A sp 2 Carbon conjugated two-dimensional polymer thin film and preparation method and application thereof

Abstract

The application discloses a kind of sp 2 A carbon conjugated two-dimensional polymer film and its preparation method and application.The preparation method comprises: the surface of substrate is treated with amino, and amino substrate is prepared;And the amino substrate is formed with organic monomer, catalyst, organic solvent mixed reaction system, then the mixed reaction system is heated to occur Schiff base reaction, hydroxy aldehyde polymerization, to obtain nanoscale sp 2 Carbon conjugated two-dimensional polymer film.The application first uses self-assembled monolayer assisted surface to initiate in-situ synthesis sp 2 Carbon conjugated two-dimensional polymer film, and the method is suitable for in-situ, rapid and large-area preparation of uniform nanoscale film on any substrate.The two-dimensional polymer film prepared has highly ordered structure, high specific surface area, high chemical stability and excellent in-plane conjugation, and can be widely used in harsh working environment, adsorption separation, energy conversion or optoelectronic devices and other fields.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic two-dimensional materials, and relates to a kind of sp 2 Carbon conjugated two-dimensional polymer film and its preparation method and application, especially a kind of preparation method for synthesizing nanoscale organic conjugated two-dimensional polymer film in situ on the surface of any substrate by using self-assembled monolayer assisted surface initiation, and the application of the conjugated two-dimensional polymer film. BACKGROUND

[0002] Two-dimensional covalent organic frameworks (2D COFs) are an important branch of two-dimensional polymer materials, which have ordered π-stacking, rich active sites, tunable open nanochannel structure, customizable molecular building blocks and strong covalent bonds. Among them, due to the enhanced π-conjugated electron transition of carbon-carbon double bond, ultra-high chemical / thermal stability and high electron mobility, sp 2 Efficient construction of carbon-bridged fully conjugated 2D COFs is a hot research topic in the field of emerging technologies such as energy storage, semiconductor devices, energy conversion, and selective separation membranes, and harsh environments.

[0003] However, the reported sp 2 Carbon conjugated 2D COFs are in the form of powder, and the insolubility of powder and the difficulty in preparing covalent organic films hinder the application of these materials in related separation membranes, energy or optoelectronic devices. Therefore, it is of great significance to prepare large-area defect-free sp 2 Carbon conjugated 2D COF film (or sp 2 Carbon conjugated two-dimensional polymer) has important significance. However, the formation of carbon-carbon double bond requires high temperature, making the synthesis of sp 2 Carbon conjugated two-dimensional polymer film is quite challenging, which cannot be prepared by classical methods widely used for the synthesis of two-dimensional polymer films connected by imine bonds, such as interfacial polymerization, vapor assisted transformation and vacuum assisted filtration. Therefore, it is very necessary to develop a strategy for manufacturing large-area sp 2 Carbon conjugated two-dimensional polymer film for the application of many potential fields. SUMMARY

[0004] The main purpose of the present application is to provide a kind of sp 2 Carbon conjugated two-dimensional polymer film and its preparation method and application to overcome the deficiencies of the prior art.

[0005] To achieve the aforementioned application purposes, the technical solutions adopted by the present application include:

[0006] The present application provides a kind of sp 2 Carbon conjugated two-dimensional polymer film and its preparation method, which comprises:

[0007] amino group to the surface of the substrate to obtain an amino group treated substrate;

[0008] and forming a mixed reaction system of the amino group treated substrate, an organic monomer, a catalyst and an organic solvent, and then heating the mixed reaction system to generate a Schiff base reaction and an aldol polymerization reaction, thereby obtaining the sp 2 a carbon conjugated two-dimensional polymer film; wherein the organic monomer comprises an aldehyde group monomer and a methyl monomer.

[0009] The embodiment of the present application also provides the sp 2 a carbon conjugated two-dimensional polymer film, and the sp 2 The carbon conjugated two-dimensional polymer film has a porous structure.

[0010] The embodiment of the present application also provides the sp 2 application of the carbon conjugated two-dimensional polymer film in the fields of adsorption separation, energy conversion or photoelectric devices.

