CN114524419B - Castor-like graphite carbon nitride nanotube/cobalt/carbon composite material and preparation method thereof - Google Patents
Castor-like graphite carbon nitride nanotube/cobalt/carbon composite material 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 104
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 54
- 239000010941 cobalt Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000002071 nanotube Substances 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 40
- 239000010439 graphite Substances 0.000 title claims abstract description 40
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000004443 Ricinus communis Nutrition 0.000 claims abstract description 24
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011358 absorbing material Substances 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 238000004729 solvothermal method Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 27
- 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 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 21
- 229920000877 Melamine resin Polymers 0.000 abstract description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 abstract description 4
- 229940044175 cobalt sulfate Drugs 0.000 abstract description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 abstract description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 abstract description 4
- 235000013399 edible fruits Nutrition 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 abstract 1
- 239000013110 organic ligand Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910021389 graphene Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 150000001868 cobalt Chemical class 0.000 description 4
- 240000000528 Ricinus communis Species 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
Abstract
The invention discloses a castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material and a preparation method thereof. Cobalt nitrate hexahydrate (cobalt chloride and cobalt sulfate) is used as metal salt, tribenzoic acid and polyvinylpyrrolidone are used as organic ligands, N, N-dimethylformamide is used as organic solvent, and a cobalt-metal organic framework is obtained through a solvothermal method. Grinding and mixing the cobalt-metal organic framework and melamine, and performing carbonization and pyrolysis to obtain the castor-bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material. The composite wave-absorbing material is formed by taking graphite carbon nitride nano-tubes as fruit thorns and spherical cobalt/carbon as fruit cores to form a special castor fruit-shaped morphology structure; the preparation process is simple and effective, and the cost is low. The prepared composite wave-absorbing material can meet the requirements of wide absorption bandwidth and high absorption strength at the same time under the ultra-thin thickness, and has important application value in the microwave absorption field.
Description
Technical Field
The invention belongs to the technical field of microwave absorbing materials, and particularly relates to a castor-bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material and a preparation method thereof.
Background
With the widespread and massive use of radio frequency devices, such as radio broadcasting, television, electromagnetic wave instruments, etc., electromagnetic wave interference or radiation pollution is caused. Electromagnetic wave pollution not only interferes with the normal operation of precision instruments, but also seriously damages human health. Electromagnetic wave absorbing materials are considered as effective measures for controlling electromagnetic wave pollution, and have been rapidly developed and intensively studied in recent years. Conventional magnetic microwave absorbing materials have been widely studied, which are mainly based on alloys or oxides of iron, nickel, cobalt. Although such magnetic absorbers have good microwave absorption properties, practical applications are limited due to excessive density.
The metal-organic frameworks are ideal precursors for novel microwave absorbing materials. The metal/carbon or metal oxide/carbon composite wave-absorbing material can be obtained through carbonization and pyrolysis. By adding the carbon component, the density of the material is effectively reduced. Meanwhile, the magnetic metal cobalt has high saturation magnetization and high Snoke limit, and electromagnetic microwave energy is mainly consumed through magnetic loss. The combination of a metal organic framework with a carbon material is considered to be an effective way to develop novel high performance electromagnetic microwave absorbing materials. The melamine can generate graphite carbon nitride nano-tubes through high-temperature pyrolysis. The melamine is used as the precursor of the graphite carbon nitride nano tube, and has the advantages of low cost, no need of acidification pretreatment, nitrogen introduction, material defect increase and the like. Therefore, melamine and cobalt-metal organic frameworks are used as raw materials, and the castor-bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material is designed and prepared, so that the castor-bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material can be considered to have important application value in the field of microwave absorption.
Disclosure of Invention
The invention aims to provide a castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material and a preparation method thereof. The composite material has the advantages of simple synthesis method, controllable microscopic morphology and adjustable microwave absorption performance; can simultaneously meet the requirements of wide absorption bandwidth and high absorption strength.
The technical scheme of the invention is as follows:
a castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material is composed of spherical cobalt/carbon surface-loaded graphite carbon nitride nanotubes.
