CN117659325B - Preparation method of covalent organic framework material with electrochemical activity - Google Patents
Preparation method of covalent organic framework material with electrochemical activity Download PDFInfo
- Publication number
- CN117659325B CN117659325B CN202410133323.1A CN202410133323A CN117659325B CN 117659325 B CN117659325 B CN 117659325B CN 202410133323 A CN202410133323 A CN 202410133323A CN 117659325 B CN117659325 B CN 117659325B
- Authority
- CN
- China
- Prior art keywords
- cof
- reaction
- ethanol
- covalent organic
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 14
- 230000000694 effects Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- SAFRFSWGAIUFAY-UHFFFAOYSA-N cyclopenta-1,3-diene-1-carbaldehyde;iron(2+) Chemical compound [Fe+2].O=CC1=CC=C[CH-]1.O=CC1=CC=C[CH-]1 SAFRFSWGAIUFAY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 108091070501 miRNA Proteins 0.000 claims abstract description 4
- 239000002679 microRNA Substances 0.000 claims abstract description 4
- 210000004881 tumor cell Anatomy 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- -1 4' -amino [1,1 '-biphenyl ] -4-yl Chemical group 0.000 claims description 5
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 3
- NOESMJBODNBEAM-UHFFFAOYSA-N 4-[2,6-bis(4-aminophenyl)pyridin-4-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=C1 NOESMJBODNBEAM-UHFFFAOYSA-N 0.000 claims description 3
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 3
- 239000013474 COF-1 Substances 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 abstract description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052737 gold Inorganic materials 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000002262 Schiff base Substances 0.000 abstract description 3
- 150000004753 Schiff bases Chemical class 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000002048 multi walled nanotube Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- DJAVGLSMAXSAJE-UHFFFAOYSA-N 4-[4-[4-(4-aminophenyl)-N-[4-(4-aminophenyl)phenyl]anilino]phenyl]aniline Chemical compound NC1=CC=C(C=C1)C1=CC=C(C=C1)N(C1=CC=C(C=C1)C1=CC=C(C=C1)N)C1=CC=C(C=C1)C1=CC=C(C=C1)N DJAVGLSMAXSAJE-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000872 buffer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention relates to the technical field of covalent organic frameworks, and particularly discloses a preparation method of a covalent organic framework material with electrochemical activity, which comprises the following steps: preparation of electrochemically active COF nanoparticles, synthesis of COF/Au, and synthesis of COF/Au/CNT-COOH. The ternary amino ligand and 1,1' -ferrocene dicarboxaldehyde are condensed through Schiff base reaction, ethanol, acetonitrile and dichloromethane are used as solvents, acetic acid is used as a catalyst, a high-yield high-purity product is obtained, and then the synthesized novel covalent organic framework is modified by gold nano particles and carboxyl functionalized multiwall carbon nano tubes, so that the novel covalent organic framework can be used for high-sensitivity detection of miRNA in tumor cells.
Description
Technical Field
The invention relates to the technical field of covalent organic frameworks, in particular to a preparation method of a covalent organic framework material with electrochemical activity.
Background
Covalent organic framework COFs are crystalline porous polymers formed by the linkage of organic monomers through strong covalent bonds. COFs have been used in the fields of gas storage, proton conduction, photocatalysis, drug delivery, etc. due to their advantages of good thermal and chemical stability, ultra-high surface area, good biocompatibility, unique uniform pore structure, etc. By using electrochemically active monomers, some electrochemically active COFs can be prepared and used as reference or response signals to construct highly sensitive biosensors. COFs are rarely used in the field of electrochemical biosensing due to their poor conductivity.
In order to solve the above problems, a technical solution is now provided.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, the present invention provides a method for preparing an electrochemically active covalent organic framework material, comprising: preparing COF nano particles with electrochemical activity; synthesis of COF/Au (COF/gold nanoparticles); synthesis of COF/Au/CNT-COOH (COF/gold nanoparticles/carboxylated carbon nanotubes). Condensing a ternary amino ligand and 1,1' -ferrocene dicarboxaldehyde through Schiff base reaction, stirring at room temperature for 12-36 hours by taking ethanol, acetonitrile and dichloromethane as solvents and acetic acid as catalysts to obtain a crude product, centrifugally separating, purifying and vacuum drying the crude product to obtain a high-yield high-purity product, and then modifying a synthesized novel covalent organic framework by gold nano particles and carboxyl functionalized multi-wall carbon nano tubes to improve the conductivity of the material, thereby being used for high-sensitivity detection of miRNA in tumor cells.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing a covalent organic framework material with electrochemical activity, which is characterized by comprising the following specific steps:
step one, preparing electrochemically active COF nano particles;
step two, synthesizing COF/Au (COF/gold nanoparticles);
step three, synthesis of COF/Au/CNT-COOH (COF/gold nanoparticles/carboxylated carbon nanotubes).