[0011] Compared with the prior art, the present application has the following beneficial effects:

[0012] (1) The present application first uses a methyl monomer and an aldehyde group monomer to synthesize a conjugated two-dimensional polymer film with ethylene bond connection on the surface of a substrate;

[0013] (2) The present application uses a monolayer surface as a reaction interface, and uses an initiator containing an amino group to graft on various substrates, so that the surface-initiated polymerization can be effectively used for various substrates, has a large lateral size, a controllable thickness (50 nanometers to 1 micrometer) and is easy to peel off, the lateral size and uniformity of the two-dimensional polymer film are improved, and the complexity of the experimental device is reduced. Meanwhile, the preparation method can quickly, economically and in a large area prepare a uniform nanoscale film, and the production efficiency of the two-dimensional polymer film is improved;

[0014] (3) The present application takes advantage of the characteristics of covalent connection of two monomers, can not only provide a uniform porous structure, but also can make the material stably exist in various organic solvents and acid-base solutions, and the synthesized conjugated two-dimensional polymer film is in an amorphous state, so that the two-dimensional polymer film has the characteristics of flexibility and self-supporting, and the application place of the material is expanded;

[0015] (4) The conjugated two-dimensional polymer prepared by the present application can be applied to the fields of adsorption separation, energy conversion or photoelectric devices due to its highly ordered structure, high specific surface area and strong interlayer π-π interaction force. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the accompanying drawings needed to be used in the embodiments or prior art description will be briefly introduced. Obviously, the accompanying drawings in the following description only represent some embodiments described in the present application, and for those skilled in the art, other drawings can also be obtained without creative labor on the basis of these drawings.

[0017] Figure 1 is a sp 2 - Reaction mechanism diagram of carbon conjugated two-dimensional polymer film;

[0018] Figure 2 is an optical photo of the conjugated two-dimensional polymer film prepared in Example 1 of the present application;

[0019] Figure 3 is a scanning electron microscope photo of the conjugated two-dimensional polymer film prepared in Example 1 of the present application;

[0020] Figure 4 is a transmission electron microscope photo of the conjugated two-dimensional polymer film prepared in Example 1 of the present application;

[0021] Figure 5 is a permeation power density diagram of the conjugated two-dimensional polymer film prepared in Example 1 of the present application;

[0022] Figure 6 is a photo of the film prepared in Comparative Example 1 and Example 1 of the present application;

[0023] Figure 7 is a contact angle test photo in Comparative Example 2 of the present application. DETAILED DESCRIPTION

[0024] In view of the problems in the prior art described above, after long-term research and a large number of experiments, the present inventors have proposed the technical solutions, which are mainly based on a self-assembled monolayer assisted surface initiation method to in-situ synthesize sp 2 - Carbon conjugated two-dimensional polymer film, in the preparation process, different thickness of the film can be obtained by adjusting the monomer concentration, and the two-dimensional polymer film prepared by the method can be transferred to any substrate as needed, which is conducive to the construction of different structure application devices.

[0025] The present application first utilizes methyl monomer and aldehyde monomer to synthesize sp 2 - Carbon conjugated two-dimensional polymer film, and provides a preparation method of sp 2The growth conditions of the carbon conjugated two-dimensional polymer film. Since the surface-initiated polymerization can be applied to a large-size substrate, the preparation method can quickly, economically and large-area prepare a uniform nanoscale film and improve the production efficiency of the two-dimensional polymer film. Meanwhile, the carbon conjugated two-dimensional polymer film prepared by the method can be widely applied to the energy conversion field due to the unique porous structure and the surface charged groups.

[0026] Specifically, as one aspect of the technical scheme of the application, the application relates to a kind of sp 2 The preparation method of the carbon conjugated two-dimensional polymer film comprises:

[0027] The surface of the substrate is subjected to amino treatment to obtain an amino substrate;

[0028] The amino substrate is mixed with an organic monomer, a catalyst and an organic solvent to form a mixed reaction system, and then the mixed reaction system is heated to generate a Schiff base reaction and an aldol polymerization reaction, so that a nanoscale sp 2 The carbon conjugated two-dimensional polymer film; wherein the organic monomer comprises an aldehyde monomer and a methyl monomer.

[0029] In the application, the sp 2 The reaction mechanism diagram of the carbon conjugated two-dimensional polymer film is shown in Figure 1 .

[0030] In some preferred embodiments, the sp 2 The preparation method of the carbon conjugated two-dimensional polymer film comprises:

[0031] The surface of the substrate is subjected to amino treatment, and then a uniform mixed reaction system is formed with an organic monomer, a catalyst and an organic solvent;

[0032] The uniform mixed reaction system is heated under the action of high temperature to accelerate the Schiff base reaction and the aldol polymerization reaction on the surface of the substrate, so that a nanoscale sp 2 The carbon conjugated two-dimensional polymer film is obtained on the surface of the substrate.

[0033] In the application, the aldehyde monomer in the uniform mixed reaction system first undergoes a Schiff base condensation reaction with the amino monolayer to form a uniform monolayer with an aldehyde end group; then, the aldehyde monolayer can act as a nucleation site of the reactant to undergo an aldol condensation reaction with the methyl monomer in the solution, and finally, with the growth of the polymer, a uniform sp 2 c-COF film is obtained by in-situ growth.

