Metal Organic Framework (MOF) is a new material formed by coordination of metal sites and organic ligands. Due to the dual advantages of metal ions and organic complexes contained in the metal/carbon composite material, the metal oxide, the carbon material and the metal/carbon-containing composite material can be derived in situ. The derivative material can inherit structural information of MOF precursors, for example: specific shapes (icosahedron, regular octahedron, rod-shaped and the like), pore channel structures, pore size distribution and the like. The advantageous synthesis methods of MOF precursors are therefore particularly important for the preparation of their derivative materials. In addition, the hollow structure has larger cavity and specific surface area compared with the solid structure, which is beneficial to improving the active area of the material.
The invention patent with the application number of CN201010128464.2, a preparation method of monodisperse hollow carbon spheres and the invention patent with the application number of CN201010128464.2 disclose a method for preparing hollow carbon spheres by adopting a template method, wherein the method needs a specific template and is usually accompanied with a secondary treatment process, so that environmental pollution and structural damage are easily caused; the invention patent with application number CN201910670472.0 discloses a preparation method of hollow carbon spheres, which needs a proper pyrolysis carbon source. Meanwhile, the conventional carbon material needs to be activated before being used as an electrode material, so that the active sites and the active specific surface area of the material are improved. The in-situ activated carbon material can avoid adding an activating agent and subsequent activating agent treatment steps, so that energy is saved, emission is reduced, and the economic value of the carbon material is improved. Therefore, the preparation method of the hollow carbon sphere derived from the in-situ activated hollow metal organic framework is more beneficial to obtaining materials with excellent structure and better performance and has higher economic value.
Disclosure of Invention
The invention aims to provide a preparation method of metal organic framework in-situ activated hollow carbon spheres, which is simple, easy to operate, good in expandability and capable of being widely applied in large scale
Specific surface area, active sites, cycling stability and reduced volume expansion of the high carbon spheres.
The invention also aims to provide the metal organic framework in-situ activated hollow carbon sphere prepared by the preparation method, and the hollow carbon sphere has the advantages of high specific surface, more active sites and good cycle stability.
Still another object of the present invention is to provide the use of the hollow carbon spheres as described above in the field of super capacitors and lithium/sodium/potassium ion batteries, which can improve the specific capacity of super capacitors and the capacity and cycle performance of lithium/sodium/potassium batteries.
In order to realize the purpose, the invention adopts the following technical scheme:
the metal organic framework in-situ activated hollow carbon sphere has the outer diameter of 0.45-1.15 mu m, the inner diameter of 0.35-0.95 mu m, and the specific surface area of 600-1500 cm-3 g-1。
Further, the hollow carbon spheres are composed of the following components: c95.5 at.% to 99.2 at.%, N0.8 at.% to 3.7 at.%, and O0 to 0.8 at.%.
A preparation method of the metal organic framework in-situ activated hollow carbon sphere comprises the following steps:
(1) adding polyvinylpyrrolidone (PVP), ligand and zinc salt into an organic solvent, and stirring to obtain a clear solution; then, carrying out solvothermal reaction on the clear solution, naturally cooling to room temperature after the reaction is finished, washing and drying to obtain light yellow metal organic framework particles;
(2) placing the light yellow metal organic framework particles obtained in the step (1) into a ceramic boat, and pretreating the ceramic boat under protective gas to obtain dark gray hollow carbon spheres;
(3) and (3) placing the dark gray hollow carbon spheres obtained in the step (2) in a ceramic boat, activating the ceramic boat under protective gas, cooling to obtain hollow carbon spheres, cleaning, and drying to obtain the hollow carbon sphere particles with the metal organic framework activated in situ.
Preferably, the metal salt in the step (1) is one or a mixture of two of zinc nitrate, zinc acetate and zinc sulfate, the ligand is phthalic acid or trimesic acid, the PVP is 1-130 million, the organic solvent is a mixed solution of N, N-dimethylformamide and ethanol, and the volume ratio of the N, N-Dimethylformamide (DMF) to the ethanol is 0-15: 20-50 parts of; the mass-volume ratio of the zinc salt, the ligand, the polyvinylpyrrolidone and the organic solvent in the step (1) is 430 mg: (100-200) mg: 1000 mg: (30-50) mL.