Further, in the first step, the reaction solvent is 8mL of ethanol, acetonitrile or dichloromethane, the reaction monomers are a ternary amino ligand and 1,1 '-ferrocene dicarboxaldehyde, the catalyst is 0.2mL of acetic acid, the ternary amino ligand comprises 1,3, 5-tri (4-aminophenyl) benzene, 4- (4-aminophenyl) -2, 6-di (4-aminophenyl) pyridine, tri (4-aminophenyl) amine, 5' '- (4' -amino 1,1 '-biphenyl 1-4-yl), 4' '',4'' '' '' - (1, 3, 5-triazine-2, 4, 6-triyl) tris ([ [1,1 '-biphenyl ] -4-amine ]), and the mass ratio of N4, N4-bis (4' -amino- [1,1 '-biphenyl ] -4-yl) - [1,1' -biphenyl ] -4,4 '-diamine to 1,1' -ferrocene dicarboxaldehyde is respectively 1:1,2:1,1:2,3:2,2:3, wherein the specific steps for preparing the electrochemically active COF nano particles are as follows:
step A1, mixing ethanol, acetonitrile or dichloromethane, a tertiary amino ligand, 1' -ferrocene dicarboxaldehyde and acetic acid;
step A2, stirring at room temperature for reaction for 12-36 hours to obtain a crude product;
step A3, centrifugally separating the crude product, washing the crude product in ethanol, acetonitrile and dichloromethane three times for purification, and drying the crude product in vacuum at 50-70 ℃ for 6-12 hours to obtain products FC-COF-1 to FC-COF-6.
Further, in the second step, the reaction compound synthesized by COF/Au (COF/gold nanoparticle) contains: 1mg of the dried COF nanoparticles prepared in the first step, 5mL of ultrapure water or ethanol, chloroauric acid solution with a concentration of 1.5mg/mL and sodium borohydride solution with a concentration of 1.5mg/mL, and the reaction steps are as follows:
step B1, 1mg of the dried COF nano particles are dispersed in 5mL of ultrapure water or ethanol in an ultrasonic manner to form a reaction system solution;
step B2, sequentially adding chloroauric acid solution with the volume of 0.1mL, 0.2mL, 0.4mL and 0.8mL and the concentration of 1.5mg/mL into the reaction system solution, and stirring at room temperature or carrying out ultrasonic stirring reaction for 2-6 hours to form a mixed reaction system;
step B3, adding a proper amount of sodium borohydride solution with the concentration of 1.5mg/mL into the reaction system rapidly, and continuing stirring at room temperature or ultrasonic stirring for 2 hours to obtain a COF/Au (COF/gold nanoparticles) crude product;
and step B4, centrifugally washing the product, and drying.
Further, in the third step, the reaction compound synthesized by COF/Au/CNT-COOH (COF/gold nanoparticle/carboxylated carbon nanotube) contains: 1mg of the COF/Au nano-particles and carboxylated carbon nano-tubes prepared in the second step, wherein the reaction steps are as follows:
step C1, dispersing 1mg of the dried COF/Au nanoparticles and CNT-COOH of different masses (0.01 mg, 0.05mg, 0.1mg, 0.5mg, 1mg, 5 mg) in a beaker containing 5mL of ultrapure water, respectively;
step C2, mixing the two solutions in different beakers, performing ultrasonic treatment for 1 hour, and stirring at room temperature for 3 hours;
step C3, centrifuging, washing with water and drying, collecting target COF/Au/CNT-COOH (COF/gold nanoparticles/carboxylated carbon nanotubes) products, which appear as black powder.
