CN113563551A - Covalent organic framework material based on metalloporphyrin and preparation method and application thereof - Google Patents
Covalent organic framework material based on metalloporphyrin and preparation method and application thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 239000013499 TP-COF Substances 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- -1 (p-aminophenyl) cobalt porphyrin Chemical compound 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002262 Schiff base Substances 0.000 claims description 4
- 150000004753 Schiff bases Chemical class 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000010257 thawing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000006722 reduction reaction Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000003708 ampul Substances 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- 238000004364 calculation method Methods 0.000 description 2
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- 239000006230 acetylene black Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- 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
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to the technical field of electrocatalytic oxygen reduction, and in particular relates to a covalent organic framework material based on metalloporphyrin as well as a preparation method and application thereof. The structure of the covalent organic framework material based on metalloporphyrin is shown as a formula I:
the synthesized covalent organic framework material based on metalloporphyrin has good crystallinity and good chemical stability, and can be directly used as a catalyst for electrocatalytic oxygen reduction reaction; compared with a commercial platinum-carbon catalyst, the covalent organic framework material synthesized by the method based on metalloporphyrin does not contain noble metal, and has lower cost; the covalent organic framework material based on metalloporphyrin prepared by the invention has good electrocatalytic oxygen reduction catalytic performance.
Description
Technical Field
The invention relates to the technical field of electrocatalytic oxygen reduction, and in particular relates to a covalent organic framework material based on metalloporphyrin as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The fuel cell is a power generation device which converts chemical energy into electric energy through electrochemical reaction, is efficient and environment-friendly, and has wide application prospect. The Oxygen Reduction Reaction (ORR) is a cathode process of a fuel cell, and its kinetic process is slow, which severely restricts the application of the fuel cell. Commercial platinum carbon is a highly efficient ORR catalyst, but platinum resources are scarce and expensive. The development of inexpensive and efficient ORR catalysts is a significant problem facing fuel cells.
Covalent organic framework materials (COFs) are novel crystalline porous materials, have large specific surface, regular pore channel structures and adjustable pore channel sizes, and can be doped with heteroatoms and loaded with metal atoms through monomer design. The COFs has a huge application prospect in the aspect of electrocatalysis, the advantages of the COFs materials need to be fully exerted, and more ORR catalysts based on the COFs materials are developed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a covalent organic framework material based on metalloporphyrin and a preparation method and application thereof. Due to the introduction of cobalt porphyrin and an organic unit, the covalent organic framework based on metalloporphyrin obtained by the invention can be directly used as an electrocatalytic ORR catalyst and shows good catalytic performance.
In order to achieve the above object, the technical solution of the present invention is as follows:
in a first aspect of the present invention, a metalloporphyrin-based covalent organic framework material is provided, which has a structure represented by formula i:
in a second aspect of the present invention, a preparation method of the covalent organic framework material based on metalloporphyrin in the first aspect is provided, wherein the preparation method comprises the steps of taking 5,10,15, 20-tetra (p-aminophenyl) cobalt porphyrin and 4',4 ", 4" "', 4" "" "" '- (ethylene-1, 1,2, 2-tetra-yl) tetra { [ (1,1' -biphenyl) -4-formaldehyde ] } as reaction monomers, and performing condensation reaction through schiff base to generate the covalent organic framework material based on metalloporphyrin, which has a structural formula shown in formula i.
Specifically, the preparation method comprises the following steps: sequentially adding o-dichlorobenzene and dioxane into 5,10,15, 20-tetra (p-aminophenyl) cobalt porphyrin and 4', 4' - (ethylene-1, 1,2, 2-tetra-yl) tetra-yl { [ (1,1' -biphenyl) -4-formaldehyde ] }, adding an acetic acid aqueous solution, carrying out three cycles of freezing, vacuumizing and unfreezing, sealing a tube, heating, cooling to room temperature, washing and extracting to obtain Co-TP-COF.
In a third aspect of the invention, there is provided a use of the metalloporphyrin-based covalent organic framework material of the first aspect for electrocatalytic oxygen reduction.
The specific embodiment of the invention has the following beneficial effects:
1. the synthesized covalent organic framework material based on metalloporphyrin has good crystallinity and good chemical stability, and can be directly used as a catalyst for electrocatalytic oxygen reduction reaction;
2. compared with a commercial platinum-carbon catalyst, the covalent organic framework material synthesized by the method based on metalloporphyrin does not contain noble metal, and has lower cost;
3. the covalent organic framework material based on metalloporphyrin prepared by the invention has good electrocatalytic oxygen reduction catalytic performance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a powder X-ray diffraction pattern of Co-TP-COF synthesized in example 1 of the present invention;
FIG. 2 is an IR spectrum of Co-TP-COF synthesized in example 1 of the present invention;
FIG. 3 is a solid nuclear magnetic diagram of Co-TP-COF synthesized in example 1 of the present invention;
FIG. 4 is a graph showing a nitrogen adsorption-desorption curve and a pore size distribution of Co-TP-COF synthesized in example 1 of the present invention;
FIG. 5 is a LSV diagram of the synthesized Co-TP-COF of example 1 of the present invention;
FIG. 6 is a graph of LSV at different rotational speeds for the Co-TP-COF synthesized in example 1 of the present invention;
FIG. 7 is Tafel plot of Co-TP-COF synthesized in example 1 of the present invention;
FIG. 8 is a graph showing the electron transfer number and the hydrogen peroxide yield during the oxygen reduction of Co-TP-COF synthesized in example 1 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In one embodiment of the present invention, a metalloporphyrin-based covalent organic framework material is provided, which has a structure represented by formula i:
in the covalent organic framework material Co-TP-COF based on metalloporphyrin shown in the formula I, organic units of cobalt porphyrin and tetraphenylethylene structures are connected, and the Co-TP-COF is a covalent organic framework material formed by AA accumulation, and has better crystallinity and good chemical stability. Due to the introduction of cobalt porphyrin and an organic unit, the metalloporphyrin covalent organic framework obtained by the invention can be directly used as an electrocatalytic ORR catalyst, the ORR electron transfer number (n) in an alkaline medium is between 3.6 and 4.0, the process belongs to a four-electron transfer process and is more beneficial to oxygen reduction cathode reaction, and the yield of hydrogen peroxide is less than 20 percent, which indicates that the synthesized Co-TP-COF has better electrocatalytic oxygen reduction performance.
In an embodiment of the invention, the preparation method of the covalent organic framework material based on metalloporphyrin is provided, and the preparation method comprises the steps of taking 5,10,15, 20-tetra (p-aminophenyl) cobalt porphyrin and 4', 4' - (ethylene-1, 1,2, 2-tetra-yl) tetra-yl { [ (1,1' -biphenyl) -4-formaldehyde ] } as reaction monomers, and carrying out condensation reaction through Schiff base to generate the covalent organic framework material Co-TP-COF based on metalloporphyrin, wherein the structural formula is shown as formula I.
The reaction process is as follows:
specifically, the preparation method comprises the following steps: sequentially adding o-dichlorobenzene and dioxane into 5,10,15, 20-tetra (p-aminophenyl) cobalt porphyrin and 4', 4' - (ethylene-1, 1,2, 2-tetra-yl) tetra-yl { [ (1,1' -biphenyl) -4-formaldehyde ] }, adding an acetic acid aqueous solution, carrying out three cycles of freezing, vacuumizing and unfreezing, sealing a tube, heating, cooling to room temperature, washing and extracting to obtain Co-TP-COF.
Further, the molar ratio of 5,10,15, 20-tetrakis (p-aminophenyl) cobalt porphyrin to 4',4 ", 4" "', 4" "" '- (ethylene-1, 1,2, 2-tetrayl) tetrayl { [ (1,1' -biphenyl) -4-carbaldehyde ] } was 1: 1;
further, the volume ratio of the o-dichlorobenzene to the dioxane to the acetic acid aqueous solution is 4-6:4-6: 1;
further, the heating temperature is 110-; the heating time is 70 to 74 hours, preferably 72 hours;
further, the freezing, vacuumizing and unfreezing are carried out for three times, and the tube is sealed under the vacuum condition;
further, the washing method comprises the steps of carrying out suction filtration on the system, and washing with tetrahydrofuran and dichloromethane;
further, the extraction is performed by soxhlet extraction with tetrahydrofuran.
In a third aspect of the invention, there is provided a use of the metalloporphyrin-based covalent organic framework material of the first aspect for electrocatalytic oxygen reduction.
The invention will be further explained and illustrated with reference to specific examples.
Example 1
A covalent organic framework material based on metalloporphyrin is prepared by the following steps: to a 5mL ampoule was added 5,10,15, 20-tetrakis (p-aminophenyl) cobalt porphyrin (14.62mg,0.02mmol), and 4',4 ", 4" "', 4" "" '- (ethylene-1, 1,2, 2-tetrayl) tetrayl { [ (1,1' -biphenyl) -4-carbaldehyde ] } (14.98mg,0.02mmol), 0.5mL of o-dichlorobenzene, 0.5mL of dioxane in this order, and the mixture was ultrasonically dispersed to homogeneity, followed by addition of 0.1mL of 6M aqueous acetic acid. The ampoule is put into liquid nitrogen, frozen, vacuumized and unfrozen, and after three cycles, the ampoule is sealed in vacuum. The ampoule was placed in an oven and reacted at 120 ℃ for 72 hours. After cooling to room temperature, suction filtration and washing with tetrahydrofuran and dichloromethane were carried out, and Soxhlet extraction with tetrahydrofuran was carried out for 3 days to obtain a purple black solid powder Co-TP-COF with a yield of 85%.
As shown in FIG. 1, the powder X-ray diffraction pattern shows that Co-TP-COF has obvious diffraction peaks at 4.45 degrees and 8.89 degrees, which indicates that Co-TP-COF has better crystallinity. By comparing theoretical simulation results and experimental results, Co-TP-COF is shown to be AA stacking forming covalent organic framework materials.
As shown in FIG. 2, the infrared spectrum is at 1620cm-1The new peak appearing there is ascribed to the peak of the imine bond, indicating the occurrence of the Schiff base reaction. FIG. 3 solid nuclear magnetism further demonstrates the successful synthesis of Co-TP-COF materials.
As shown in FIG. 4, from nitrogen adsorption-Desorption curve analysis, the specific surface area of the Co-TP-COF material is 348m2In terms of a pore size of about 1.8nm per gram.
3mg of catalyst and 7mg of acetylene black are weighed and dispersed in 1.25mL of ethanol, and the mixture is ultrasonically dispersed for 30min to obtain black ink. Then 36. mu.L of ink was applied by pipetting onto a pre-polished rotating disk electrode (diameter 4 mm). Finally, a layer of Nafion solution (0.5 wt%) was applied and dried at room temperature. A commercial Pt/C catalyst (20 wt%) was prepared as a comparative sample under the same conditions.
Electrochemical testing: the electrolyte was basic 0.1M KOH. All electrochemical tests were carried out using electrochemical workstation (Chenghua, China, CHI 760E) and RRDE-3A (ALS, Japan) devices for ORR performance measurements. A saturated Ag/AgCl electrode and a graphite rod electrode are respectively used as a reference electrode and a counter electrode, and a rotating ring disk electrode is used as a working electrode. Oxygen saturation of the electrolyte by pre-aeration for 30 minutes before the test, linear sweep voltammetry (LSV, sweep Rate 5 mV. s)-1At a rotation speed of 1600rpm/min) are respectively in N2Saturation and O2In a saturated electrolyte, N2For deducting background, O2For testing performance. The platinum ring potential of the Rotating Ring Disk Electrode (RRDE) was fixed at 0.7V.
Electron transfer number calculation:
hydrogen peroxide yield (%) calculation:
(N＝42.4％)
as shown in FIG. 5, the LSV curve indicates that the initial potential of the Co-TP-COF material is 0.81V and the half-wave potential is 0.73V. The limiting current density is 4.9mA/cm2Surpass the commercial Pt/C catalyst; as shown in fig. 6, the LSV curves for different rotational speeds show that the limiting diffusion current density increases with increasing rotational speed; as shown in FIG. 7, the Tafel slope of the Co-TP-COF material was 39mV dec-1Less than commercial Pt/C catalysts; as shown in FIG. 8, the ORR electron transfer number (n) of the Co-TP-COF catalyst in the alkaline medium is between 3.6 and 4.0The method belongs to a four-electron transfer process, and is more beneficial to oxygen reduction cathode reaction, and the yield of hydrogen peroxide is less than 20%, which shows that the synthesized Co-TP-COF has better electrocatalytic oxygen reduction performance.
Example 2
A covalent organic framework material based on metalloporphyrin is prepared by the following steps: 5,10,15, 20-tetrakis (p-aminophenyl) cobalt porphyrin (29.24mg,0.04mmol), and 4',4 ", 4" "', 4" "" '- (ethylene-1, 1,2, 2-diyl) tetrayl { [ (1,1' -biphenyl) -4-carbaldehyde ] } (29.96mg,0.04mmol), 1mL of o-dichlorobenzene, 1mL of dioxane were sequentially added to a 5mL ampoule, and the mixture was ultrasonically dispersed to uniformity, followed by addition of 0.2mL of a 6M aqueous acetic acid solution. The ampoule is put into liquid nitrogen, frozen, vacuumized and unfrozen, and after three cycles, the ampoule is sealed in vacuum. The ampoule was placed in an oven and reacted at 120 ℃ for 72 hours. After cooling to room temperature, suction filtration and washing with tetrahydrofuran and dichloromethane were carried out, and Soxhlet extraction with tetrahydrofuran was carried out for 3 days to obtain a purple black solid powder Co-TP-COF with a yield of 83%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A covalent organic framework material based on metalloporphyrin is characterized in that the structure is shown as formula I:
2. the method for preparing a covalent organic framework material based on metalloporphyrin as claimed in claim 1, wherein the preparation method comprises the steps of using 5,10,15, 20-tetra (p-aminophenyl) cobalt porphyrin and 4',4 ", 4" "', 4" "" '- (ethylene-1, 1,2, 2-tetra-yl) tetra-yl { [ (1,1' -biphenyl) -4-formaldehyde ] } as reaction monomers, and carrying out condensation reaction by Schiff base to generate the covalent organic framework material Co-TP-COF based on metalloporphyrin, wherein the structural formula is shown as formula I.
3. The method of claim 2, comprising the steps of: sequentially adding o-dichlorobenzene and dioxane into 5,10,15, 20-tetra (p-aminophenyl) cobalt porphyrin and 4', 4' - (ethylene-1, 1,2, 2-tetra-yl) tetra-yl { [ (1,1' -biphenyl) -4-formaldehyde ] }, adding an acetic acid aqueous solution, carrying out three cycles of freezing, vacuumizing and unfreezing, sealing a tube, heating, cooling to room temperature, washing and extracting to obtain Co-TP-COF.
4. The method of claim 3, wherein the molar ratio of 5,10,15, 20-tetrakis (p-aminophenyl) cobalt porphyrin to 4',4 ", 4" "', 4" "" "'- (ethylene-1, 1,2, 2-tetrayl) tetrayl { [ (1,1' -biphenyl) -4-carbaldehyde ] } is 1: 1.
5. The method according to claim 3, wherein the volume ratio of o-dichlorobenzene, dioxane and aqueous acetic acid solution is 4-6:4-6: 1.
6. The method according to claim 3, wherein the heating temperature is 110-; the heating time is 70 to 74 hours, preferably 72 hours.
7. The method of claim 3, wherein the freezing, vacuuming and thawing are performed in three cycles, and the tube is sealed under vacuum.
8. The process according to claim 3, wherein the washing is carried out by suction-filtering the system and washing with tetrahydrofuran and methylene chloride.
9. The method according to claim 3, wherein the extraction is performed by Soxhlet extraction using tetrahydrofuran.
10. Use of a metalloporphyrin-based covalent organic framework material according to claim 1 for electrocatalytic oxygen reduction.
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Cited By (4)
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| CN114736344A (en) * | 2022-04-19 | 2022-07-12 | 国家纳米科学中心 | Grid covalent organic framework containing different pore environments and preparation method and application thereof |
| CN114774984A (en) * | 2022-05-05 | 2022-07-22 | 辽宁大学 | Preparation method and application of CoTPP-COFs/CNT (carbon nanotube) electrocatalyst |
| CN114539605B (en) * | 2022-01-11 | 2023-03-14 | 农业农村部环境保护科研监测所 | Sponge-supported porphyrin covalent organic framework integrated material and preparation method and application thereof |
| CN116333304A (en) * | 2023-04-07 | 2023-06-27 | 福州大学 | Porphyrin-based covalent organic framework material connected with viologen as well as preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539605B (en) * | 2022-01-11 | 2023-03-14 | 农业农村部环境保护科研监测所 | Sponge-supported porphyrin covalent organic framework integrated material and preparation method and application thereof |
| CN114736344A (en) * | 2022-04-19 | 2022-07-12 | 国家纳米科学中心 | Grid covalent organic framework containing different pore environments and preparation method and application thereof |
| CN114774984A (en) * | 2022-05-05 | 2022-07-22 | 辽宁大学 | Preparation method and application of CoTPP-COFs/CNT (carbon nanotube) electrocatalyst |
| CN114774984B (en) * | 2022-05-05 | 2023-11-10 | 辽宁大学 | Preparation method and application of CoTPP-COFs/CNT electrocatalyst |
| CN116333304A (en) * | 2023-04-07 | 2023-06-27 | 福州大学 | Porphyrin-based covalent organic framework material connected with viologen as well as preparation method and application thereof |
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