Preferably, the solvothermal reaction temperature in the step (2) is 110-200 ℃, and the heat preservation time is 1-24 hours; the solvent adopted for washing is ethanol; the drying temperature is 60-120 ℃, and the drying time is 24-72 hours.
Preferably, the pretreatment temperature in the step (3) is 550-750 ℃, and the pretreatment time is 1-10 hours.
Preferably, the temperature rise rate in the step (4) is 1-10 ℃/min, the heat treatment temperature is 800-1400 ℃, the heat treatment time is 1-10 hours, and the acid is a sulfuric acid aqueous solution with the concentration of 0.1-10M.
Preferably, the protective gas in the steps (3) and (4) is nitrogen, argon or a hydrogen-argon mixed gas.
More preferably, the specific preparation method of the preparation method comprises the following steps:
(1) taking 30-50 mL of a DMF and ethanol mixed solution into a beaker, adding 1g of PVP with the average molecular weight of 1-130 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved; then stirring the zinc salt with the mass of 430 mg by using a magnetic stirrer until the salt solution is completely dissolved to obtain a clear and transparent solution;
(2) transferring the solution in the beaker to a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven at 90-200 ℃, preserving heat for 1-24 hours, naturally cooling to room temperature, cleaning with ethanol, placing light yellow powder in the oven at 60-120 ℃, preserving heat for 24-72 hours, and obtaining light yellow metal organic framework particles;
(3) placing light yellow metal organic frame particles into a magnetic ceramic boat, placing the ceramic boat into a tube furnace, heating to 550-750 ℃ at the heating rate of 5 ℃/min, preserving heat for 1-10 hours, and naturally cooling to obtain dark gray hollow carbon spheres;
(4) and (2) placing the dark gray hollow carbon spheres in a ceramic boat, placing the ceramic boat in a tube furnace, heating to 800-1400 ℃ at a heating rate of 1-10 ℃/min, preserving the temperature for 1-10 hours, naturally cooling, putting into 0.1-10M sulfuric acid, cleaning, and drying to obtain the dark black hollow carbon sphere particles activated in situ by the metal organic framework.
The hollow carbon sphere with the hollow metal organic framework activated in situ is prepared by the preparation method.
The application of the hollow carbon spheres activated in situ by the metal organic framework is applied to the fields of supercapacitors, lithium/sodium/potassium ion batteries or catalysis.
Advantageous effects
(1) The invention provides a new method for preparing the hollow carbon spheres, the preparation method is simple, does not need an additional activator, is simple and convenient to operate, has low cost and less pollution in the activation process, and has good expandability and large-scale application.
(2) The metal organic framework in-situ activated hollow carbon spheres prepared by the invention have the advantages of high specific surface, more active sites and good cycle stability.
(3) The hollow carbon spheres prepared by the method can be used in the fields of super capacitors and lithium/sodium/potassium ion batteries, and can improve the performance of the super capacitors and lithium batteries.
Drawings
Fig. 1 is an SEM image of hollow carbon spheres prepared in example 1;
fig. 2 is an XRD spectrum of the hollow carbon sphere of example 1;
fig. 3 is an SEM image of the hollow carbon spheres prepared in example 2;
fig. 4 is an XRD spectrum of the hollow carbon sphere of example 2;
fig. 5 is an SEM image of hollow carbon spheres prepared in example 3;
fig. 6 is an XRD spectrum of the hollow carbon sphere of example 3;
fig. 7 is an SEM image of hollow carbon spheres prepared in example 4;
fig. 8 is an XRD spectrum of the hollow carbon sphere of example 4;
fig. 9 is an SEM image of the hollow carbon spheres prepared in comparative example 1;
fig. 10 is an SEM image of the hollow carbon spheres prepared in comparative example 2;
fig. 11 is an SEM image of the hollow carbon spheres prepared in comparative example 3;
fig. 12 is an SEM image of the hollow carbon spheres prepared in comparative example 4.
Detailed Description
The invention is further described in detail by the following drawings, examples and comparative examples in order to further understand the features and technical means of the invention and achieve the specific objects and functions of the invention. However, it should not be understood that the scope of the present invention as defined above is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
In the following examples 1 to 4, zinc nitrate, zinc acetate, zinc sulfate, phthalic acid or trimesic acid, N-Dimethylformamide (DMF), ethanol and PVP were used as raw materials, and self-assembled hollow carbon spheres were prepared by a solvothermal method in combination with subsequent pretreatment and heat treatment.