The invention provides a preparation method of a castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material, which comprises the following steps:
(1) Stirring and ultrasonically treating N, N-dimethylformamide, cobalt salt and trimesic acid, and taking out after the treatment is finished to obtain a solution A;
(2) Stirring and ultrasonically treating absolute ethyl alcohol and polyvinylpyrrolidone, and taking out after the treatment is finished to obtain a solution B;
(3) Fully stirring the solution B, adding the solution A into the solution B for mixing and stirring treatment, and taking out after stirring to obtain a solution C;
(4) Transferring the solution C into a hydrothermal reaction kettle, performing solvothermal reaction, and performing cooling treatment and washing treatment after the reaction is finished to obtain a bottom precipitate;
(5) Drying the bottom sediment to constant weight, and taking out to obtain a cobalt-metal organic framework;
(6) Grinding and mixing the cobalt-metal organic frame and melamine powder, and taking out after uniform mixing to obtain light powder;
(7) And (3) carrying out high-temperature carbonization pyrolysis treatment on the light powder toner under the protection of nitrogen, then cooling, and cooling to room temperature to obtain the graphite carbon nitride nanotube/cobalt/carbon composite material.
Further, the cobalt salt in step (1) is one or more selected from cobalt nitrate, cobalt chloride and cobalt sulfate.
Further, in the step (1), the molar ratio of the cobalt nitrate to the trimesic acid is (4-n): (n), and the value range of n is an integer from 1 to 3.
Further, the volume ratio of the N, N-dimethylformamide in the step (1) to the absolute ethyl alcohol in the step (2) is 1:1.
Further, the mass of polyvinylpyrrolidone in the step (2) is 1g.
Further, the solvothermal reaction in the step (4) is carried out at a temperature of 120-200 ℃ for 10-20 hours.
Further, in the step (6), the mass ratio of the cobalt-metal organic framework to the melamine powder is 1:n, and the value range of n is an integer ranging from 1 to 7.
Further, the condition of the high-temperature carbonization pyrolysis treatment in the step (7) is that the temperature is firstly increased to 450-550 ℃, the temperature is kept for 2-4 hours, then the temperature is increased to 650-850 ℃, and the temperature is kept for 2-4 hours.
The invention provides a preparation method of a castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material, which has the following advantages:
first: the graphite carbon nitrogen nanotube/cobalt/carbon composite wave-absorbing material is prepared by adopting two steps of solvothermal and carbonization pyrolysis, and has the advantages of simple operation and unique appearance. Second,: the invention adopts N, N-dimethylformamide and absolute ethyl alcohol as organic solvents to obtain a spherical cobalt-metal organic framework. Third,: according to the invention, the composite wave-absorbing material for growing the graphite carbon nitride nano tube on the cobalt/carbon surface is obtained by carbonizing and pyrolyzing mixed powder of the cobalt-metal organic frame and the melamine at high temperature. By varying the mass ratio of the cobalt-metal organic framework and the melamine powder, the electromagnetic wave absorption capacity can be varied. Fourth,: the graphite carbon nitrogen nanotube/cobalt/carbon composite material prepared by the invention has excellent electromagnetic wave absorption performance, and can simultaneously realize the characteristics of thin thickness, strong absorption, wide frequency band and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a castor bean-shaped carbon nanotube/cobalt/carbon composite material according to examples 1-3;
FIG. 2 is an XRD spectrum of the graphite carbon nitride nanotube/cobalt/carbon composite material prepared in examples 1-3 in the preparation method of the castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material of the present invention;
FIG. 3 is a graph showing the Raman spectra of the graphite carbon nitride nanotube/cobalt/carbon composite materials prepared in examples 1-3 in the preparation method of the castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material;
FIG. 4 is an SEM image of the graphite carbon nitride nanotube/cobalt/carbon composite material prepared in examples 1-3 in the preparation method of the castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material of the present invention;
FIG. 5 is a TEM image of a graphene/cobalt/carbon composite material prepared in example 2 of a method for preparing a castor bean-shaped graphene/cobalt/carbon composite material according to the present invention;
FIG. 6 is a graph showing the reflection loss of the graphene/cobalt/carbon composite material with frequency obtained in example 1 of the preparation method of the graphene/cobalt/carbon composite material with castor bean shape according to the present invention;
FIG. 7 is a graph showing the reflection loss of the graphene/cobalt/carbon composite material with frequency obtained in example 2 of the preparation method of the graphene/cobalt/carbon composite material with castor bean shape according to the present invention;
FIG. 8 is a graph showing the reflection loss of the graphene/cobalt/carbon composite material with frequency obtained in example 3 of the preparation method of the graphene/cobalt/carbon composite material with castor bean shape according to the present invention.
Detailed Description
A preparation method of a castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material comprises the following steps:
step one: stirring and ultrasonically treating N, N-dimethylformamide, cobalt salt and trimesic acid, and taking out after the treatment is finished to obtain a solution A;
step two: fully stirring absolute ethyl alcohol and polyvinylpyrrolidone, fully carrying out ultrasonic treatment, and taking out after the treatment is finished to obtain a solution B.
Step three: and fully stirring the solution B, adding the solution A into the solution B for mixing and stirring treatment, and taking out after stirring to obtain a solution C.
Step four: transferring the solution C into a hydrothermal reaction kettle, performing solvothermal reaction, reacting for 10-20h at 120-200 ℃, and performing cooling treatment and washing treatment after the reaction is finished to obtain a bottom precipitate.
Step five: and (3) drying the bottom sediment at 60 ℃ for 24 hours until the weight is constant, and taking out to obtain the cobalt-metal organic framework.
Step six: and grinding and mixing the cobalt-metal organic frame and melamine powder, and taking out after uniformly mixing to obtain the light powder.
Step seven: and (3) under the protection atmosphere of nitrogen, carrying out high-temperature carbonization pyrolysis treatment on the light powder toner, firstly heating to 450-550 ℃, preserving heat for 2-4h, then heating to 650-850 ℃, and preserving heat for 2-4h. And then cooling to room temperature to obtain the graphite carbon nitride nanotube/cobalt/carbon composite material.
Wherein the cobalt salt in the step (1) is one or more selected from cobalt nitrate, cobalt chloride and cobalt sulfate; in the step (1), the total substance amount of the cobalt nitrate and the trimesic acid is 4mmol, the molar ratio of the cobalt nitrate to the trimesic acid is (4-n): (n), and the value range of n is an integer from 1 to 3; the volume ratio of the N, N-dimethylformamide in the step (1) to the absolute ethyl alcohol in the step (2) is 1:1, and is 20mL; the mass of the polyvinylpyrrolidone in the step (2) is 1g; in the step (6), the mass ratio of the cobalt-metal organic framework to the melamine powder is 1:n, and the value range of n is an integer ranging from 1 to 7.
In order to make the above objects, features and advantages of the present invention more comprehensible, the following embodiments accompanied with examples are further described. The invention is not limited to the embodiments listed but includes any other known modification within the scope of the claims that follow.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The preparation method of the castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material is shown as follows:
step one: 20mL of N, N-dimethylformamide, 3mmol of cobalt nitrate and 1mmol of trimesic acid are stirred for 60min, ultrasonic treatment is carried out for 30min, and after the treatment is finished, the solution A is obtained.
Step two: stirring 20mL of absolute ethyl alcohol and 1g of polyvinylpyrrolidone for 60min, carrying out ultrasonic treatment for 30min, and taking out after the treatment is finished to obtain a solution B.
Step three: and fully stirring the solution B, adding the solution A into the solution B, mixing and stirring for 60min, and taking out after stirring to obtain a solution C.
Step four: transferring the solution C into a hydrothermal reaction kettle, performing solvothermal reaction, reacting for 10 hours at 120 ℃, and performing cooling treatment and washing treatment after the reaction is finished to obtain a bottom precipitate.
Step five: and (3) drying the bottom sediment at 60 ℃ for 24 hours until the weight is constant, and taking out to obtain the cobalt-metal organic framework.
Step six: and grinding and mixing 0.2g of the cobalt-metal organic framework and 0.2g of melamine powder, and taking out after uniform mixing to obtain the light powder.
Step seven: and (3) under the protection atmosphere of nitrogen, carrying out high-temperature carbonization pyrolysis treatment on the light powder toner, firstly heating to 450 ℃, preserving heat for 2 hours, then heating to 650 ℃, and preserving heat for 2 hours. And then cooling to room temperature to obtain the graphite carbon nitride nanotube/cobalt/carbon composite material.
Example 2
The preparation method of the castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material is shown as follows:
step one: 20mL of N, N-dimethylformamide, 2mmol of cobalt chloride and 2mmol of trimesic acid are stirred for 60min, ultrasonic treatment is carried out for 30min, and after the treatment is finished, the solution A is obtained.
Step two: stirring 20mL of absolute ethyl alcohol and 1g of polyvinylpyrrolidone for 60min, carrying out ultrasonic treatment for 30min, and taking out after the treatment is finished to obtain a solution B.
Step three: and fully stirring the solution B, adding the solution A into the solution B, mixing and stirring for 60min, and taking out after stirring to obtain a solution C.
Step four: transferring the solution C into a hydrothermal reaction kettle, performing solvothermal reaction, reacting for 15 hours at 150 ℃, and performing cooling treatment and washing treatment after the reaction is finished to obtain a bottom precipitate.
Step five: and (3) drying the bottom sediment at 60 ℃ for 24 hours until the weight is constant, and taking out to obtain the cobalt-metal organic framework.
Step six: grinding and mixing 0.2g of the cobalt-metal organic framework and 0.6g of melamine powder, and taking out after uniform mixing to obtain the light powder.
Step seven: and (3) under the protection atmosphere of nitrogen, carrying out high-temperature carbonization pyrolysis treatment on the light powder toner, firstly heating to 500 ℃, preserving heat for 3 hours, then heating to 700 ℃, and preserving heat for 3 hours. And then cooling to room temperature to obtain the graphite carbon nitride nanotube/cobalt/carbon composite material.
Example 3
The preparation method of the castor bean-shaped graphite carbon nitride nanotube/cobalt/carbon composite material is shown as follows:
step one: 20mL of N, N-dimethylformamide, 1mmol of cobalt sulfate and 3mmol of trimesic acid are stirred for 60min, ultrasonic treatment is carried out for 30min, and after the treatment is finished, the solution A is obtained.
Step two: stirring 20mL of absolute ethyl alcohol and 1g of polyvinylpyrrolidone for 60min, carrying out ultrasonic treatment for 30min, and taking out after the treatment is finished to obtain a solution B.
Step three: and fully stirring the solution B, adding the solution A into the solution B, mixing and stirring for 60min, and taking out after stirring to obtain a solution C.
Step four: transferring the solution C into a hydrothermal reaction kettle, performing solvothermal reaction, reacting for 20 hours at 200 ℃, and performing cooling treatment and washing treatment after the reaction is finished to obtain a bottom precipitate.
Step five: and (3) drying the bottom sediment at 60 ℃ for 24 hours until the weight is constant, and taking out to obtain the cobalt-metal organic framework.
Step six: and grinding and mixing 0.2g of the cobalt-metal organic framework and 1.4g of melamine powder, and taking out after uniform mixing to obtain the light powder.
Step seven: and (3) under the protection atmosphere of nitrogen, carrying out high-temperature carbonization pyrolysis treatment on the light powder toner, firstly heating to 550 ℃, preserving heat for 4 hours, then heating to 850 ℃, and preserving heat for 4 hours. And then cooling to room temperature to obtain the graphite carbon nitride nanotube/cobalt/carbon composite material.
From the test results, the following conclusions were drawn:
XRD spectra of the samples of examples 1 to 3 are shown in FIG. 2, diffraction peaks of examples 1 to 3 at 44.2 °,51.5 ° and 75.8 ° coincide with positions corresponding to (111), (200) and (220) crystal planes of cobalt (JCCPDSNo. 15-0806), and diffraction peaks of 26.4 ° coincide with positions corresponding to (002) crystal planes of graphitic carbon (JCCPDS No. 41-1478). This indicates that the composite wave-absorbing material is composed of metallic cobalt and carbon. Raman spectra of the samples of examples 1-3 are shown in fig. 3; examples 1-3 samples at 1580cm -1 (G band) 1358cm -1 There are two distinct diffraction peaks near (D band), I D /I G The values of (2) are 0.85, 0.88 and 0.89, respectively.
SEM of samples of examples 1-3 is shown in FIG. 4. FIG. 4 (a) is an SEM image of a sample of example 1; the cobalt/carbon microspheres of the example 1 sample exhibited a distinct dispersed state, with a smaller number and shorter length of graphitic carbon nitride nanotubes. SEM photographs of the sample of example 2 are shown in fig. 4 (b); the cobalt/carbon microspheres of the sample of example 2 are in a dispersed state, the number of graphite carbon nitride nanotubes is obviously increased, and a good castor bean-shaped structure is formed. SEM photographs of the sample of example 3 are shown in fig. 4 (c); example 3 the cobalt/carbon microspheres in the sample aggregated severely, but the presence of graphitic carbon nitride nanotubes was also seen. TEM photograph of example 2 sample is shown in FIG. 5; it can be seen that the apparent spherical cobalt/carbon core and the nano-tubular graphite carbon nitride nano-tubes.
Pressing the samples of the examples 1-3 and paraffin according to the mass ratio of 4:6 to obtain a coaxial ring sample, testing electromagnetic parameters of the coaxial ring sample by using an AV3629D vector network analyzer, and calculating to obtain the wave absorbing performance, wherein the frequency range is 2.0-18.0GHz. The reflection loss versus frequency curve for the sample of example 1 is shown in FIG. 6, and the maximum absorption intensity reaches-15.55 dB when the matching thickness is 4.00 mm. The reflection loss versus frequency curve for the sample of example 2 is shown in FIG. 7, and the maximum absorption intensity reaches-63.90 dB when the matching thickness is 1.96 mm. When the matching thickness is 1.51mm, the maximum absorption bandwidth reaches 4.44GHz, and the corresponding absorption intensity is-43.86 dB. The reflection loss versus frequency curve of the sample of example 3 is shown in FIG. 8, and the maximum absorption intensity is-32.87 dB when the matching thickness is 1.55mm, corresponding to a maximum absorption bandwidth of 3.44GHz.
According to the test results of the embodiment, the graphite carbon nitride nano tube/cobalt/carbon composite material is prepared by adopting a solvothermal and carbonization pyrolysis method, the special castor bean-shaped morphology structure is formed by taking the graphite carbon nitride nano tube as a fruit thorn and taking spherical cobalt/carbon as a fruit core, the preparation process is simple and effective, the cost is low, the microcosmic morphology and the microwave absorption performance of the prepared composite material can be effectively regulated by changing the mass ratio of the cobalt-metal organic framework precursor to melamine, and the wide absorption band and the high absorption strength under the ultra-thin thickness are realized, so that the castor bean-shaped graphite carbon nitride nano tube/cobalt/carbon composite material is a novel microwave absorption material with potential application value.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (3)
1. The application of the castor bean-shaped graphite carbon nitride nano tube/cobalt/carbon composite material in the microwave absorbing material is characterized in that the method comprises the following steps: (1) Stirring and ultrasonically treating N, N-dimethylformamide, cobalt nitrate and trimesic acid, and taking out after the treatment is finished to obtain a solution A;
in the step (1), the molar ratio of the cobalt nitrate to the trimesic acid is (4-n): (n), and the value range of n is an integer from 1 to 3;
(2) Stirring and ultrasonically treating absolute ethyl alcohol and polyvinylpyrrolidone, and taking out after the treatment is finished to obtain a solution B; the mass of the polyvinylpyrrolidone in the step (2) is 1g;
(3) Fully stirring the solution B, adding the solution A into the solution B for mixing and stirring treatment, and taking out after stirring to obtain a solution C;
(4) Transferring the solution C into a hydrothermal reaction kettle, performing solvothermal reaction, and performing cooling treatment and washing treatment after the reaction is finished to obtain a bottom precipitate;
(5) Drying the bottom sediment to constant weight, and taking out to obtain a cobalt-metal organic framework;
(6) Grinding and mixing the cobalt-metal organic frame and melamine powder, and taking out after uniform mixing to obtain light powder;
in the step (6), the mass ratio of the cobalt-metal organic framework to the melamine powder is 1:n, and the value range of n is an integer of 1-7;
(7) Carrying out high-temperature carbonization pyrolysis treatment on the light powder toner under the protection of nitrogen, then cooling to room temperature to obtain a graphite carbon nitride nanotube/cobalt/carbon composite material;
the conditions of the high-temperature carbonization pyrolysis treatment in the step (7) are that the temperature is firstly increased to 450-550 ℃, the heat is preserved for 2-4 hours, then the temperature is increased to 650-850 ℃, and the heat is preserved for 2-4 hours.
2. The use of a castor bean-shaped graphitic carbon nitride nanotube/cobalt/carbon composite material according to claim 1 in a microwave absorbing material, wherein: the volume ratio of the N, N-dimethylformamide in the step (1) to the absolute ethyl alcohol in the step (2) is 1:1.
3. The use of a castor bean-shaped graphitic carbon nitride nanotube/cobalt/carbon composite material according to claim 1 in a microwave absorbing material, wherein: the solvothermal reaction in the step (4) is carried out at a temperature of 120-200 ℃ for 10-20 hours.
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| CN110773217A (en) * | 2019-09-24 | 2020-02-11 | 嘉兴学院 | Preparation method of nitrogen-doped carbon nanotube material containing transition metal |
| CN110721750A (en) * | 2019-10-14 | 2020-01-24 | 浙江海洋大学 | Preparation method of graphite-like phase carbon nitride/MOFs catalytic material |
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