The preparation method of the covalent organic framework material with electrochemical activity has the technical effects and advantages that:
according to the invention, the high-conductivity material (such as noble metal, graphene and carbon nano tube) and the COFs are compounded to prepare the functionalized COFs nano composite material, so that the conductivity of the composite material can be effectively improved to realize excellent electrochemical performance.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing an electrochemically active covalent organic framework material according to the present invention;
FIG. 2 is a schematic representation of the synthesis of an electrochemically active ferrocenyl covalent organic framework of the present invention;
FIG. 3 is a graph showing DPV of COF/GCE of the present invention in 0.1M PBS buffer at pH 7.4;
FIG. 4 is a sheet morphology of an electrochemically active ferrocenyl covalent organic framework of the present invention;
FIG. 5 is a bar-shaped morphology of an electrochemically active ferrocenyl covalent organic framework of the present invention;
FIG. 6 is a diagram of a spherical morphology of an electrochemically active ferrocenyl covalent organic framework of the present invention;
FIG. 7 is a graph of the spherical morphology of an electrochemically active ferrocenyl covalent organic framework of the present invention.
Detailed Description
The technical solutions of the present embodiment will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is apparent that the described embodiment is only a part of the embodiment of the present invention, not all the embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A method for preparing a covalent organic framework material with electrochemical activity, which is characterized by comprising the following specific steps:
step one, preparing electrochemically active COF nano particles;
step two, synthesizing COF/Au (COF/gold nanoparticles);
step three, synthesis of COF/Au/CNT-COOH (COF/gold nanoparticles/carboxylated carbon nanotubes).
In the first step of the embodiment of the invention, the reaction solvent is 8mL of ethanol, acetonitrile or dichloromethane, the reaction monomers are a ternary amino ligand and 1,1' -ferrocene dicarboxaldehyde, the catalyst is 0.2mL of acetic acid, the ternary amino ligand comprises 1,3, 5-tri (4-aminophenyl) benzene, 4- (4-aminophenyl) -2, 6-di (4-aminophenyl) pyridine, tri (4-aminophenyl) amine, 5 ' ' - (4 ' -amino 1,1' -biphenyl 1-4-yl), 4' ' ',4' ' ' ' ' - (1, 3, 5-triazine-2, 4, 6-triyl) tris ([ [1,1' -biphenyl ] -4-amine ])), and N4, N4-bis (4 ' -amino- [1,1' -biphenyl ] -4-yl) - [1,1' -biphenyl ] -4,4' -diamine, and the mass ratio of the 1,1' -ferrocene dicarboxaldehyde is respectively 1:1,2:1,1:2,3:2,2:3, wherein the specific steps for preparing the electrochemically active COF nano particles are as follows:
step A1, mixing ethanol, acetonitrile or dichloromethane, a tertiary amino ligand, 1' -ferrocene dicarboxaldehyde and acetic acid;
step A2, stirring at room temperature for reaction for 12-36 hours to obtain a crude product;
step A3, centrifugally separating the crude product, washing the crude product in ethanol, acetonitrile and dichloromethane three times for purification, and drying the crude product in vacuum at 50-70 ℃ for 6-12 hours to obtain products FC-COF-1 to FC-COF-6.
In the second step of the embodiment of the present invention, the reaction compound synthesized by COF/Au (COF/gold nanoparticle) contains: 1mg of the dried COF nanoparticles prepared in the first step, 5mL of ultrapure water or ethanol, chloroauric acid solution with a concentration of 1.5mg/mL and sodium borohydride solution with a concentration of 1.5mg/mL, and the reaction steps are as follows:
step B1, 1mg of the dried COF nano particles are dispersed in 5mL of ultrapure water or ethanol in an ultrasonic manner to form a reaction system solution;
step B2, sequentially adding chloroauric acid solution with the volume of 0.1mL, 0.2mL, 0.4mL and 0.8mL and the concentration of 1.5mg/mL into the reaction system solution, and stirring at room temperature or carrying out ultrasonic stirring reaction for 2-6 hours to form a mixed reaction system;
step B3, adding a proper amount of sodium borohydride solution with the concentration of 1.5mg/mL into the reaction system rapidly, and continuing stirring at room temperature or ultrasonic stirring for 2 hours to obtain a COF/Au (COF/gold nanoparticles) crude product;
and step B4, centrifugally washing the product, and drying.