Example 1
(1) Pouring 30 mL of DMF and 15 mL of ethanol into a beaker, adding 1g of PVP with the average molecular weight of 4 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 400 mg of zinc nitrate, 30 mg of zinc acetate and 100mg of phthalic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution into a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction for 24 hours at 110 ℃;
(4) washing a sample subjected to solvent thermal reaction by using ethanol, centrifuging to obtain a light yellow precipitate, and drying the precipitate for 24 hours in a 60 ℃ drying oven;
(5) grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing hydrogen-argon mixed gas for 20 minutes, heating to 550 ℃, keeping the temperature for 10 hours at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain dark gray hollow carbon spheres;
(6) putting the dark gray hollow carbon spheres in the tubular furnace again, introducing hydrogen-argon mixed gas for 20 minutes, heating to 800 ℃ at the speed of 1 ℃/min under the protection of the hydrogen-argon mixed gas, preserving the temperature for 10 hours, and naturally cooling to room temperature to obtain a black sample; placing the black sample in 10M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain the dark black hollow carbon sphere particles with the metal organic framework in-situ activation, wherein the outer diameter size is 0.45 mu M, the inner diameter size is 0.35 mu M, and the specific surface area is 600 cm-3 g-199.1 at.% of C, 0.8 at.% of N, and 0.1 at.% of O;
the dark black hollow carbon sphere particles prepared in example 1 were used as electrode raw materials, and a supercapacitor electrode and an alkali metal negative electrode were prepared respectively by a preparation method of literature (preparation and characterization of a Chenjiali heteroatom-doped porous carbon material and electrochemical performance research thereof [ D ] Master academic thesis 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 1 is an SEM picture of the hollow carbon spheres prepared in example 1. Fig. 2 is an XRD spectrum of the hollow carbon sphere prepared in example 1.
Example 2
(1) Pouring 40 mL of DMF and 5 mL of ethanol into a beaker, adding 1g of PVP with the average molecular weight of 1 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 400 mg of zinc nitrate, 30 mg of zinc sulfate and 120 mg of trimesic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution into a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction for 6 hours at 120 ℃;
(4) cleaning a sample subjected to solvent thermal reaction by using ethanol, centrifuging to obtain light yellow powder, and drying the yellow powder in a 120 ℃ oven for 12 hours;
(5) grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing argon gas for 20 minutes, heating to 600 ℃, keeping the temperature for 5 hours at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain dark gray hollow carbon spheres;
(6) placing the dark gray hollow carbon spheres in a tubular furnace again, introducing argon for 20 minutes, heating to 900 ℃ at the speed of 3 ℃/min under the protection of the argon, preserving the temperature for 5 hours, and naturally cooling to room temperature to obtain a black sample; placing the black sample in 1M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain the dark black hollow carbon sphere particles with the metal organic framework in-situ activation, wherein the outer diameter size is 0.55 mu M, the inner diameter size is 0.45 mu M, and the specific surface area is 800 cm-3 g-1C content of 96.7 at.%, N content of 2.5 at.%, and O contentIn an amount of 0.8 at.%;
the dark black hollow carbon sphere particles prepared in example 2 were used as electrode raw materials, and a supercapacitor electrode and an alkali metal negative electrode were prepared respectively by a preparation method of literature (preparation and characterization of a Chenjiali heteroatom-doped porous carbon material and electrochemical performance research [ D ] Master academic thesis 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 3 is an SEM picture of the hollow carbon spheres prepared in example 2. Fig. 4 is an XRD spectrum of the hollow carbon sphere prepared in example 2.
