CN113842947A - Two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles and synthesis method and application thereof - Google Patents
Two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles and synthesis method and application thereof Download PDFInfo
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
The invention provides a two-dimensional metal/Covalent Organic Framework (COF) based photocatalytic composite material carrying metal nanoparticles, a synthetic method and application thereof. The material mainly comprises three parts, namely a two-dimensional metal material, a two-dimensional COF material and metal nano particles, wherein the three components are mixed according to the mass ratio of 1: 0.4-0.7: 6.4-14.5, further optimizing reaction parameters such as stirring speed, reaction time, temperature and the like. The two-dimensional metal and the COF material are connected through the covalent bond to form a stable two-dimensional heterojunction, so that the lattice adaptation limit is reduced, and the photocatalytic performance is enhanced; the metal nano particles are carried by the two-dimensional composite material, so that the release rate of metal ions can be greatly reduced, the bacteriostatic life can be prolonged, and the pollution to the environment can be reduced. The synthesized composite structure can be applied to marine antifouling coatings and has the performances of environmental protection, long-acting property, high efficiency and the like.
Description
Technical Field
The invention relates to a two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles, a synthetic method and application thereof, and belongs to the field of two-dimensional photocatalytic antifouling.
Background
With the great step of developing marine resources, a great deal of marine engineering facilities are put into the sea, such as a cross-sea bridge, an offshore oil drilling platform, a port wharf and the like. These facilities are not protected from marine biofouling when exposed to the marine environment. The attachment of marine organisms can greatly reduce the service life of the marine engineering facility. Therefore, it is imperative to implement effective marine antifouling means.
Under the constraints of environmental protection, high efficiency, long service life, spectral property and the like, the photocatalytic antifouling method gradually attracts attention in the antifouling field. The photocatalytic antifouling technology utilizes the photovoltaic effect to generate a large amount of active oxygen molecules under the irradiation of sunlight so as to effectively sterilize. However, most of the existing photocatalytic materials have the disadvantages of larger forbidden band width, short carrier lifetime, and the like.
Two-dimensional materials are due to their unique physicochemical properties and can be integrated into heterojunctions and are less affected by lattice constant adaptation. Therefore, the development of two-dimensional photocatalytic antifouling materials is imminent.
With the great step of developing marine resources, a great deal of marine engineering facilities are put into the sea, such as a cross-sea bridge, an offshore oil drilling platform, a port wharf and the like. These facilities are not protected from marine biofouling when exposed to the marine environment. The attachment of marine organisms can greatly reduce the service life of the marine engineering facility. Therefore, it is imperative to implement effective marine antifouling means.
Under the constraints of environmental protection, high efficiency, long service life, spectral property and the like, the photocatalytic antifouling method gradually attracts attention in the antifouling field. The photocatalytic antifouling technology utilizes the photovoltaic effect to generate a large amount of active oxygen molecules under the irradiation of sunlight so as to effectively sterilize. However, most of the existing photocatalytic materials have the disadvantages of larger forbidden band width, short carrier lifetime, and the like.
Two-dimensional materials are due to their unique physicochemical properties and can be integrated into heterojunctions and are less affected by lattice constant adaptation. Therefore, the development of two-dimensional photocatalytic antifouling materials is imminent.
Disclosure of Invention
The technical task of the invention is to provide a two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles, a synthetic method and application thereof aiming at the defects of the prior art.
The invention connects two-dimensional materials through covalent bonds, has stable structure and is more beneficial to the transmission of electrons. By introducing the metal nanoparticles, the antifouling performance is improved, the release of metal ions can be prolonged, and long-acting sterilization is realized.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1. a two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles is characterized by mainly comprising three parts, namely a two-dimensional metal material, a two-dimensional COF material and metal nanoparticles;
wherein the two-dimensional metal material, the two-dimensional COF material and the metal nano particles are mixed according to the mass ratio of 1: 0.4-0.7: 6.4-14.5 compounding;
wherein the two different two-dimensional materials are connected by covalent bonds to form a vertical structure heterojunction.