In step three of the embodiment of the present invention, the reaction compound synthesized by COF/Au/CNT-COOH (COF/gold nanoparticle/carboxylated carbon nanotube) contains: 1mg of the COF/Au nano-particles and carboxylated carbon nano-tubes prepared in the second step, wherein the reaction steps are as follows:
step C1, dispersing 1mg of the dried COF/Au nanoparticles and CNT-COOH of different masses (0.01 mg, 0.05mg, 0.1mg, 0.5mg, 1mg, 5 mg) in a beaker containing 5mL of ultrapure water, respectively;
step C2, mixing the two solutions in different beakers, performing ultrasonic treatment for 1 hour, and stirring at room temperature for 3 hours;
step C3, centrifuging, washing with water and drying, collecting target COF/Au/CNT-COOH (COF/gold nanoparticles/carboxylated carbon nanotubes) products, which appear as black powder.
According to the embodiment of the invention, the ternary amino ligand and 1,1' -ferrocene dicarboxaldehyde are condensed through Schiff base reaction, ethanol, acetonitrile and methylene dichloride are used as solvents, acetic acid is used as a catalyst, the crude product is obtained after stirring for 12-36 hours at room temperature, the crude product is subjected to centrifugal separation, purification and vacuum drying to obtain a high-yield high-purity product, and then the synthesized novel covalent organic framework is modified by gold nano particles and carboxyl functionalized multiwall carbon nano tubes, so that the conductivity of the material is improved, and the novel covalent organic framework is used for high-sensitivity detection of miRNA in tumor cells.
The foregoing is merely specific embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think about changes or substitutions within the technical scope of the present application, and the changes and substitutions are intended to be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Finally: the foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (1)
1. A method for preparing a covalent organic framework material with electrochemical activity, which is characterized by comprising the following specific steps:
step one, preparing electrochemically active COF nano particles; the reaction solvent is 8mL of ethanol, acetonitrile or methylene dichloride, the reaction monomers are a ternary amino ligand and 1,1 '-ferrocene dicarboxaldehyde, the catalyst is 0.2mL of acetic acid, the ternary amino ligand comprises 1,3, 5-tris (4-aminophenyl) benzene, 4- (4-aminophenyl) -2, 6-bis (4-aminophenyl) pyridine, tris (4-aminophenyl) amine, 5' '- (4' -amino [1,1 '-biphenyl ] -4-yl) [1,1':4', 1' ': 3' ',1' '' -pentabiphenyl ] -4,4'' '-diamine, 4' '',4'' '' - (1, 3, 5-triazine-2, 4, 6-triyl) tris (([ [1,1 '-biphenyl ] -4-amine ])), N4-bis (4' -amino- [1,1 '-biphenyl ] -4-yl) - [1,1' -biphenyl ] -4,4 '-diamine, and the mass ratio of the 1' '-dicarboxaldehyde to the 1,1' -dicarboxaldehyde is respectively: 1,2:1,1:2,3:2,2:3, a step of; the preparation steps of the electrochemically active COF nano-particles specifically comprise:
step A1, mixing ethanol, acetonitrile or dichloromethane, a tertiary amino ligand, 1' -ferrocene dicarboxaldehyde and acetic acid;
step A2, stirring at room temperature for reaction for 12-36 hours to obtain a crude product;
step A3, centrifugally separating the crude product, washing the crude product in ethanol, acetonitrile and methylene dichloride for three times for purification, and vacuum drying the crude product at 50-70 ℃ for 6-12 hours to obtain products FC-COF-1 to FC-COF-6;
step two, synthesizing COF/Au; the reaction compound for synthesizing the COF/Au comprises 1mg of the dried COF nano particles prepared in the first step, 5mL of ultrapure water or ethanol, chloroauric acid solution with the concentration of 1.5mg/mL and sodium borohydride solution with the concentration of 1.5mg/mL, and the reaction steps are as follows:
step B1, 1mg of the dried COF nano particles are dispersed in 5mL of ultrapure water or ethanol in an ultrasonic manner to form a reaction system solution;
step B2, sequentially adding chloroauric acid solution with the volume of 0.1mL, 0.2mL, 0.4mL and 0.8mL and the concentration of 1.5mg/mL into the reaction system solution, and stirring at room temperature or carrying out ultrasonic stirring reaction for 2-6 hours to form a mixed reaction system;