Example 3
(1) Pouring 20 mL of DMF and 10 mL of ethanol into a beaker, adding 1g of PVP with the average molecular weight of 5 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 430 mg of zinc nitrate and 150 mg of phthalic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution into a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction at 180 ℃ for 12 hours;
(4) cleaning a sample subjected to solvent thermal reaction by using ethanol, centrifuging to obtain light yellow powder, and drying the yellow powder in an oven at the temperature of 80 ℃ for 72 hours;
(5) grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing high-purity nitrogen for 20 minutes, heating to 750 ℃, keeping the temperature for 8 hours at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain dark gray hollow carbon spheres;
(6) placing the dark gray hollow carbon spheres in a tubular furnace again, introducing high-purity nitrogen for 20 minutes, heating to 1400 ℃ at the speed of 5 ℃/min under the protection of the nitrogen, preserving the heat for 1 hour, and naturally cooling to room temperature to obtain black hollow carbon spheres;placing the black sample in 1M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain the dark black hollow carbon sphere particles with the metal organic framework in-situ activation, wherein the outer diameter size is 1.15 mu M, the inner diameter size is 0.95 mu M, and the specific surface area is 1500 cm-3 g-195.5 at.%, 3.7 at.% N and 0.8 at.% O;
the dark black hollow carbon sphere particles prepared in example 3 were used as electrode raw materials, and a supercapacitor electrode and an alkali metal negative electrode were prepared respectively by a preparation method of literature (preparation and characterization of a Chenjiali heteroatom-doped porous carbon material and electrochemical performance research [ D ] Master academic thesis 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 5 is an SEM picture of the hollow carbon spheres prepared in example 3. Fig. 6 is an XRD spectrum of the hollow carbon sphere prepared in example 3.
Example 4
(1) Pouring 50 mL of DMF into a beaker, adding 1g of PVP with the average molecular weight of 130 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 30 mg of zinc acetate, 400 mg of zinc sulfate and 200 mg of trimesic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution into a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction at 200 ℃ for 1 hour;
(4) washing a sample subjected to solvent heating by adopting ethanol, centrifuging to obtain light yellow powder, and drying the yellow powder in an oven at 100 ℃ for 24 hours; (ii) a
(5) Grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing high-purity nitrogen for 20 minutes, heating to 750 ℃ at the speed of 5 ℃/min, preserving the temperature for 1 hour, and naturally cooling to room temperature to obtain dark gray hollow carbon spheres;
(6) placing the dark gray hollow carbon spheres in a tubular furnace again, introducing high-purity nitrogen for 20 minutes, heating to 1300 ℃ at the speed of 5 ℃/min under the protection of the nitrogen, preserving the temperature for 6 hours, and naturally cooling to room temperature to obtain a black sample; placing the black sample in 0.1M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain the dark black hollow carbon sphere particles with the in-situ activated metal organic framework, the outer diameter size of 1.05 mu M, the inner diameter size of 0.85 mu M, the specific surface area of 1300 cm-3 g-197.1 at.%, 2.7 at.% N and 0.2 at.% O;
the dark black hollow carbon sphere particles prepared in example 4 were used as electrode raw materials, and a supercapacitor electrode and an alkali metal negative electrode were prepared respectively by a preparation method of literature (preparation and characterization of a Chenjiali heteroatom-doped porous carbon material and electrochemical performance research [ D ] Master academic thesis 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 7 is an SEM picture of the hollow carbon spheres prepared in example 4. Fig. 8 is an XRD spectrum of the hollow carbon sphere prepared in example 4.
Comparative example 1
(1) Pouring 40 mL of DMF into a beaker, adding 1g of PVP with the average molecular weight of 5 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 400 mg of zinc acetate, 30 mg of zinc sulfate and 170 mg of phthalic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution to a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction for 6 hours at 100 ℃;
(4) cleaning a sample subjected to solvent thermal reaction by using ethanol, centrifuging to obtain light yellow powder, and drying the yellow powder in a drying oven at 100 ℃ for 36 hours;
(5) grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing high-purity nitrogen for 20 minutes, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 3 hours, and naturally cooling to room temperature to obtain dark gray solid carbon spheres;
(6) uniformly mixing dark gray solid carbon spheres and KOH according to the mass ratio of 3:1, putting the mixture into a tubular furnace again, introducing high-purity nitrogen for 20 minutes, heating the mixture to 1000 ℃ at the speed of 5 ℃/min under the protection of the nitrogen, preserving the heat for 4 hours, and naturally cooling the mixture to room temperature to obtain a black sample; placing a black sample in 1M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain a dark black activated solid carbon sphere derived from a metal organic framework, wherein the diameter of the activated solid carbon sphere is 0.55 mu M;
the deep black carbon spheres prepared in the comparative example 1 are used as electrode raw materials, and a supercapacitor electrode and an alkali metal negative electrode are respectively prepared by a preparation method of a literature (preparation and characterization of a Chenguo heteroatom-doped porous carbon material and electrochemical performance research thereof [ D ] Master academic paper 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 9 is an SEM picture of the carbon material prepared in comparative example 1.
Comparative example 2
(1) Pouring 45 mL of DMF into a beaker, adding 0.5 g of PVP with the average molecular weight of 5 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 400 mg of zinc acetate and 160 mg of trimesic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution into a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction for 6 hours at 150 ℃;
(4) cleaning a sample subjected to solvent thermal reaction by using ethanol, centrifuging to obtain light yellow powder, and drying the yellow powder in an oven at 100 ℃ for 24 hours;
(5) grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing high-purity nitrogen for 20 minutes, heating to 500 ℃ at the speed of 2 ℃/min, preserving the temperature for 10 hours, and naturally cooling to room temperature to obtain a dark gray carbon material;
(6) uniformly mixing a dark gray carbon material and KOH according to the mass ratio of 3:1, introducing high-purity nitrogen for 20 minutes, heating to 800 ℃ at the speed of 2 ℃/min under the protection of the nitrogen, preserving the temperature for 2 hours, and naturally cooling to room temperature to obtain a black sample; placing a black sample in a 1M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain a dark black carbon material;
the deep black carbon spheres prepared in the comparative example 2 are used as electrode raw materials, and a supercapacitor electrode and an alkali metal negative electrode are respectively prepared by a preparation method of a literature (preparation and characterization of a Chenguo heteroatom-doped porous carbon material and electrochemical performance research thereof [ D ] Master academic paper 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 10 is an SEM picture of the carbon material prepared in comparative example 2.
Comparative example 3
(1) Pouring 35 mL of DMF into a beaker, adding 1g of PVP with the average molecular weight of 1 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 430 mg of zinc acetate and 180 mg of terephthalic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution into a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction for 8 hours at 160 ℃;
(4) cleaning a sample subjected to solvent thermal reaction by using ethanol, centrifuging to obtain light yellow powder, and drying the yellow powder in a drying oven at 110 ℃ for 24 hours;
(5) grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing high-purity nitrogen for 20 minutes, heating to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 3 hours, and naturally cooling to room temperature to obtain a dark gray carbon material;
(6) placing the dark gray carbon material in a tubular furnace again, introducing high-purity nitrogen for 20 minutes, heating to 900 ℃ at the speed of 1 ℃/min under the protection of the nitrogen, preserving the heat for 2 hours, and naturally cooling to room temperature to obtain a black sample; placing the black sample in 0.5M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain a dark black metal organic framework activated carbon material;
the deep black carbon material prepared in the comparative example 3 is used as an electrode raw material, and a supercapacitor electrode and an alkali metal negative electrode are respectively prepared by a preparation method of a literature (preparation and characterization of a Chenguo heteroatom-doped porous carbon material and electrochemical performance research thereof [ D ] Master academic paper 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 11 is an SEM picture of the carbon material prepared in comparative example 3.
Comparative example 4
(1) Pouring 40 mL of DMF into a beaker, adding 1g of PVP with the average molecular weight of 5 ten thousand, and stirring by using a magnetic stirrer until the PVP is completely dissolved to obtain a clear and transparent solution;
(2) adding 430 mg of zinc nitrate and 150 mg of trimesic acid into the solution in the step (1), continuously stirring until all salts are dissolved to obtain a clear and transparent solution, and then transferring the solution into a 50 mL reaction kettle;
(3) placing the reaction kettle filled with the solution in an oven, and carrying out solvothermal reaction for 8 hours at 150 ℃;
(4) cleaning a sample subjected to solvent thermal reaction by using ethanol, centrifuging to obtain light yellow powder, and drying the yellow powder in a 60 ℃ oven for 48 hours;
(5) grinding and dispersing the dried pale yellow powder, placing the powder into a ceramic boat, placing the ceramic boat into a tube furnace, introducing high-purity nitrogen for 20 minutes, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 3 hours, and naturally cooling to room temperature to obtain a dark gray carbon material;
(6) placing the dark gray carbon material in a tubular furnace again, introducing high-purity nitrogen for 20 minutes, heating to 900 ℃ at the speed of 12 ℃/min under the protection of the nitrogen, preserving the heat for 2 hours, and naturally cooling to room temperature to obtain a black sample; placing a black sample in a 1M sulfuric acid aqueous solution, soaking for 24 hours, cleaning until the pH value is neutral, and drying to obtain a dark black metal organic framework activated carbon material;
the deep black carbon material prepared in the comparative example 4 is used as an electrode raw material, and a supercapacitor electrode and an alkali metal negative electrode are respectively prepared by a preparation method of a literature (preparation and characterization of a Chenguo heteroatom-doped porous carbon material and electrochemical performance research thereof [ D ] Master academic paper 2018 Anhui university of industry). Then respectively testing the performance of the super capacitor in a three-electrode system in 6M KOH aqueous solution; and its capacity and cycle performance in a lithium/sodium/potassium battery when used as the negative electrode, are shown in table 1.