2. The invention also provides a synthetic method of the two-dimensional metal/COF-based photocatalytic composite material carrying the metal nanoparticles, which comprises the following specific implementation steps
1) Amination of two-dimensional metal material: mixing 1 part by weight of two-dimensional metal material with a solvent, adding a silane coupling agent, and stirring at the rotation speed of 600-800rpm for 20-24 hours at the temperature of 20-35 ℃;
2) in-situ composite growth of two-dimensional material: fully mixing a main material for preparing 0.4-0.7 part by weight of a two-dimensional COF material with an aminated two-dimensional metal material, and stirring at the rotating speed of 500-800rpm for 10-30h at the temperature of 120-140 ℃ in the atmosphere of inert protective gas;
3) compounding metal nanoparticles: fully mixing 6.4-14.5 parts by weight of metal nanoparticles and a two-dimensional composite material in a solvent, adding a proper amount of reducing agent at room temperature, and stirring at the rotating speed of 600-700rpm for 0.5-2h to obtain the metal nanoparticle-carried two-dimensional metal-semiconductor photocatalytic composite material.
Optionally, the two-dimensional metal material is selected from one or more of Ti3C2, Mo2C, Ti2C and Zr3C 2.
Optionally, the two-dimensional COF material is selected from one or more of TpBD, TpPa-1, TpPa-2 and COF-LZU 1.
Optionally, the silane coupling agent is one or more selected from 3-aminopropyltriethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, and (3-aminopropyl) diethoxymethylsilane.
Optionally, the metal nanoparticles are one or more selected from zinc oxide nanoparticles, cuprous oxide nanoparticles, silver nanoparticles, and magnesium oxide nanoparticles.
Optionally, the inert protective gas is selected from one or more of argon and nitrogen.
Optionally, the reducing agent is selected from one or more of hydrazine hydrate, sodium borohydride and ascorbic acid.
3. The invention also provides application of the two-dimensional metal/COF-based photocatalytic composite material carrying the metal nanoparticles, wherein the synthesized nano composite material and an organic coating are mixed according to the mass ratio of 1:5-30, coated on the surface of a metal matrix, and dried for more than 24 hours at room temperature to obtain an antifouling coating.
Optionally, the organic coating is one or more of a water-based epoxy resin coating, a polysiloxane coating, a polyurethane coating, a methacrylic resin coating and a fluorocarbon resin coating.
Compared with the prior art, the two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles and the synthesis method and application thereof have the following beneficial effects:
1. the invention provides a synthetic method of a two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles, and provides a preparation method of a photocatalytic antifouling coating. The two-dimensional material has unique physical and chemical properties, the limit of lattice constant on the formed heterojunction is small, and the obtained material has a stable structure. And the two are connected through a covalent bond, so that the transmission of a photon-generated carrier is stably promoted, and the photocatalytic performance is improved.
2. The metal nano-particles of the invention have the bactericidal property which can be greatly exerted. When the metal ion release agent is carried on a two-dimensional composite material, the release rate of metal ions can be greatly reduced.
3. The invention integrates photocatalysis antifouling and metal nano particle antifouling, and has the characteristics of environmental protection, high efficiency, stability and the like.
4. The two-dimensional metal/COF-based photocatalytic composite material carrying the metal nanoparticles can be added into an organic coating, and due to the abundant groups on the surface of the two-dimensional material, the material can be uniformly dispersed in the organic coating, so that the antifouling effect is improved.
Drawings
In order to more clearly describe the two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles and the synthesis method and the application thereof, the following schematic diagram is further illustrated.
FIG. 1 is a scanning electron micrograph of a material according to an embodiment of the present invention;
FIG. 2 is a Fourier transform infrared test chart of a material according to an embodiment of the present invention;
FIG. 3 is a bacteriostatic experiment of Escherichia coli according to an embodiment of the present invention;
FIG. 4 is a scanning electron microscope image of a second material according to an embodiment of the present invention;
FIG. 5 is a graph of a Fourier transform infrared test of a second material according to an embodiment of the present invention;
FIG. 6 is a bacteriostatic experiment of Escherichia coli according to example II of the present invention;
FIG. 7 is a scanning electron microscope image of three materials according to an embodiment of the present invention;
FIG. 8 is a Fourier transform infrared test chart of three materials according to an embodiment of the present invention;
FIG. 9 shows the bacteriostatic test of Escherichia coli according to the third embodiment of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles, which is characterized by mainly comprising three parts, namely a two-dimensional metal material, a two-dimensional COF material and metal nanoparticles;
wherein the two-dimensional metal material, the two-dimensional COF material and the metal nano particles are mixed according to the mass ratio of 1: 0.4-0.7: 6.4-14.5 compounding;
wherein the two different two-dimensional materials are connected by covalent bonds to form a vertical structure heterojunction.