step B3, adding a proper amount of sodium borohydride solution with the concentration of 1.5mg/mL into the reaction system rapidly, and continuing stirring at room temperature or ultrasonic stirring for 2 hours to obtain a COF/Au crude product;
step B4, centrifugally washing and drying the product;
step three, synthesizing COF/Au/CNT-COOH; the method is used for detecting miRNA in tumor cells; the reaction compound synthesized by the COF/Au/CNT-COOH comprises COF/Au nano-particles and carboxylated carbon nano-tubes 1mg prepared in the second step, and the reaction steps are as follows:
step C1, dispersing 1mg of the dried COF/Au nano-particles and CNT-COOH with the mass of 0.01mg, 0.05mg, 0.1mg, 0.5mg, 1mg and 5mg in a beaker containing 5mL of ultrapure water respectively;
step C2, mixing the two solutions in different beakers, performing ultrasonic treatment for 1 hour, and stirring at room temperature for 3 hours;
step C3, centrifuging, washing with water and drying, and collecting target COF/Au/CNT-COOH products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410133323.1A CN117659325B (en) | 2024-01-31 | 2024-01-31 | Preparation method of covalent organic framework material with electrochemical activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410133323.1A CN117659325B (en) | 2024-01-31 | 2024-01-31 | Preparation method of covalent organic framework material with electrochemical activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117659325A CN117659325A (en) | 2024-03-08 |
| CN117659325B true CN117659325B (en) | 2024-04-12 |
Family
ID=90064549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410133323.1A Active CN117659325B (en) | 2024-01-31 | 2024-01-31 | Preparation method of covalent organic framework material with electrochemical activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117659325B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017031062A1 (en) * | 2015-08-14 | 2017-02-23 | Cornell University | Conducting-polymer modified covalent organic frameworks and methods of making same |
| CN109288860A (en) * | 2018-10-18 | 2019-02-01 | 山东大学 | A kind of application of the gold nano grain of Aminylferrocene class molecular compound modification in pharmacy |
| CN111307895A (en) * | 2020-04-03 | 2020-06-19 | 山东农业大学 | Fast preparation COF @ NH2-method of CNT composite |
| CN111841645A (en) * | 2020-08-31 | 2020-10-30 | 江南大学 | OER catalyst compounded by carbon nano tube and covalent organic framework |
| CN113675414A (en) * | 2021-08-17 | 2021-11-19 | 青岛科技大学 | Carbon nanotube-based covalent organic framework metal monatomic catalyst and preparation method thereof |
| CN114487044A (en) * | 2022-01-20 | 2022-05-13 | 大连理工大学 | Electrochemical enzyme biosensor for detecting organophosphorus pesticide, preparation method and application |
| CN114853968A (en) * | 2022-06-16 | 2022-08-05 | 山东师范大学 | Ferrocenyl three-dimensional covalent organic framework material and preparation method thereof |
| CN117282404A (en) * | 2023-09-23 | 2023-12-26 | 福州大学 | Silver nanoparticle functionalized covalent organic framework microsphere and preparation and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101669169B1 (en) * | 2014-12-19 | 2016-10-26 | 한국생산기술연구원 | Composites of carbon materials and covalent-organic frameworks, a preparation method thereof and a use thereof |
| US20220153904A1 (en) * | 2018-11-19 | 2022-05-19 | Zhejiang University | A method for preparing and repairing covalent organic framework materials |
-
2024
- 2024-01-31 CN CN202410133323.1A patent/CN117659325B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017031062A1 (en) * | 2015-08-14 | 2017-02-23 | Cornell University | Conducting-polymer modified covalent organic frameworks and methods of making same |
| CN109288860A (en) * | 2018-10-18 | 2019-02-01 | 山东大学 | A kind of application of the gold nano grain of Aminylferrocene class molecular compound modification in pharmacy |
| CN111307895A (en) * | 2020-04-03 | 2020-06-19 | 山东农业大学 | Fast preparation COF @ NH2-method of CNT composite |
| CN111841645A (en) * | 2020-08-31 | 2020-10-30 | 江南大学 | OER catalyst compounded by carbon nano tube and covalent organic framework |
| CN113675414A (en) * | 2021-08-17 | 2021-11-19 | 青岛科技大学 | Carbon nanotube-based covalent organic framework metal monatomic catalyst and preparation method thereof |