Fig. 12 is an SEM picture of the carbon material prepared in comparative example 4.
TABLE 1 ultracapacitor and Battery Performance for examples 1, 2, 3, 4
Claims (9)
1. The metal organic framework in-situ activated hollow carbon sphere is characterized in that the outer diameter of the hollow carbon sphere is0.45-1.15 μm, inner diameter of 0.35-0.95 μm, and specific surface area of 600--3 g-1。
2. The hollow carbon sphere of claim 1, wherein the hollow carbon sphere is comprised of: c95.5 at.% to 99.2 at.%, N0.8 at.% to 3.7 at.%, and O0 to 0.8 at.%.
3. The preparation method of the metal organic framework in-situ activated hollow carbon sphere of claim 1 or 2, characterized by comprising the following steps:
(1) synthesis of metal organic framework particles:
adding polyvinylpyrrolidone, ligand and zinc salt into an organic solvent, and stirring to obtain a clear solution; then carrying out solvothermal reaction on the clear solution, cooling to room temperature after the reaction is finished, washing and drying to obtain metal organic framework particles;
(2) preparing metal organic framework in-situ activated hollow carbon spheres:
placing the metal organic framework particles obtained in the step (1) in a ceramic boat, and pretreating the ceramic boat under protective gas to obtain hollow carbon spheres;
(3) and (3) placing the hollow carbon spheres obtained in the step (2) in a ceramic boat, activating the ceramic boat under protective gas, cooling to obtain hollow carbon spheres, and cleaning and drying to obtain the metal organic framework in-situ activated hollow carbon sphere particles.
4. The preparation method according to claim 3, wherein the zinc salt in step (1) is one or two mixtures of zinc nitrate, zinc acetate and zinc sulfate; the ligand is phthalic acid or trimesic acid; the organic solvent is a mixed solution of N, N-dimethylformamide and ethanol, wherein the volume ratio of the ethanol to the N, N-dimethylformamide is (0-15): 20-50.
5. The preparation method according to claim 3, wherein the polyvinylpyrrolidone of step (1) has a molecular weight of 1 to 130 ten thousand; the mass-to-volume ratio of the metal salt, the ligand, the polyvinylpyrrolidone and the organic solvent in the step (1) is 430 mg: (100-200) mg: 1 g: (30-50) mL.
6. The preparation method according to claim 3, wherein the temperature of the solvothermal reaction in the step (1) is 110 to 200 ℃, and the reaction time is 1 to 24 hours; the solvent adopted for washing is ethanol; the drying temperature is 60-120 ℃, and the drying time is 24-72 hours.
7. The production method according to claim 3, characterized in that: in the step (2) and the step (3), the protective gas is nitrogen, argon or a hydrogen-argon mixed gas; the pretreatment temperature in the step (2) is 550-750 ℃, the heating rate is 5 ℃/min, and the pretreatment time is 1-10 hours; the activation treatment temperature of the step (3) is 800-1400 ℃, the heating rate is 1-10 ℃/min, and the activation treatment time is 1-10 hours; and (4) the cleaning in the step (3) is carried out by putting the mixture into 1-10M sulfuric acid for cleaning.
8. The method according to any one of claims 3 to 7, characterized in that the specific preparation method employs the following steps:
(1) taking 20-50 mL of N, N-dimethylformamide and 0-15 mL of ethanol mixed solution into a beaker, adding 1g of polyvinylpyrrolidone with the molecular weight of 1 ten thousand-130 ten thousand, and stirring by using a magnetic stirrer until the polyvinylpyrrolidone is completely dissolved; then adding 430 mg of zinc salt and 100-200 mg of phthalic acid or trimesic acid, and stirring by using a magnetic stirrer until the zinc salt and the phthalic acid or trimesic acid are completely dissolved to obtain a clear and transparent solution;
(2) transferring the clear transparent solution prepared in the step (1) into a polytetrafluoroethylene reaction kettle, placing the reaction kettle into an oven at the temperature of 110-200 ℃, preserving heat for 1-24 hours, naturally cooling to room temperature, cleaning a solvent DMF (dimethyl formamide) with ethanol, placing the cleaned powder into an oven at the temperature of 60-120 ℃, preserving heat for 24-72 hours, and obtaining metal organic framework particles;
(3) placing the metal organic frame particles prepared in the step (2) in a magnetic ceramic boat, placing the ceramic boat in a tube furnace under protective gas, heating to 550-750 ℃ at a heating rate of 5 ℃/min, preserving heat for 1-10 hours, and naturally cooling to obtain hollow carbon spheres;
(4) and (3) placing the pretreated sample in the step (3) in a ceramic boat, placing the ceramic boat in a tubular furnace under protective gas, heating to 800-1400 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 1-10 hours, naturally cooling, then placing in 1-10M sulfuric acid for cleaning, and drying to obtain the metal organic framework in-situ activated hollow carbon sphere particles.
9. Use of the metal organic framework in-situ activated hollow carbon spheres of claim 8, wherein: the hollow carbon spheres are used in the fields of supercapacitors, lithium/sodium/potassium ion batteries or catalysis.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114156092A (en) * | 2021-12-02 | 2022-03-08 | 济南大学 | Nitrogen-doped carbon microcube derived from metal organic framework and preparation method and application thereof |
| CN114220665A (en) * | 2021-12-14 | 2022-03-22 | 济南大学 | Metal organic framework derived nitrogen-doped carbon nanosheet and preparation method and application thereof |
| CN114797797A (en) * | 2022-03-11 | 2022-07-29 | 湖北工业大学 | Preparation method of hollow carbon nanocage hydrogel adsorption material with anion recognition function |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| EP2971277A1 (en) * | 2013-03-11 | 2016-01-20 | UTI Limited Partnership | Metal organic framework, production and use thereof |
| CN106904596A (en) * | 2017-03-06 | 2017-06-30 | 武汉理工大学 | The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application |
| KR20200021217A (en) * | 2018-08-20 | 2020-02-28 | 주식회사 엘지화학 | Metal Organic Framework, Method for Preparing the Same and Method for Preparing Porous Carbon Structure Using the Same |
| CN111453712A (en) * | 2019-01-21 | 2020-07-28 | 金华晨阳科技有限公司 | Hollow carbon ball with multistage pore structure and preparation method thereof |
-
2020
- 2020-10-09 CN CN202011069474.3A patent/CN112079346B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2971277A1 (en) * | 2013-03-11 | 2016-01-20 | UTI Limited Partnership | Metal organic framework, production and use thereof |
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| CN106904596A (en) * | 2017-03-06 | 2017-06-30 | 武汉理工大学 | The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application |
| KR20200021217A (en) * | 2018-08-20 | 2020-02-28 | 주식회사 엘지화학 | Metal Organic Framework, Method for Preparing the Same and Method for Preparing Porous Carbon Structure Using the Same |
| CN111453712A (en) * | 2019-01-21 | 2020-07-28 | 金华晨阳科技有限公司 | Hollow carbon ball with multistage pore structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHOI,S.等: "Facile Synthesis of Au or Ag Nanoparticles-Embedded Hollow Carbon Microspheres from Metal-Organic Framework Hybrids and Their Efficient Catalytic Activities", 《SMALL》, vol. 12, no. 18, 22 March 2016 (2016-03-22), pages 2425 - 2431 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114156092A (en) * | 2021-12-02 | 2022-03-08 | 济南大学 | Nitrogen-doped carbon microcube derived from metal organic framework and preparation method and application thereof |
| CN114220665A (en) * | 2021-12-14 | 2022-03-22 | 济南大学 | Metal organic framework derived nitrogen-doped carbon nanosheet and preparation method and application thereof |
| CN114797797A (en) * | 2022-03-11 | 2022-07-29 | 湖北工业大学 | Preparation method of hollow carbon nanocage hydrogel adsorption material with anion recognition function |
| CN114797797B (en) * | 2022-03-11 | 2023-04-28 | 湖北工业大学 | Preparation method of hollow carbon nano-cage hydrogel adsorption material with anion recognition function |
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