The invention provides a two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles, which is characterized in that two-dimensional metal materials, namely a two-dimensional COF material are mixed according to the mass ratio of 1: compounding according to the proportion of 0.4-0.7, and then loading metal nano particles according to the proper proportion, wherein the method comprises the following specific implementation steps:
1) amination of two-dimensional metal material: mixing 1 part by weight of two-dimensional metal material with a solvent, adding a silane coupling agent, and stirring at the rotation speed of 600-800rpm for 20-24 hours at the temperature of 20-35 ℃;
2) in-situ composite growth of two-dimensional material: fully mixing a main material for preparing 0.4-0.7 part by weight of a two-dimensional COF material with an aminated two-dimensional metal material, and stirring at the rotating speed of 500-800rpm for 10-30h at the temperature of 120-140 ℃ in the atmosphere of inert protective gas;
3) compounding metal nanoparticles: fully mixing 6.4-14.5 parts by weight of metal nanoparticles and a two-dimensional composite material in a solvent, adding a proper amount of reducing agent at room temperature, and stirring at the rotating speed of 600-700rpm for 0.5-2h to obtain the metal nanoparticle-carried two-dimensional metal-semiconductor photocatalytic composite material.
Wherein the two-dimensional metallic material is selected from Ti3C2、Mo2C、Ti2C、Zr3C2One or more of them.
Wherein the two-dimensional COF material is selected from one or more of TpBD, TpPa-1, TpPa-2 and COF-LZU 1.
Wherein the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane and (3-aminopropyl) diethoxymethylsilane.
Wherein the metal nanoparticles are selected from one or more of zinc oxide nanoparticles, cuprous oxide nanoparticles, silver nanoparticles and magnesium oxide nanoparticles.
Wherein the inert protective gas is selected from one or more of argon and nitrogen.
Wherein the reducing agent is selected from one or more of hydrazine hydrate, sodium borohydride and ascorbic acid.
The synthesized nano composite material and the organic coating are mixed according to the mass ratio of 1:5-30, coated on the surface of a metal matrix, and dried for more than 24 hours at room temperature, so that the antifouling coating can be obtained.
Wherein the organic coating is one or more of water-borne epoxy resin coating, polysiloxane coating, polyurethane coating, methacrylic resin coating and fluorocarbon resin coating
Example one
A two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles is synthesized by the following specific steps:
(1) amination of two-dimensional metal material: 60mg of a small layer of Ti3C2Dissolving MXene in 15mL of ethanol and deionized water at a volume ratio of 1: 4, stirring thoroughly for 30 minutes, then slowly adding 200 microlitresThe resulting 3-aminopropyltriethoxysilane was stirred at 30 ℃ and 600rpm for 20h and the resulting sample was lyophilized.
(2) In-situ composite growth of two-dimensional material: subjecting the thus-prepared aminated Ti3C270mg of-MXene and triacyl phloroglucinol, 67mg of p-aminodimethylaniline, 1.5mL of mesitylene, 1.5mL of dioxane, and 0.5mL of 3M acetic acid aqueous solution were placed in a pyrex glass tube, stirred at the temperature of 25 ℃ and the rotation speed of 750rpm for 1 hour, and the sample was uniformly dispersed. The tubes were then snap frozen in 77K (liquid N2 bath) and degassed by three freezing cycles. The tube was sealed at 120 ℃ for 30 h. The resulting sample was then dried by centrifugation with ethanol.
(3) Compounding metal nanoparticles: 10mg of the two-dimensional material compound and 150mg of silver nitrate are dissolved in 30mL of deionized water, the temperature is 25 ℃, the rotating speed is 600rpm, and the mixture is stirred for 1 hour in a dark place. Then adding 10 mu L of hydrazine hydrate, keeping the original stirring mode, continuing stirring for 30 minutes, then centrifuging for 3 times by using ethanol, and drying to obtain the two-dimensional metal/COF-based photocatalytic composite material carrying the metal nanoparticles.
(4) Preparing a coating: mixing the synthesized composite material with a methacrylic resin coating according to the mass ratio of 1: 15, coating the mixture on the surface of carbon steel, and drying for 30 hours at 25 ℃ to obtain the antifouling coating.
Example two
(1) Amination of two-dimensional metal material: 100mg of a small layer of Ti2C-MXene was dissolved in 50mL of ethanol, followed by stepwise addition of 800. mu.L of gamma-aminopropyltriethoxysilane at 30 ℃ and 800rpm for 22h, washing the resulting sample with ethanol and freeze-drying.
(2) In-situ composite growth of two-dimensional material: subjecting the thus-prepared aminated Ti230mg of C-MXene, 60mg of potassium hydroxide and 70mg of triacyl phloroglucinol are dissolved in 10mL of deionized water, placed in a three-neck flask, subjected to oil bath at 140 ℃ under the nitrogen atmosphere, rotated at 600rpm and added for 30 minutes. Then 50mg of p-phenylenediamine is dissolved in 15mL of N, N-dimethylformamide, the mixed solution is added into a three-neck flask, the original adding state is kept, and the reaction is continued for 14 hours. Centrifuging the reacted solution with ethanol for 5 times, and separatingAnd drying the solid precipitate after centrifugation.
(3) Compounding metal nanoparticles: 8mg of the prepared two-dimensional material compound, 50mg of polyvinylpyrrolidone and 48mg of copper nitrate are dissolved in 25mL of deionized water, and the mixture is stirred for 1h at the temperature of 25 ℃ and the rotating speed of 650 rpm. And then adding 500mg of ascorbic acid, continuing stirring for 1h in the original stirring mode, centrifuging for 4 times by using ethanol, and drying to obtain the two-dimensional metal/COF-based photocatalytic composite material carrying the metal nanoparticles.
(4) Preparing a coating: mixing the synthesized composite material with a water-based epoxy resin coating according to the mass ratio of 1: 20, coating the mixture on the surface of carbon steel, and drying for 36 hours at 25 ℃ to obtain the antifouling coating.
EXAMPLE III
(1) Amination of two-dimensional metal material: dissolving 5g of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane in a mass ratio of ethanol to water of 9: 1 in 20g of the solution, and sufficiently stirring and uniformly mixing the solution. 250mg of less Mo layer2C is dissolved in the mixed solution, the temperature is 30 ℃, the rotating speed is 800rpm, and the stirring is carried out for 24 hours. The resulting solution was then centrifuged 3 times with an aqueous ethanol solution and the precipitate was lyophilized.
(2) In-situ composite growth of two-dimensional material: aminated Mo prepared from 3M acetic acid 1mL, M-trimethylbenzene 3mL, dioxane 3mL, and triacyl phloroglucinol 63mg2C27 mg and p-phenylenediamine 50mg are placed in a three-neck flask and stirred for 28h at the temperature of 120 ℃ and the rotation speed of 800rpm under the nitrogen atmosphere. After cooling to room temperature, the product was centrifuged 3 times with N, N-dimethylformamide and ethanol, respectively, and vacuum dried to obtain a sample.
(3) Compounding metal nanoparticles: 12mg of the prepared two-dimensional material composite, 400mg of zinc acetate dihydrate and 10mg of dimethyl sulfone were dissolved in 80mL of methanol. Then 15mL of 0.001M potassium hydroxide was added slowly and stirring was continued for 2h, the whole being maintained at 25 ℃ and at 700 rpm. Centrifuging for three times by using ethanol to obtain the two-dimensional metal/COF-based photocatalytic composite material carrying the metal nano particles.
(4) Preparing a coating: mixing the synthesized composite material with a polyurethane coating according to a mass ratio of 1: 20, coating the mixture on the surface of an aluminum sheet, and drying the aluminum sheet at 25 ℃ for 30 hours to obtain the antifouling coating.
The composite material prepared by the invention has antibacterial performance, can keep long-acting antibacterial effect, and has weak influence on environment.
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
In addition to the technical features described in the specification, the technology is known to those skilled in the art.
Claims (10)
1. A two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles is characterized by mainly comprising three parts, namely a two-dimensional metal material, a two-dimensional COF material and metal nanoparticles;
wherein the two-dimensional metal material, the two-dimensional COF material and the metal nano particles are mixed according to the mass ratio of 1: 0.4-0.7: 6.4-14.5 compounding;
wherein the two different two-dimensional materials are connected by covalent bonds to form a vertical structure heterojunction.
2. The two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles is characterized in that two-dimensional metal materials and two-dimensional COF materials are mixed according to a mass ratio of 1: compounding according to the proportion of 0.4-0.7, and then loading metal nano particles according to the proper proportion, wherein the method comprises the following specific implementation steps:
1) amination of two-dimensional metal material: mixing 1 part by weight of two-dimensional metal material with a solvent, adding a silane coupling agent, and stirring at the rotation speed of 600-800rpm for 20-24 hours at the temperature of 20-35 ℃;
2) in-situ composite growth of two-dimensional material: fully mixing a main material for preparing 0.4-0.7 part by weight of a two-dimensional COF material with an aminated two-dimensional metal material, and stirring at the rotating speed of 500-800rpm for 10-30h at the temperature of 120-140 ℃ in the atmosphere of inert protective gas;
3) compounding metal nanoparticles: fully mixing 6.4-14.5 parts by weight of metal nanoparticles and a two-dimensional composite material in a solvent, adding a proper amount of reducing agent at room temperature, and stirring at the rotating speed of 600-700rpm for 0.5-2h to obtain the metal nanoparticle-carried two-dimensional metal-semiconductor photocatalytic composite material.
3. The metal nanoparticle-loaded two-dimensional metal/COF-based photocatalytic composite material according to claim 1 or 2, wherein the two-dimensional metal material is selected from Ti3C2、Mo2C、Ti2C、Zr3C2One or more of them.
4. The metal nanoparticle-loaded two-dimensional metal/COF-based photocatalytic composite material according to claim 1 or 2, wherein the two-dimensional COF material is one or more selected from TpBD, TpPa-1, TpPa-2, COF-LZU 1.
5. The two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles as claimed in claim 1 or 2, wherein the silane coupling agent is one or more selected from the group consisting of 3-aminopropyltriethoxysilane, γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, γ -aminoethylaminopropyltrimethoxysilane, and (3-aminopropyl) diethoxymethylsilane.
6. The two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles as claimed in claim 1 or 2, wherein the metal nanoparticles are one or more selected from zinc oxide nanoparticles, cuprous oxide nanoparticles, silver nanoparticles, and magnesium oxide nanoparticles.
7. The metal nanoparticle-loaded two-dimensional metal/COF-based photocatalytic composite material according to claim 1 or 2, wherein the inert shielding gas is one or more selected from argon and nitrogen.
8. The metal nanoparticle-loaded two-dimensional metal/COF-based photocatalytic composite material according to claim 1 or 2, wherein the reducing agent is one or more selected from hydrazine hydrate, sodium borohydride and ascorbic acid.
9. The application of the two-dimensional metal/COF-based photocatalytic composite material carrying metal nanoparticles is characterized in that the antifouling coating can be obtained by mixing the nano composite material synthesized in the claim 1 and an organic coating according to the mass ratio of 1:5-30, coating the mixture on the surface of a metal matrix and drying the mixture for more than 24 hours at room temperature.
10. The use of the metal nanoparticle-loaded two-dimensional metal/COF-based photocatalytic composite material of claim 9, wherein the organic coating is one or more of a water-based epoxy resin coating, a polysiloxane coating, a polyurethane coating, a methacrylic resin coating, and a fluorocarbon resin coating.
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