| CN114487044A (en) * | 2022-01-20 | 2022-05-13 | 大连理工大学 | Electrochemical enzyme biosensor for detecting organophosphorus pesticide, preparation method and application |
| CN114853968A (en) * | 2022-06-16 | 2022-08-05 | 山东师范大学 | Ferrocenyl three-dimensional covalent organic framework material and preparation method thereof |
| CN117282404A (en) * | 2023-09-23 | 2023-12-26 | 福州大学 | Silver nanoparticle functionalized covalent organic framework microsphere and preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Electrochemical sensor based on covalent organic frameworks-MWCNT-NH2/AuNPs for simultaneous detection of dopamine and uric acid;Qixia Guan et al.;Journal of Electroanalytical Chemistry;20201213;第880卷;114932 * |
| Experimental Validation and Computational Predictions Join Forces to Map Catalytic C–H Activation in Ferrocene Metalated Porous Organic Polymers;Bishal Boro et al.;ACS Appl. Mater. Interfaces;20230421;第15卷(第17期);21027-21039 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117659325A (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hira et al. | Ultrasensitive detection of hydrogen peroxide and dopamine using copolymer-grafted metal-organic framework based electrochemical sensor | |
| Lin et al. | A “signal-on” chemiluminescence biosensor for thrombin detection based on DNA functionalized magnetic sodium alginate hydrogel and metalloporphyrinic metal-organic framework nanosheets | |
| Lu et al. | Electrochemical determination of rutin based on molecularly imprinted poly (ionic liquid) with ionic liquid-graphene as a sensitive element | |
| CN102850795B (en) | Preparation method of ferrocene-grafted polyethyleneimine-graphene composite material | |
| CN103447092B (en) | Graphene oxide supported Schiff base palladium catalyst as well as preparation method and application thereof | |
| Kan et al. | Molecularly imprinted polymers microsphere prepared by precipitation polymerization for hydroquinone recognition | |
| CN104833767B (en) | A kind of GR/WS 2-AuNPs-WS 2the preparation method of complex molecule trace sensor and application thereof | |
| US9067181B2 (en) | Separation of nanoparticles | |
| WO2022228025A1 (en) | Implantable glucose biosensor and preparation method therefor | |
| Sun et al. | In-situ reducing platinum nanoparticles on covalent organic framework as a sensitive electrochemical sensor for simultaneous detection of catechol, hydroquinone and resorcinol | |
| CN109270135B (en) | Modified electrode for norfloxacin molecular imprinting electrochemical sensor and preparation method thereof | |
| CN106432117A (en) | Preparation method and application of functional nano-cerium complex | |
| CN114524813B (en) | One-dimensional organic semiconductor nano material with fluorescent response to sarin and preparation method and application thereof | |
| CN114471476B (en) | Magnetic porous organic framework material and preparation method and application thereof | |
| CN107252695A (en) | Palladium base dopamine coated magnetic carbon-nano tube catalyst and preparation method and application | |
| CN113522244A (en) | Covalent organic framework composite material and preparation method and application thereof | |
| Lei et al. | In-situ benzoxazine-isocyanide chemistry (BIC)/sol-gel preparation and Pb (II) electrochemical probing investigation of modified polyamide/silica composite | |
| Xia et al. | A highly selective electrochemical sensor based on surface molecularly imprinted copolymer for the detection of 5-hydroxytryptamine | |
| Tagmatarchis et al. | Carbon-based materials: from fullerene nanostructures to functionalized carbon nanotubes | |
| CN117659325B (en) | Preparation method of covalent organic framework material with electrochemical activity | |
| US9623381B2 (en) | Separation of nanoparticles | |
| Guo et al. | A novel electrochemical sensor based on TAPT-TFP-COF/COOH-MWCNT for simultaneous detection of dopamine and paracetamol | |
| Dong et al. | In situ synthesis of gold nanoparticle on MIL-101 (Cr)-NH2 for non-enzymatic dopamine sensing | |
| CN112851954B (en) | Covalent organic framework, composite material thereof, preparation method and application | |
| CN110702759B (en) | ZIF-8 composite material electrochemical immunosensor for detecting alpha fetoprotein and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |