CN116496460B - Covalent organic framework material, ligand and application thereof - Google Patents
Covalent organic framework material, ligand and application thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000003446 ligand Substances 0.000 title claims abstract description 17
- 239000007772 electrode material Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 10
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- UHFVZQIOQVEYQM-UHFFFAOYSA-N methyl 2-amino-5-cyano-3-methylbenzoate Chemical compound COC(=O)C1=CC(C#N)=CC(C)=C1N UHFVZQIOQVEYQM-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZMJBYMUCKBYSCP-UHFFFAOYSA-N Hydroxycitric acid Chemical compound OC(=O)C(O)C(O)(C(O)=O)CC(O)=O ZMJBYMUCKBYSCP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- 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
- H01G11/48—Conductive polymers
-
- 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
Abstract
A covalent organic framework material and ligands and uses thereof. The invention belongs to the field of electrode materials. The invention provides a covalent organic framework material COF-ET11 which has higher electrochemical performance in a constant current charge-discharge test; the mass specific capacitance of the covalent organic framework material can reach 2989F/g at the time of 10A/g, and the retention rate is 98%; after 10000 times of circulation, the covalent organic framework material COF-ET11 can still keep about 98% of mass specific capacitance, and has good circulation stability, so that the covalent organic framework material COF-ET11 has good application prospect in the field of supercapacitors.
Description
Technical Field
The invention belongs to the field of electrode materials, and particularly relates to a covalent organic framework material, a ligand thereof and application thereof.
Background
The development and utilization of fossil energy meet the vast majority of energy demands of people for industrial production and daily life, however, fossil energy reserves are limited, and serious environmental pollution is caused in the process of consumption, so that the development and utilization of renewable energy are important to research of scientific researchers at present. The energy storage is an important link in the energy development and utilization process, and has important significance for the utilization and development of renewable energy.
The super capacitor is an energy storage device capable of outputting current in a short time to meet high power requirements, the performance gap between the capacitor and the battery is made up, and the energy storage is mainly from rapid physical adsorption or Faraday electrochemical reaction of an electrode/electrolyte interface. However, the energy density of existing supercapacitors is relatively low compared to secondary batteries (e.g., lithium ion batteries), which limits their wide use in high energy consumption devices. Accordingly, much research effort has focused on increasing energy density without sacrificing its inherent high power, where the construction of new electrode materials is critical.
Covalent organic framework materials (Covalent Organic Frameworks, COFs) are a class of crystalline organic porous materials composed of light weight elements (H, C, O, N, B, etc.), linked by covalent bonds. Since 2005, the porous ceramic material has the characteristics of permanent porosity, low density, adjustable structure and the like, and is widely applied to the fields of catalysis, gas adsorption separation, proton conduction and the like. Meanwhile, the covalent organic framework material has higher specific surface area and good stability, and is also considered as the most potential electrode material. Therefore, development of electrode materials having both high specific capacitance and cycle stability has been constantly being the direction of efforts by researchers in the field.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a covalent organic framework material, a ligand thereof and application.
The invention aims at being completed by the following technical scheme:
it is an object of the present invention to provide a covalent organic framework material having the following structural units:
designated COF-ET11.
It is a second object of the present invention to provide a ligand for preparing the covalent organic framework material described above, said ligand having the following structure:
。
it is a further object of the present invention to provide a use of the covalent organic framework material described above for the preparation of an electrode material.
Further defined, the electrode material is prepared from the covalent organic framework material, acetylene black and polytetrafluoroethylene described above.
Further defined, the electrode material is applied in a supercapacitor.
Compared with the prior art, the invention has the remarkable effects that:
the covalent organic framework material COF-ET11 of the invention has higher electrochemical performance in constant current charge and discharge test; the mass specific capacitance of the covalent organic framework material can reach 2989F/g at the time of 10A/g, and the retention rate is 98%; after 10000 times of circulation, the covalent organic framework material COF-ET11 can still keep about 98% of mass specific capacitance, and has good circulation stability, so that the covalent organic framework material COF-ET11 has good application prospect in the field of supercapacitors.
Drawings
FIG. 1 is a preparation route diagram of a covalent organic framework material COF-ET11 of the invention;
FIG. 2 is a nuclear magnetic resonance spectrum of a ligand in an embodiment of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of a ligand according to an embodiment of the present invention;
FIG. 4 is a mass spectrum of a ligand in an embodiment of the invention;
FIG. 5 is a mass spectrum of a covalent organic framework material COF-ET11 in an embodiment of the invention;
FIG. 6 is an infrared representation of a covalent organic framework material COF-ET11 made in accordance with an embodiment of the invention;
FIG. 7 shows a constant current charge-discharge test of the covalent organic framework material COF-ET11 prepared in the example of the present invention;
FIG. 8 is a graph showing the relationship between the mass specific capacitance and the current density of the covalent organic framework material COF-ET11 prepared by the embodiment of the invention;
FIG. 9 shows the results of the cycle stability test of the covalent organic framework material COF-ET11 prepared in the examples of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
Reference to "one embodiment" or "an embodiment" of the present invention means that a particular feature, structure, or characteristic may be included in at least one implementation of the present 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.
Methyl 2-amino-5-cyano-3-methylbenzoate (CAS: 1032667-87-0) and 1, 4-pyrazinedicarboxyaldehyde (CAS: 4164-39-0) used in the following examples were obtained by direct purchase from Shanghai Haohong biological medicine technologies Co., ltd. The instrument used for elemental analysis was an elementaruni elementary analyzer, germany.
Examples:
the synthetic route of the covalent organic framework material COF-ET11 is shown in the attached figure 1 of the specification, and the specific preparation method comprises the following steps:
first step, ligand synthesis:
to a 50 ml three-necked flask, methyl 2-amino-5-cyano-3-methylbenzoate (772 mg, 6.5 mmol) and 10 ml of chloroform were added, and the mixture was replaced with nitrogen gas 3 times, then cooled to 0℃and 2 ml of trifluoromethanesulfonic acid was added dropwise at this temperature for 20 minutes. Then, the temperature was lowered to 25℃and the reaction was carried out at this temperature for 24 hours. After the reaction, 20 ml of distilled water is added for quenching, then 2M sodium hydroxide solution is added until solid is separated out, the solid is filtered, and the filter cake is washed with 50 ml of distilled water for 3 times to obtain light yellow solid which is the ligand.
Nuclear magnetic characterization results:
as shown in fig. 2, the hydrogen spectrum: 1 H NMR (400 MHz, DMSO):δ7.93 (d, 3 H), 7.78 (d, 3 H), 6.76 (d, 3 H), 6.70 (d, 3 H), 3.86 (s, 9 H), 2.17 (s, 9 H).
as shown in fig. 3, the carbon spectrum: 13 C NMR (100 MHz, DMSO):δ168.22, 167.39, 148.09, 131.12, 129.55, 129.25, 129.05, 115.45, 52.78, 18.22.
elemental analysis test results: calcd for C 30 H 30 N 6 O 6 C, 63.15; H, 5.30; N, 14.73; O, 16.82. Found: C, 63.21; H, 5.25; N, 14.87; O, 16.63.
As shown in fig. 4, the mass spectrum characterization results: ESI (m/z): [ M+H ]] ＋ Calcd. for C 30 H 30 N 6 O 6 , 570.22；found, 571.18.
From the above analysis data, the ligand structure obtained was:
。
second step, preparation of covalent organic framework material COF-ET 11:
the above ligand (0.25 g, 2 mmol) and 1.4-pyrazinedicarboxydim (0.42 g, 3 mmol) were dissolved in 10 ml dimethyl sulfoxide, respectively, 1.5 ml 2-hydroxycitric acid was added to the dimethyl sulfoxide solution of the above ligand, then the dimethyl sulfoxide solution of 1.4-pyrazinedicarboxydim was added at 25 ℃, nitrogen was replaced 3 times after the dropwise addition, and then the above mixed solution was stirred at 180 ℃ for 72 hours. After the reaction is finished, separating white solid by a centrifugal machine, and sequentially adding dimethyl sulfoxide,N,N-dimethylformamide and ethanol for 3 times, followed by vacuum drying at 120 ℃ to obtain white powder, namely covalent organic framework material COF-ET11.
Elemental analysis test results: calcd for C 234 H 258 N 42 O 36 C, 66.37; H, 6.14; N, 13.89; O, 13.60. Found: C, 66.27; H, 6.18; N, 13.96; O, 13.57.
As shown in fig. 5, the mass spectrum characterization results: TOF-MS (m/z): [ M+H ]] ＋ Calcd. for C 234 H 258 N 42 O 36 , 4233.97；found, 4234.82.
From the above analysis data, the obtained covalent organic framework material COF-ET11 has the structure:
。
the covalent organic framework material COF-ET11 obtained by the embodiment of the invention is subjected to infrared characterization:
the test instrument is an IRAfforescence-1 Fourier transform infrared spectrometer, KBr tablets are pressed, and the test result is shown in figure 6 of the specification.
As can be seen from the figure 6 of the specification, in the infrared spectrum of the covalent organic framework material COF-ET11, the original N-H on the ligand (3468-3131 cm -1 ) The stretching vibration disappeared, and the original hc=o of 1, 4-pyrazinedicarboxymethylene (1649 cm) -1 ) The stretching vibration disappeared and a new bond c=n appeared (1707 cm -1 ) The occurrence of the aldehyde-amine condensation reaction was demonstrated, demonstrating the success of the construction of the covalent organic framework material COF-ET11.
Application example:
the preparation method of the electrode material of the covalent organic framework material COF-ET11 based on the embodiment of the invention comprises the following steps:
after mixing covalent organic framework material COF-ET11, acetylene black and polytetrafluoroethylene according to the mass ratio of 80:15:5, adding the mixture into ethanol solution (0.25 wt%) to form a uniform mixed solution by ultrasonic dispersion, then uniformly coating the mixed solution on nickel foam, and drying at 70 ℃ overnight.
The traditional three-electrode system is adopted, 6 mol/L sodium hydroxide aqueous solution is used as electrolyte, the electrode material prepared in the application example is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and the electrode material is electrically connected with the counter electrode and the reference electrodeFlow Density of 1.0 Ag -1 Constant current charge and discharge test was carried out under the conditions shown in figure 7 of the specification. As can be seen from fig. 7, the covalent organic framework material COF-ET11 of the present invention shows good symmetry, and a distinct charge-discharge plateau appears, indicating good electrochemical performance.
Description figure 8 shows the decay of the mass specific capacitance value of the covalent organic framework material COF-ET11 with increasing current density, and it can be seen that the COF material has good rate capability. With the increase of current density, the mass specific capacitance retention of the covalent organic framework material COF-ET11 is reduced, and the mass specific capacitance of the COF-ET11 can still reach 2989F/g at 10A/g, and the retention rate is 98%, so that the material has good rate capability.
The super capacitor has the important characteristics of being capable of being charged and discharged rapidly and long in service life, so that the cycle stability test is an important performance index. Thus, the cyclic stability of the covalent organic framework material COF-ET11 was tested at a current density of 5.0A/g and the test results are shown in figure 9 of the specification. After 10000 cycles of charge and discharge tests, the COF-ET11 can still maintain 98% of capacitance, which shows that the COF-ET has good cycle stability.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (3)
1. Use of a covalent organic framework material, characterized in that the covalent organic framework material has the following structural units:
，
designated COF-ET11, the covalent organic framework material is used to prepare electrode materials for use in supercapacitors.
2. Use of a covalent organic framework material according to claim 1, characterized in that the ligand for preparing the covalent organic framework material has the following structure:
。
3. the use of a covalent organic framework material according to claim 1, characterized in that said electrode material is prepared from said covalent organic framework material, acetylene black and polytetrafluoroethylene.
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