CN114261950A - Tubular cobalt hybrid g-C3N4Material, microwave synthesis method thereof and application of material in field of super capacitor - Google Patents
Tubular cobalt hybrid g-C3N4Material, microwave synthesis method thereof and application of material in field of super capacitor Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 46
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- 239000003990 capacitor Substances 0.000 title abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 39
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000007974 melamines Chemical class 0.000 claims abstract description 12
- 238000001953 recrystallisation Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 21
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- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 150000007973 cyanuric acids Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 5
- NVLDSCWHEUSPCV-UHFFFAOYSA-N [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NVLDSCWHEUSPCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000012047 saturated solution Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
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- 239000012921 cobalt-based metal-organic framework Substances 0.000 abstract description 2
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- 238000009776 industrial production Methods 0.000 abstract description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 abstract 2
- BPGLMKMMPBQINX-UHFFFAOYSA-N C(#N)N1C(=O)NC=2NC(=O)NC2C1=O.N1=C(N)N=C(N)N=C1N Chemical compound C(#N)N1C(=O)NC=2NC(=O)NC2C1=O.N1=C(N)N=C(N)N=C1N BPGLMKMMPBQINX-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
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- 229920000877 Melamine resin Polymers 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000002131 composite material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a tubular cobalt hybridized g-C3N4The material and the microwave synthesis method and the application in the super capacitor field are that first, the saturated melamine solution and the saturated melamine solution are utilized to prepare the melamine-cyanuric acid supermolecule aggregate, then the rodlike melamine-cyanuric acid supermolecule precursor is obtained by hydrothermal recrystallization, and then the rodlike melamine-cyanuric acid supermolecule precursor is obtained by rodlike melamine-cyanuric acidCoating a layer of two-dimensional cobalt-based MOF material on the surface of the cyanic acid supermolecule precursor, and finally quickly synthesizing tubular cobalt hybrid g-C by a microwave method3N4A material. The material has a large specific surface area and a high capacitance performance, shows good charge and discharge performance, and has a good application prospect in the field of supercapacitors. The method has the advantages of simple steps, convenient operation, greatly reduced preparation energy consumption and synthesis time, energy conservation and environmental protection, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of preparation and application of energy storage materials, in particular to tubular cobalt hybridized g-C3N4A material, a microwave synthesis method thereof and application thereof in the field of supercapacitors.
Background
The carbon material has the advantages of good conductivity, stable chemical properties and the like, and is widely researched in the field of super capacitors. At present, a great deal of research reports prove that the capacitance performance of the carbon material can be effectively improved by doping of heteroatoms (O, B, N, P, S and the like). Wherein, the doping effect of N atoms is more remarkable, and the graphite phase carbon nitride (g-C)3N4) Has great application prospect in the field of energy storage as a carbon material with high nitrogen content, and g-C is different from the traditional carbon material doped with N atoms3N4The raw materials are rich, the preparation is simple, and the preparation process is safe and nontoxic.
However, the blocks g-C obtained directly by thermal polymerization3N4The self capacitance is poor, the traditional muffle furnace heating mode has high energy consumption and low heat utilization rate, and the large-scale application of the muffle furnace is severely limited. Thus, how to increase g-C3N4The capacitance of the capacitor is reduced, and the energy consumption of the preparation is reduced, which becomes a hot point of research.
Specific surface lifting pair lifting g-C3N4The capacitance of (a) has an important role. Mesoporous g-C3N4Material, effectively improves g-C3N4Capacitive (electrochimica acta,2019,303:219- & 230). In addition, in g-C3N4The introduction of a material with a high theoretical specific capacitance into the material also has a significant effect. Such as A.ChandraBose, Nikhitha Joseph, et al (Electrochimica acta,2019,301:401-410) by mixing at g-C3N4Introduction of MoS into material2High performance MoS is obtained2/g-C3N4Compounding supercapacitor electrodes; guangzhidong, Huiqingfan, etc. prepared sandwich structured g-C3N4The/polypyrrole composite electrodes exhibit excellent capacitive stability (composite part b: Engineering,2019,162: 369-377).
In addition to increasing g-C3N4How to reduce g-C in addition to the capacitive properties of the material3N4The energy consumption for preparation is another key problem. The microwave method has the advantages of extremely high heating speed, fixed-point heating and the like, and has been successfully applied to the synthesis of nano materials. However, due to the application in the preparation of g-C3N4The precursors of the material (such as melamine, dicyandiamide, urea, thiourea and the like) are not sensitive to microwaves, and the microwave method is seriously limited to the g-C3N4Application in preparation.
Disclosure of Invention
One purpose of the invention is to provide tubular cobalt hybridized g-C3N4The microwave synthesis method of the material has the advantages of simple steps, convenient operation, greatly reduced preparation energy consumption and synthesis time, energy conservation and environmental protection.
The second purpose of the invention is to provide tubular cobalt hybridized g-C prepared by the synthesis method3N4The material has larger specific surface area and higher capacitance performance.
The invention also aims to provide the tubular cobalt hybridized g-C3N4The application of the material in the field of supercapacitors.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a tubular cobalt hybrid g-C3N4The microwave synthesis method of the material comprises the following steps:
s1, mixing the saturated melamine clear solution and the saturated cyanuric acid clear solution in an equimolar manner to form a melamine-cyanuric acid supramolecular aggregate with a loose structure;
s2, centrifugally cleaning the melamine-cyanuric acid supramolecular aggregate, dispersing the supramolecular aggregate in an aqueous solution again, and performing hydrothermal treatment and recrystallization; after the reaction is finished, centrifuging, freezing and drying to obtain a rod-shaped melamine-cyanuric acid supramolecular precursor with uniform size and good crystallization;
s3, dispersing the rodlike melamine-cyanuric acid supramolecular precursor in absolute ethyl alcohol, adding surfactant polyvinylpyrrolidone, fully stirring for reaction to form a mixed solution, and centrifugally cleaning with absolute methyl alcohol to obtain polyvinylpyrrolidone-modified rodlike supramolecules;
s4, dispersing the rodlike supramolecules modified by polyvinylpyrrolidone into anhydrous methanol, adding a cobalt nitrate methanol solution and a 2-methylimidazole methanol solution, fully stirring for reaction to form a mixed solution, centrifuging by using the anhydrous methanol, cleaning and drying to obtain a two-dimensional MOF-coated rodlike supramolecular precursor;
s5, placing the two-dimensional MOF coated rodlike supramolecular precursor in a crucible, and heating by using microwaves to obtain tubular cobalt hybridized g-C3N4A material.
Preferably, in step S2, the mass ratio of the melamine-cyanuric acid supramolecular aggregate to water is (0.02-0.04): 1; the hydrothermal treatment temperature is 120-150 ℃, and the hydrothermal treatment time is 6-12 h.
Preferably, in step S3, the mass ratio of the rod-like melamine-cyanuric acid supramolecular precursor to the absolute ethyl alcohol to the polyvinylpyrrolidone is (0.1-0.5): 20: 0.1; the stirring speed is 60-120 rpm, and the stirring time is 3-12 hours.
Preferably, in step S4, the mass ratio of the polyvinylpyrrolidone-modified rodlike supramolecules, the anhydrous methanol, the cobalt nitrate, and the 2-methylimidazole in the mixed solution is (0.1 to 0.5): 24: 0.9: 0.07; the stirring speed is 60-120 rpm, and the stirring time is 12-24 hours.
Preferably, in step S5, the microwave heating power is 700-1000W, and the microwave time is 20-40 min.
Preferably, in step S1, the saturated melamine clear solution and the saturated cyanuric acid clear solution are both saturated solutions formed when heated to 80 ℃ in a water bath.
In a second aspect, the invention also provides tubular cobalt hybridized g-C obtained by adopting the synthesis method3N4A material.
Preferably, said g-C3N4The material is tubular, and the cobalt hybrid is coated on the tubular g-C3N4The surface of the material.
In a third aspect, the invention also provides the tubular cobalt hybridized g-C3N4The application of the material in the field of supercapacitors.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, saturated melamine and a saturated melamine solution under a hydrothermal condition are used for preparing a supramolecular precursor, a high-yield supramolecular aggregate is obtained, and the supramolecular precursor with uniform appearance and good crystallization can be obtained through hydrothermal recrystallization;
(2) the invention grows a layer of two-dimensional cobalt MOF (metal organic framework) material on the surface of a rodlike melamine-cyanuric acid supermolecule precursor, the two-dimensional cobalt MOF material has a microwave absorption function and can be used as a microwave absorbent, and tubular cobalt hybridized g-C is quickly obtained by direct microwave heating3N4The method is simple and convenient, is easy to operate, greatly reduces the preparation energy consumption and the synthesis time, is energy-saving and environment-friendly, and is suitable for large-scale industrial production;
(3) the invention controls g-C3N4The precursor shape is used for obtaining g-C with larger specific surface area3N4Material to increase g-C3N4The capacitive properties of the material; the invention realizes g-C by introducing a second-phase two-dimensional cobalt MOF material with a microwave absorption function3N4Microwave synthesis and simultaneous decomposition of materialsSolves the existing g-C3N4The capacitance of the material is low and the energy consumption for preparation is high;
(4) tubular cobalt hybridized g-C obtained by the invention3N4Due to the advantages of the tubular structure and the doping of the cobalt element which is a high theoretical capacitance material, the material shows good charge and discharge performance and has good application prospect in the field of super capacitors.
Drawings
FIG. 1 is the preparation of tubular cobalt hybrid g-C of the present invention3N4A process schematic of a material;
FIG. 2 is an SEM image of a rodlike melamine-cyanuric acid supramolecular precursor prepared by the invention;
FIG. 3 is a graph of tubular g-C prepared from a comparative example of the present invention3N4A microscopic view of the material, (b) an SEM view, (c) a TEM view;
FIG. 4 shows the tubular cobalt hybridized g-C prepared in the first embodiment of the present invention3N4A microscopic image of the material, (d) an SEM image; (e) a TEM image;
FIG. 5 shows the tubular cobalt hybridized g-C prepared in the first embodiment of the present invention3N4Analyzing the element content spectrogram of the material;
FIG. 6 shows the tubular cobalt hybridized g-C prepared in the first embodiment of the present invention3N4XPS spectrogram of the material, (a) XPS general spectrogram, (b) Co element high-resolution spectrogram;
FIG. 7 is a tubular g-C prepared for the comparative example3N4Material and tubular cobalt hybridized g-C prepared in first embodiment of the invention3N4The comparative schematic diagram of the super-electric performance of the material is shown in the following steps of (a) a cyclic voltammetry curve, (b) a charge-discharge performance curve under the condition of 2A/g current density, and (c) a charge-discharge performance curve under the condition of different current densities.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example one
As shown in figure 1, a tubular cobalt hybrid g-C3N4The microwave synthesis method of the material comprises the following steps:
s1, respectively dissolving 8g of melamine and 8g of cyanuric acid powder in 400ml of deionized water, respectively heating in a water bath to 80 ℃ to form saturated solutions, and mixing the saturated melamine clear solution and the saturated cyanuric acid clear solution to form a melamine-cyanuric acid supramolecular aggregate with a loose structure;
s2, after centrifugally cleaning the melamine-cyanuric acid supramolecular aggregate, re-dispersing the melamine-cyanuric acid supramolecular aggregate into 400ml of aqueous solution to form 450ml of mixed solution, dividing the mixed solution into 6 parts of mixed solution with the volume of 75ml, respectively transferring the 6 parts of mixed solution with the volume of 75ml into 6 polytetrafluoroethylene reaction kettles with the volume of 100ml, and performing hydrothermal reaction in an oven at 150 ℃ for 12 hours to perform recrystallization; centrifuging and freeze-drying after the reaction is finished to obtain a rodlike melamine-cyanuric acid supramolecular precursor with uniform size and good crystallization, wherein an SEM image of the supramolecular precursor is shown in figure 2, and the supramolecular precursor can be seen to be in a rodlike structure with uniform size;
s3, dispersing 0.5g of rodlike melamine-cyanuric acid supramolecular precursor into 20ml of absolute ethyl alcohol, and adding 0.1g of surfactant polyvinylpyrrolidone, wherein the mass ratio of the rodlike melamine-cyanuric acid supramolecular precursor to the absolute ethyl alcohol to the polyvinylpyrrolidone is 0.5: 20: 0.1, fully stirring to react to form a mixed solution, wherein the stirring speed is 60 revolutions per minute, the stirring time is 12 hours, and finally, carrying out centrifugal cleaning by using absolute methanol to obtain polyvinylpyrrolidone modified rodlike supramolecules;
s4, dispersing the rodlike supramolecules modified by the polyvinylpyrrolidone into 10ml of anhydrous methanol, respectively adding 10ml of cobalt nitrate methanol solution with the concentration of 0.3mol/L and 10ml of 2-methylimidazole methanol solution with the concentration of 0.08mol/L, fully stirring and reacting to form a mixed solution, wherein the mass ratio of the rodlike supramolecules modified by the polyvinylpyrrolidone, the anhydrous methanol, the cobalt nitrate and the 2-methylimidazole in the mixed solution is 0.5: 24: 0.9: 0.07, the stirring speed is 60 revolutions per minute, and the stirring time is 24 hours; finally, centrifuging, cleaning and drying the mixture by using anhydrous methanol to obtain a two-dimensional MOF coated rod-shaped supramolecular precursor;
s5, mixingPlacing 0.5g of two-dimensional MOF coated rodlike supramolecular precursor in a 25ml crucible, placing in a 50ml large crucible, and heating with 700W microwave for 40min to obtain tubular cobalt-hybridized g-C3N4The microscopic picture, the element content analysis spectrogram and the XPS spectrogram of the material are respectively shown in fig. 4, fig. 5 and fig. 6, and as can be seen from fig. 4, the prepared material still keeps a good tubular structure, and the tube wall is coated with a layer of flaky material, namely the flaky two-dimensional cobalt-based MOF material; as can be seen from fig. 5, the resulting material is enriched in C, N, O, Co four elements; as can be seen from FIG. 6, (a) the total spectrum shows that the surface of the material is rich in C, N, O, Co four elements, (b) the cobalt element high resolution spectrum shows that the peak is 2p at 781.3eV3/2(CoOx) Illustrates the conversion of two-dimensional cobalt MOF material to CoO during microwave heatingx(CoO and Co)3O4Mixed materials).
Comparison group
The rodlike melamine-cyanuric acid supermolecule precursor prepared in the step S2 of the embodiment is roasted at 520 ℃ in a muffle furnace, the heating rate is 5 ℃/min, and the heat preservation time is 2h to obtain tubular g-C3N4The microscopic picture is shown in fig. 3, and it can be seen that the obtained tubular material has uniform size and complete structure, and the wall of the tubular material is rich in abundant pore structures.
FIG. 7 is a tubular g-C prepared for the comparative example3N4Materials and preparation of tubular cobalt hybrid g-C in this example3N4And (5) testing the super-electric performance of the material. The cyclic voltammogram results of FIG. 7(a) show that the pure tubular g-C3N4In contrast, tubular cobalt hybridized g-C3N4The material has a higher electrochemical window, indicating that it has better electrochemical activity. FIG. 7(b) Charge/discharge Performance results at 2A/g show that tubular cobalt hybridizes to g-C3N4The capacitance performance of the material is about pure g-C3N43.3 times of the total weight of the powder. FIG. 7(C) shows tubular cobalt hybridization g-C at 1A/g3N4The maximum capacitance of the material can be as high as 830F/g, which is much higher than that of other g-C in the literature3N4A base material.
Example two
As shown in figure 1, a tubular cobalt hybrid g-C3N4The microwave synthesis method of the material comprises the following steps:
s1, respectively dissolving 8g of melamine and 8g of cyanuric acid powder in 400ml of deionized water, respectively heating in a water bath to 80 ℃ to form saturated solutions, and mixing the saturated melamine clear solution and the saturated cyanuric acid clear solution to form a melamine-cyanuric acid supramolecular aggregate with a loose structure;
s2, after centrifugally cleaning the melamine-cyanuric acid supramolecular aggregate, re-dispersing the melamine-cyanuric acid supramolecular aggregate into 400ml of aqueous solution to form 450ml of mixed solution, dividing the mixed solution into 6 parts of mixed solution with the volume of 75ml, respectively transferring the 6 parts of mixed solution with the volume of 75ml into 6 polytetrafluoroethylene reaction kettles with the volume of 100ml, and performing hydrothermal reaction in an oven at 150 ℃ for 9 hours to perform recrystallization; after the reaction is finished, centrifuging, freezing and drying to obtain a rod-shaped melamine-cyanuric acid supramolecular precursor with uniform size and good crystallization;
s3, dispersing 0.1g of rodlike melamine-cyanuric acid supramolecular precursor into 20ml of absolute ethyl alcohol, and adding 0.1g of surfactant polyvinylpyrrolidone, wherein the mass ratio of the rodlike melamine-cyanuric acid supramolecular precursor to the absolute ethyl alcohol to the polyvinylpyrrolidone is 0.1: 20: 0.1, fully stirring to react to form a mixed solution, wherein the stirring speed is 90 revolutions per minute, the stirring time is 7 hours, and finally, carrying out centrifugal cleaning by using absolute methanol to obtain polyvinylpyrrolidone modified rodlike supramolecules;
s4, dispersing the rodlike supramolecules modified by the polyvinylpyrrolidone into 10ml of anhydrous methanol, respectively adding 10ml of cobalt nitrate methanol solution with the concentration of 0.3mol/L and 10ml of 2-methylimidazole methanol solution with the concentration of 0.08mol/L, fully stirring and reacting to form a mixed solution, wherein the mass ratio of the rodlike supramolecules modified by the polyvinylpyrrolidone, the anhydrous methanol, the cobalt nitrate and the 2-methylimidazole in the mixed solution is 0.1: 24: 0.9: 0.07, the stirring speed is 90 r/min, and the stirring time is 18 h; finally, centrifuging, cleaning and drying the mixture by using anhydrous methanol to obtain a two-dimensional MOF coated rod-shaped supramolecular precursor;
s5, two-dimensional mixing of 0.5gPlacing the MOF coated rod-shaped supermolecule precursor in a 25ml crucible, placing in a 50ml large crucible, and heating with 850W microwave for 30min to obtain tubular cobalt hybridized g-C3N4A material.
EXAMPLE III
As shown in figure 1, a tubular cobalt hybrid g-C3N4The microwave synthesis method of the material comprises the following steps:
s1, respectively dissolving 8g of melamine and 8g of cyanuric acid powder in 400ml of deionized water, respectively heating in a water bath to 80 ℃ to form saturated solutions, and mixing the saturated melamine clear solution and the saturated cyanuric acid clear solution to form a melamine-cyanuric acid supramolecular aggregate with a loose structure;
s2, after centrifugally cleaning the melamine-cyanuric acid supramolecular aggregate, re-dispersing the melamine-cyanuric acid supramolecular aggregate into 400ml of aqueous solution to form 450ml of mixed solution, dividing the mixed solution into 6 parts of mixed solution with the volume of 75ml, respectively transferring the 6 parts of mixed solution with the volume of 75ml into 6 polytetrafluoroethylene reaction kettles with the volume of 100ml, and performing hydrothermal reaction in an oven at 120 ℃ for 12 hours to perform recrystallization; after the reaction is finished, centrifuging, freezing and drying to obtain a rod-shaped melamine-cyanuric acid supramolecular precursor with uniform size and good crystallization;
s3, dispersing 0.2g of rodlike melamine-cyanuric acid supramolecular precursor into 20ml of absolute ethyl alcohol, and adding 0.1g of surfactant polyvinylpyrrolidone, wherein the mass ratio of the rodlike melamine-cyanuric acid supramolecular precursor to the absolute ethyl alcohol to the polyvinylpyrrolidone is 0.2: 20: 0.1, fully stirring to react to form a mixed solution, wherein the stirring speed is 120 r/min, the stirring time is 3h, and finally, carrying out centrifugal cleaning by using absolute methanol to obtain polyvinylpyrrolidone modified rodlike supramolecules;
s4, dispersing the rodlike supramolecules modified by the polyvinylpyrrolidone into 10ml of anhydrous methanol, respectively adding 10ml of cobalt nitrate methanol solution with the concentration of 0.3mol/L and 10ml of 2-methylimidazole methanol solution with the concentration of 0.08mol/L, fully stirring and reacting to form a mixed solution, wherein the mass ratio of the rodlike supramolecules modified by the polyvinylpyrrolidone, the anhydrous methanol, the cobalt nitrate and the 2-methylimidazole in the mixed solution is 0.2: 24: 0.9: 0.07, the stirring speed is 120 r/min, and the stirring time is 12 h; finally, centrifuging, cleaning and drying the mixture by using anhydrous methanol to obtain a two-dimensional MOF coated rod-shaped supramolecular precursor;
s5, placing 0.5g of two-dimensional MOF coated rod-like supramolecular precursor in a 25ml crucible, placing the crucible in a 50ml large crucible, and heating the crucible for 20min by using 1000W microwave to obtain tubular cobalt hybridized g-C3N4A material.
Claims (9)
1. Tubular cobalt hybrid g-C3N4The microwave synthesis method of the material is characterized by comprising the following steps:
s1, mixing the saturated melamine clear solution and the saturated cyanuric acid clear solution in an equimolar manner to form a melamine-cyanuric acid supramolecular aggregate with a loose structure;
s2, centrifugally cleaning the melamine-cyanuric acid supramolecular aggregate, dispersing the supramolecular aggregate in an aqueous solution again, and performing hydrothermal treatment and recrystallization; after the reaction is finished, centrifuging, freezing and drying to obtain a rod-shaped melamine-cyanuric acid supramolecular precursor with uniform size and good crystallization;
s3, dispersing the rodlike melamine-cyanuric acid supramolecular precursor into absolute ethyl alcohol, adding surfactant polyvinylpyrrolidone, fully stirring and reacting to form a mixed solution, and centrifugally cleaning with absolute methyl alcohol to obtain a polyvinylpyrrolidone-modified rodlike supramolecular precursor;
s4, dispersing the polyvinylpyrrolidone modified rodlike supramolecular precursor into anhydrous methanol, adding a cobalt nitrate methanol solution and a 2-methylimidazole methanol solution, fully stirring for reaction to form a mixed solution, centrifuging with the anhydrous methanol, cleaning, and drying to obtain a two-dimensional MOF coated rodlike supramolecular precursor;
s5, placing the two-dimensional MOF coated rodlike supramolecular precursor in a crucible, and heating by using microwaves to obtain tubular cobalt hybridized g-C3N4A material.
2. A tubular cobalt hybrid g-C as claimed in claim 13N4Microwave of materialThe synthesis method is characterized in that in step S2, the mass ratio of the melamine-cyanuric acid supramolecular aggregate to water is (0.02-0.04): 1; the hydrothermal treatment temperature is 120-150 ℃, and the hydrothermal treatment time is 9-12 h.
3. A tubular cobalt hybrid g-C according to claim 1 or 23N4The microwave synthesis method of the material is characterized in that in the step S3, the mass ratio of the rodlike melamine-cyanuric acid supramolecular precursor to the absolute ethyl alcohol to the polyvinylpyrrolidone is (0.1-0.5): 20: 0.1; the stirring speed is 60-120 rpm, and the stirring time is 3-12 hours.
4. A tubular cobalt hybrid g-C according to claim 1 or 23N4The microwave synthesis method of the material is characterized in that in step S4, the mass ratio of the polyvinylpyrrolidone-modified rodlike supramolecules, anhydrous methanol, cobalt nitrate and 2-methylimidazole in the mixed solution is (0.1-0.5): 24: 0.9: 0.07; the stirring speed is 60-120 rpm, and the stirring time is 12-24 hours.
5. A tubular cobalt hybrid g-C according to claim 1 or 23N4The microwave synthesis method of the material is characterized in that in the step S5, the microwave heating power is 700-1000W, and the microwave time is 20-40 min.
6. A tubular cobalt hybrid g-C according to claim 1 or 23N4The microwave synthesis method of the material is characterized in that in the step S1, the saturated melamine clear solution and the saturated cyanuric acid clear solution are both saturated solutions formed when the saturated melamine clear solution and the saturated cyanuric acid clear solution are heated to 80 ℃ in a water bath.
7. Tubular cobalt hybrid g-C3N4A material characterized by: obtained by the synthesis method of any one of claims 1 to 6.
8. A tubular cobalt hybrid g-C according to claim 73N4A material characterized by: the g to C3N4The material is tubular, and the cobalt hybrid is coated on the tubular g-C3N4The surface of the material.
9. A tubular cobalt hybrid g-C according to claim 7 or 83N4The application of the material in the field of supercapacitors.
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| CN106169381A (en) * | 2016-07-26 | 2016-11-30 | 北京工业大学 | A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67 |
| CN108579787A (en) * | 2018-04-26 | 2018-09-28 | 天津大学 | A kind of preparation method for the regenerated heterojunction photocatalysts of NADH |
| CN113801631A (en) * | 2021-11-09 | 2021-12-17 | 西北大学 | MnCo2O4@ ZIF-67/Ni wave-absorbing material and preparation method thereof |
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| CN106169381A (en) * | 2016-07-26 | 2016-11-30 | 北京工业大学 | A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67 |
| CN108579787A (en) * | 2018-04-26 | 2018-09-28 | 天津大学 | A kind of preparation method for the regenerated heterojunction photocatalysts of NADH |
| CN113801631A (en) * | 2021-11-09 | 2021-12-17 | 西北大学 | MnCo2O4@ ZIF-67/Ni wave-absorbing material and preparation method thereof |
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