[0034] In some preferred embodiments, the method for efficiently preparing the sp2-carbon conjugated two-dimensional polymer thin film of the present application comprises the following steps: sequentially adding a methyl-containing monomer (such as a triazine monomer), an aldehyde group-containing monomer (such as an aromatic aldehyde group-containing monomer), and a catalyst into a reaction container, accelerating the reaction at high temperature, and obtaining an sp2-carbon conjugated two-dimensional polymer thin film on the surface of a substrate. 2 - carbon conjugated two-dimensional polymer thin film.

[0035] In some preferred embodiments, the method comprises: mixing an organic monomer, an organic solvent, and a catalyst, and then performing ultrasonic dispersion treatment, adding an aminated substrate to form the mixed reaction system, then performing freeze-thaw treatment under liquid nitrogen conditions, and then allowing the obtained substrate to react at 20-180°C for 3-5 days in a protective atmosphere, to obtain the nanoscale sp2-carbon conjugated two-dimensional polymer thin film. 2 - carbon conjugated two-dimensional polymer thin film.

[0036] Further, the freeze-thaw treatment is performed 2-10 times.

[0037] In some preferred embodiments, the method comprises:

[0038] The organic monomer, the organic solvent, the catalyst, and the aminated substrate are sequentially added into the reaction container, and vacuum is applied under liquid nitrogen conditions, and then the substrate is thawed, and the reaction container is heated in an inert atmosphere by repeating the freeze-thaw treatment multiple times.

[0039] Further, the method comprises: mixing the monomer, the catalyst, and the organic solvent, and then performing ultrasonic dispersion treatment for 1-10 min to form a uniformly dispersed monomer solution.

[0040] Further, the method comprises: performing freeze-thaw treatment under liquid nitrogen conditions for 5-10 min, and then thawing, and repeating the freeze-thaw treatment 2-10 times, and then sealing the reaction container after introducing nitrogen gas.

[0041] Further, the method comprises: accelerating the polymer reaction on the surface of the substrate, and the time is 3-4 days.

[0042] Further, the polymer reaction at the interface is a Schiff base polycondensation reaction and a hydroxy aldehyde condensation reaction, and the reaction temperature is 120-180°C.

[0043] Further, the nanoscale sp2-carbon conjugated two-dimensional polymer thin film is obtained on the surface of the substrate. 2 - carbon conjugated two-dimensional polymer thin film, and then the two-dimensional polymer thin film is transferred by etching.

[0044] Further, the monomer concentration is adjusted to increase the thickness of the sp2-carbon conjugated two-dimensional polymer thin film, and the monomer concentration is 0.5-6 mg / mL. 2 - carbon conjugated two-dimensional polymer thin film, and then the two-dimensional polymer thin film is transferred by etching.

[0045] Further, by the treatment of amination on various substrates, polymerization can occur on the aminated silicon wafer, aluminum sheet, copper sheet, iron sheet, glass and polyacrylonitrile surface, thereby obtaining nanoscale sp 2 - carbon conjugated two-dimensional polymer thin film.

[0046] In some more preferred embodiments, the organic monomer and catalyst are uniformly dispersed in a specific solution, comprising the following steps:

[0047] (1) The organic monomer and catalyst are added to an organic solvent and ultrasonically dispersed for 5-10 min to uniformly disperse the monomer, and if necessary, the undissolved monomer deposited at the bottom is mixed uniformly.

[0048] (2) The aminated substrate is placed in a reaction container.

[0049] Further, the reaction container is repeatedly frozen and thawed under liquid nitrogen conditions, sealed and heated at 120-180°C under an inert atmosphere.

[0050] In some preferred embodiments, the aldehyde group monomer is a monomer comprising nineteen aldehyde groups, and the aldehyde group monomer has a clear planar structure.

[0051] In some preferred embodiments, the aldehyde group monomer includes any one of or a combination of two or more of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine monomer, trimesaldehyde monomer, 1,3,5-tris(4-formylphenyl)benzene, 1,3,5-tris(4-formylphenyl)amine, 2,5-dihydroxyterephthaldehyde, hexakis(4-formylphenyl)benzene, 5,5'-(1,4-phenylene)bis(pyridine-2-carboxaldehyde), tetrakis(4-formylphenyl)pyrene, tetrakis(4-formylphenyl)ethylene, tetrakis(4-formylphenyl)ethylene, tetrakis(4-formylphenyl)methane, tetrakis(4-formylphenyl)silane, tris(4-formylphenoxy)-1,3,5-triazine, 2,5-diformylpyrazine, tetrakisformylbiphenyl, 2,6-hydroxy-1,5-diformylnaphthalene, tris(4-hydroxy-3'-formylphenyl)benzene, tris(4-methoxy-3'-formylphenyl)benzene, tris(4'-formyl[1,1'-biphenyl]-4-yl)benzene, and the like, and is not limited thereto.

[0052] In some preferred embodiments, the methyl monomer is a monomer comprising eleven methyl groups.

[0053] In some preferred embodiments, the methyl monomer includes any one of 2,4,6-trimethyl-1,3,5-triazine monomer, 2,4,6-trimethylpyridine, 2,5-dimethylpyrazine, 2,4,6-tricyano-1,3,5-trimethylbenzene, 2,4,6-trimethylpyridine-3,5-dinitrile, 4,4'-diphenyldiacetonitrile, 2,2'-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(4,1-phenylene))diacetonitrile, 2,2'-(5'-(4-(cyanomethyl)phenyl)-[1,1':3',1'-terphenyl]-4,4"-diyl)diacetonitrile, 2,2',2",2"'-(ethene-1,1,2,2-tetrayltetrakis([1,1'-biphenyl]-4',4-diyl))tetracetonitrile, tri(4-(3-methylthiophen-2-yl)phenyl)amine, or a combination of two or more thereof, and is not limited thereto.

[0054] In some preferred embodiments, the catalyst includes a Lewis acid and / or acetic acid, and is not limited thereto.

[0055] Further, the Lewis acid includes any one of trifluoroacetic acid, triflic acid, p-toluenesulfonic acid, benzoic acid, benzoic anhydride, or a combination of two or more thereof, and is not limited thereto.

[0056] In some preferred embodiments, the organic solvent includes any one of mesitylene, dioxane, o-dichlorobenzene, n-butanol, N,N-dimethylformamide, or a combination of two or more thereof, and is not limited thereto.

[0057] Further, a molar ratio of the aldehyde monomer to the methyl monomer in the organic monomer is 1:(2-6).

[0058] In some preferred embodiments, a molar ratio of the catalyst to the methyl monomer is (0.5-2):(0.35-1.5).

[0059] In some preferred embodiments, the preparation method includes:

[0060] performing a plasma cleaning process on a surface of a substrate to obtain a hydroxylated substrate;

[0061] and, reacting the hydroxylated substrate with an amino initiator at 60-120°C for 1-3h using a vapor deposition method to obtain an aminated substrate.

[0062] In some preferred embodiments, the preparation method comprises: plasma cleaning a clean substrate surface to hydroxylate the substrate surface, then, in a glove box, adding an amino initiator into a glass bottle, placing the glass bottle and the hydroxylated substrate in a large surface dish, and placing at 100℃ for 1-3 hours after sealing, and grafting the amino initiator to the substrate surface by vapor deposition, and then cleaning with anhydrous ethanol to obtain a substrate with a surface amino group.

[0063] In some preferred embodiments, the substrate comprises any one of a silicon wafer, an aluminum wafer, an iron wafer, a copper wafer, glass, polyacrylonitrile, and the like, but is not limited thereto.

[0064] In some preferred embodiments, the preparation method further comprises: after the Schiff base reaction and the aldol polymerization reaction are completed, transferring the sp 2 a carbon-conjugated two-dimensional polymer film.

[0065] In some preferred embodiments, the preparation method further comprises: after the substrate surface obtains a nanoscale sp 2 a carbon-conjugated two-dimensional polymer film, transferring the two-dimensional polymer film by etching, or adjusting the monomer concentration to increase the thickness of the two-dimensional polymer film.

[0066] Further, the concentration for increasing the thickness of the film by adjusting the monomer concentration is 0.5-6 mg / mL.

[0067] In some more specific embodiments, the preparation method of the sp 2 a carbon-conjugated two-dimensional polymer film can comprise the following steps:

[0068] First step: aminoating the substrate surface;

[0069] Second step: sequentially adding the weighed organic monomer, catalyst, organic solvent, and substrate into a quartz glass tube;

[0070] Third step: freeze-thawing under liquid nitrogen and repeating the process multiple times;

[0071] Fourth step: accelerating the polymerization reaction by heating under an inert atmosphere to obtain a nanoscale sp 2 a carbon-conjugated two-dimensional polymer film on the substrate surface;

[0072] Fifth step: further, transferring or standing to grow to increase the thickness of the film, and then transferring the film to various substrate surfaces to construct corresponding application devices.

[0073] Another aspect of the embodiments of the present application also provides the sp 2a carbon conjugated two-dimensional polymer film, the sp 2 The carbon conjugated two-dimensional polymer film has a porous structure.

[0074] Further, the sp 2 The carbon conjugated two-dimensional polymer film has a pore size of 0.9-3 nm, a specific surface area of 100-1000 m 2 g -1 , and a porosity of 0.2-0.7.

[0075] Further, the sp 2 The carbon conjugated two-dimensional polymer film has a thickness of 50 nm-1 μm.

[0076] The present application provides a uniform porous structure by virtue of the covalent connection of two monomers, and the material can stably exist in various organic solvents and strong acid and strong base solutions, and the two-dimensional polymer film is flexible and self-supporting, thus expanding the application of the material.

[0077] Another aspect of the embodiment of the present application also provides the aforementioned sp 2 The carbon conjugated two-dimensional polymer film is applied in the fields of adsorption separation, energy conversion or optoelectronic devices.

[0078] According to the foregoing technical solution, the present application uses a monomolecular layer surface as a reaction interface, and grafts an initiator containing an amino group on various substrates, so as to effectively utilize the surface-initiated polymerization suitable for various substrates, large lateral size, controllable thickness and easy peeling, improve the lateral size and uniformity of the two-dimensional polymer film, and reduce the complexity of the experimental device.

[0079] The present application first uses a self-assembled monomolecular layer to assist in situ synthesis of a sp 2 carbon conjugated two-dimensional polymer film. Meanwhile, the method is suitable for in situ, rapid and large-area preparation of uniform nanoscale films on any complex substrate (such as a silicon wafer, an aluminum sheet, a copper sheet, an iron sheet, glass, polyacrylonitrile, etc.), and the obtained two-dimensional polymer film can be widely used in the fields related to adsorption separation, energy conversion or optoelectronic devices due to its highly ordered structure, high specific surface area, high chemical stability and excellent in-plane conjugation.

[0080] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments and the accompanying drawings. The embodiments are implemented on the premise of the technical solutions of the present application, and detailed implementation manners and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0081] The experimental materials used in the following examples are commercially available from routine biochemical reagent companies, unless otherwise specified.

[0082] Example 1

[0083] 1. A mixture of 0.025 mmol 2,4,6-trimethyl-1,3,5-triazine monomer and 0.025 mmol 1,3,5-tris(4-formylphenyl)triazine and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) was loaded into a quartz glass tube. After adding 0.40 mL trifluoroacetic acid, 0.05 mL acetonitrile and an amino-functionalized silicon wafer substrate, the reaction mixture was ultrasonicated to obtain a uniform suspension.

[0084] 2. The quartz glass tube was frozen in liquid nitrogen and vacuumized for 10 min, then thawed at room temperature, and this process was repeated three times. The quartz glass tube was sealed.

[0085] 3. The reaction tube was heated to 150 °C under N2 atmosphere for 3 days. After that, the reacted silicon wafer was taken out of the solution and cleaned with tetrahydrofuran and acetone three times to obtain sp2 conjugated two-dimensional polymer film grown on the surface of the silicon wafer. 2 - carbon conjugated two-dimensional polymer film.

[0086] 4. A layer of polymethyl methacrylate (PMMA) was spin-coated on the surface of the silicon wafer. Then the silicon wafer was placed in a 2% HF solution to etch the SiO2 layer, and the COF / PMMA film floating on the solution was transferred to another substrate. Finally, the PMMA protective layer was removed with acetone to obtain a self-supporting two-dimensional polymer film that can be transferred to any substrate. The optical photograph of the two-dimensional polymer film is shown in Figure 2 , and the scanning electron microscope and transmission electron microscope pictures are shown in Figure 3 , 4 .

[0087] 5. The two-dimensional polymer film at the interface was transferred using a silicon wafer with a 3 μm single hole on the surface with a size of 5*5 mm to prepare a salt concentration difference power conversion device for converting green energy in seawater. As shown in Figure 5 , the maximum power output density can reach 55.3 W / m 2 .

[0088] Example 2

[0089] 1. A mixture of 0.025 mmol 2,4,6-trimethyl-1,3,5-triazine monomer and 0.025 mmol 1,3,5-tris(4-formylphenyl)triazine and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) was loaded into a quartz glass tube. After adding 0.40 mL trifluoroacetic acid, 0.05 mL acetonitrile and an amino-functionalized silicon wafer substrate, the reaction mixture was ultrasonicated to obtain a uniform suspension.

[0090] 2. Freeze in liquid nitrogen and vacuum for 10 min, then thaw at room temperature, repeat this process three times, seal the quartz glass tube.

[0091] 3. Heat the reaction tube to 150°C for 3 days under N2 atmosphere. After that, take out the reacted silicon wafer from the solution, clean it with tetrahydrofuran and acetone three times, get sp 2 - Carbon conjugated two-dimensional polymer thin film.

[0092] 4. Spin a layer of polymethyl methacrylate (PMMA) on the surface of the silicon wafer. Then place the silicon wafer in a 2% HF solution to etch the SiO2 layer, transfer the COF / PMMA film floating on the solution to other substrates. Finally, remove the PMMA protective layer with acetone to get a self-supporting two-dimensional polymer thin film that can be transferred to any substrate.

[0093] Example 3

[0094] 1. A mixture of 0.025 mmol 2,4,6-trimethyl-1,3,5-triazine monomer and 0.025 mmol 1,3,5-tris(4-formylphenyl)benzene and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) was loaded into a heat-resistant glass tube. After adding 0.40 mL benzoic anhydride, 0.05 mL acetonitrile and amino-silicon wafer substrate, the reaction mixture was ultrasonically treated to obtain a uniform suspension.

[0095] 2. Freeze in liquid nitrogen and vacuum for 10 min, then thaw at room temperature, repeat this process three times, seal the quartz glass tube.

[0096] 3. Heat the reaction tube to 150°C for 3 days under N2 atmosphere. After that, take out the reacted silicon wafer from the solution, clean it with tetrahydrofuran and acetone three times, get sp 2 - Carbon conjugated two-dimensional polymer thin film.

[0097] 4. Spin a layer of polymethyl methacrylate (PMMA) on the surface of the silicon wafer. Then place the silicon wafer in a 2% HF solution to etch the SiO2 layer, transfer the COF / PMMA film floating on the solution to other substrates. Finally, remove the PMMA protective layer with acetone to get a self-supporting two-dimensional polymer thin film that can be transferred to any substrate.

[0098] Example 4

[0099] 1. A mixture of 0.025 mmol 2,4,6-trimethyl-1,3,5-triazine monomer and 0.025 mmol 1,3,5-tris(4-formylphenyl)amine and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) was loaded into a heat-resistant glass tube. After adding 0.40 mL benzoic acid, 0.05 mL acetonitrile and an amino-functionalized silicon wafer substrate, the reaction mixture was sonicated to obtain a uniform suspension.

[0100] 2. The quartz glass tube was frozen in liquid nitrogen and vacuumed for 10 min, then thawed at room temperature, and this process was repeated three times.

[0101] 3. The reaction tube was heated to 150 °C for 3 days under N2 atmosphere. After that, the reacted silicon wafer was taken out of the solution and washed with tetrahydrofuran and acetone three times to obtain sp 2 - carbon conjugated two-dimensional polymer thin film.

[0102] 4. A layer of polymethyl methacrylate (PMMA) was spin-coated on the surface of the silicon wafer. Then the silicon wafer was placed in a 2% HF solution to etch the SiO2 layer, and the COF / PMMA film floating on the solution was transferred to other substrates. Finally, the PMMA protective layer was removed with acetone to obtain a self-supporting two-dimensional polymer thin film that can be transferred to any substrate.

[0103] Example 5

[0104] 1. A mixture of 0.025 mmol 2,4,6-trimethylpyridine monomer and 0.025 mmol 1,3,5-tris(4-formylphenyl)triazine and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) was loaded into a heat-resistant glass tube. After adding 0.40 mL acetic acid, 0.05 mL acetonitrile and an amino-functionalized silicon wafer substrate, the reaction mixture was sonicated to obtain a uniform suspension.

[0105] 2. The quartz glass tube was frozen in liquid nitrogen and vacuumed for 10 min, then thawed at room temperature, and this process was repeated three times.

[0106] 3. The reaction tube was heated to 150 °C for 3 days under N2 atmosphere. After that, the reacted silicon wafer was taken out of the solution and washed with tetrahydrofuran and acetone three times to obtain sp 2 - carbon conjugated two-dimensional polymer thin film.

[0107] 4. A layer of polymethyl methacrylate (PMMA) was spin-coated on the surface of the silicon wafer. Then the silicon wafer was placed in a 2% HF solution to etch the SiO2 layer, and the COF / PMMA film floating on the solution was transferred to other substrates. Finally, the PMMA protective layer was removed with acetone to obtain a self-supporting two-dimensional polymer thin film that can be transferred to any substrate.

[0108] Example 6

[0109] 1. A mixture of 0.025 mmol 2,4,6-trimethylpyridine monomer and 0.025 mmol 1,3,5-triformylphenyl and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) was loaded into a heat-resistant glass tube. After adding 0.40 mL trifluoromethanesulfonic acid, 0.05 mL acetonitrile and aminated silicon wafer substrate, the reaction mixture was ultrasonically treated to obtain a uniform suspension.

[0110] 2. The quartz glass tube was frozen under liquid nitrogen and vacuumized for 10 min, then thawed at room temperature, and this method was repeated three times, and the quartz glass tube was sealed.

[0111] 3. The reaction tube was heated to 150°C under N2 atmosphere for 3 days. After that, the reacted silicon wafer was taken out of the solution and cleaned with tetrahydrofuran and acetone three times to obtain sp2 carbon conjugated two-dimensional polymer thin film grown on the surface of the silicon wafer. 2 - carbon conjugated two-dimensional polymer thin film.

[0112] 4. A layer of polymethyl methacrylate (PMMA) was spin-coated on the surface of the silicon wafer. Then the silicon wafer was placed in a 2% HF solution to etch the SiO2 layer, and the COF / PMMA film floating on the solution was transferred to other substrates. Finally, the PMMA protective layer was removed with acetone to obtain a self-supporting two-dimensional polymer thin film that can be transferred to any substrate.

[0113] Example 7

[0114] 1. A mixture of 0.025 mmol 2,4,6-trimethylpyridine monomer and 0.025 mmol 1,3,5-triformylphenyl and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) was loaded into a heat-resistant glass tube. After adding 0.40 mL trifluoromethanesulfonic acid, 0.05 mL acetonitrile and aminated silicon wafer substrate, the reaction mixture was ultrasonically treated to obtain a uniform suspension.

[0115] 2. The quartz glass tube was frozen under liquid nitrogen and vacuumized for 10 min, then thawed at room temperature, and this method was repeated three times, and the quartz glass tube was sealed.

[0116] 3. The reaction tube was heated to 150°C under N2 atmosphere for 3 days. After that, the reacted silicon wafer was taken out of the solution and cleaned with tetrahydrofuran and acetone three times to obtain sp2 carbon conjugated two-dimensional polymer thin film grown on the surface of the silicon wafer. 2 - carbon conjugated two-dimensional polymer thin film.

[0117] 4. A layer of polymethyl methacrylate (PMMA) is spin-coated on the surface of the silicon wafer. The silicon wafer is then etched in 2% HF solution to remove the SiO2layer and the COF / PMMA film floating on the solution is transferred to another substrate. Finally, the PMMA protective layer is removed with acetone to obtain a self-supported two-dimensional polymer film, which can be transferred to any substrate.

[0118] Example 8

[0119] 1. A mixture of 0.025 mmol 2,4,6-trimethylpyridine monomer and 0.025 mmol 1,3,5-tri(4-formylphenyl)amine and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) is loaded into a heat-resistant glass tube. After adding 0.40 mL p-toluenesulfonic acid, 0.05 mL acetonitrile and an aminated silicon wafer substrate, the reaction mixture is ultrasonically treated to obtain a uniform suspension.

[0120] 2. The quartz glass tube is frozen under liquid nitrogen conditions and vacuumized for 10 min, and then thawed at room temperature. This process is repeated three times, and the quartz glass tube is sealed.

[0121] 3. The reaction tube is heated to 150°C under N2atmosphere for 3 days. After that, the reacted silicon wafer is taken out of the solution and cleaned with tetrahydrofuran and acetone three times to obtain sp 2 - carbon conjugated two-dimensional polymer film.

[0122] 4. A layer of polymethyl methacrylate (PMMA) is spin-coated on the surface of the silicon wafer. The silicon wafer is then etched in 2% HF solution to remove the SiO2layer and the COF / PMMA film floating on the solution is transferred to another substrate. Finally, the PMMA protective layer is removed with acetone to obtain a self-supported two-dimensional polymer film, which can be transferred to any substrate.

[0123] Example 9

[0124] 1. A mixture of 0.025 mmol 2,4,6-trimethylpyridine monomer and 0.025 mmol 1,3,5-tri(4-formylphenyl)benzene and mesitylene / 1,4-dioxane (1:1, v / v, 1.8 mL) is loaded into a heat-resistant glass tube. After adding 0.40 mL trifluoromethanesulfonic acid, 0.05 mL acetonitrile and an aminated silicon wafer substrate, the reaction mixture is ultrasonically treated to obtain a uniform suspension.

[0125] 2. The quartz glass tube is frozen under liquid nitrogen conditions and vacuumized for 10 min, and then thawed at room temperature. This process is repeated three times, and the quartz glass tube is sealed.

[0126] 3. The reaction tube was heated to 180 °C under N2atmosphere for 4 days. After that, the reacted silicon wafer was taken out of the solution and cleaned with tetrahydrofuran and acetone for three times to get sp 2 - Carbon conjugated two-dimensional polymer thin film.

[0127] 4. A layer of polymethyl methacrylate (PMMA) was spin-coated on the surface of the silicon wafer. Then the silicon wafer was placed in a 2% HF solution to etch the SiO2layer, and the COF / PMMA film floating on the solution was transferred to other substrates. Finally, the PMMA protective layer was removed with acetone to obtain a self-supporting two-dimensional polymer thin film, which can be transferred to any substrate.

[0128] Comparative Example 1

[0129] The method was the same as Example 1, except that the substrate was not aminated. As shown in the figure, the left side is the unaminated substrate in Comparative Example 1, and the surface has no COF film after reaction, and the right side is the aminated substrate in Example 1, and the surface has a clear COF film after reaction. Figure 6

[0130] Comparative Example 2

[0131] The method was the same as Example 1, except that the organic monomer only included an aldehyde monomer, and no film was generated on the surface of the substrate. As shown in the figure, the change in contact angle test proves that the Schiff base reaction occurs only by adding an aldehyde monomer, and an aldehyde monolayer is generated, thereby proving the reaction mechanism. Figure 7

[0132] Comparative Example 3

[0133] The method was the same as Example 1, except that the organic monomer only included a methyl monomer, and there was no change on the surface of the substrate.

[0134] In addition, the inventors of the present case also carried out tests with other raw materials, process operations, and process conditions described in the specification with reference to the foregoing examples, and all obtained relatively ideal results.

[0135] It should be understood that the technical solutions of the present application are not limited to the specific implementation cases described above, and any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims falls within the protection scope of the present application.​​

Claims

1. A sp 2 - A method for producing a carbon conjugated two-dimensional polymer thin film, characterized by The method comprises: amino group treatment is carried out on the surface of the substrate to obtain an amino group treated substrate; And, the aminoated substrate is mixed with an organic monomer, a catalyst, and an organic solvent to form a mixed reaction system, and then the mixed reaction system is heated to generate a Schiff base reaction and an aldol polymerization reaction, thereby obtaining a nanoscale sp 2 A carbon conjugated two-dimensional polymer film; wherein the organic monomer comprises an aldehyde monomer and a methyl monomer; the aldehyde monomer comprises any one of 2,4,6-tris(4-aldehyde phenyl)-1,3,5-triazine monomer, trimesaldehyde monomer, 1,3,5-tris(4-formyl phenyl) benzene, 1,3,5-tris(4-formyl phenyl) amine, 2,5-dihydroxy-p-xylylene glycol, hexa(4-formyl phenyl) benzene, 5,5'-(1,4-phenylene) bis(pyridine-2-carboxaldehyde), tetra(4-formaldehyde phenyl) pyrene, tetra(4-aldehyde phenyl) ethylene, tetra-(4-aldehyde-(1,1-biphenyl)) ethylene, tetra(4-formyl phenyl) methane, tetra(4-formyl phenyl) silane, tris(4-formyl phenoxy)-1,3,5-triazine, 2,5-dialdehyde pyrazine, tetraaldehyde biphenyl, 2,6-hydroxy-1,5-dialdehyde naphthalene, tris(4-hydroxy-3'-aldehyde phenyl) benzene, tris(4-methoxy-3'-aldehyde phenyl) benzene, tris(4'-aldehyde[1,1'-biphenyl]-4-yl) benzene; and the methyl monomer comprises any one of 2,4,6-trimethyl-1,3,5-triazine monomer, 2,4,6-trimethylpyridine, 2,5-dimethylpyrazine, 2,4,6-tricyano-1,3,5-trimethylbenzene, 2,4,6-trimethylpyridine-3,5-dicyanide, tris(4-(3-methylthiophene-2-yl) phenyl) amine.

2. The method of claim 1, wherein: the catalyst comprises Lewis acid and / or acetic acid; the Lewis acid comprises any one of trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzoic acid and benzoic anhydride.

3. The method of claim 1, wherein: the organic solvent comprises any one of mesitylene, dioxane, o-dichlorobenzene, n-butanol and N,N-dimethylformamide.

4. The method of claim 1, wherein: the molar ratio of aldehyde monomer to methyl monomer in the organic monomer is 1: (2-6).

5. The method of claim 1, wherein: the molar ratio of the catalyst to the methyl monomer is (0.5-2):(0.35-1.5).

6. The method of claim 1, wherein The method comprises: the surface of the substrate is hydroxylated by plasma cleaning, and then in a glove box, an amino initiator is added into a glass bottle, the glass bottle and the hydroxylated substrate are placed in a large surface dish, and after being sealed, the amino initiator is grafted onto the surface of the substrate by gas phase deposition at a high temperature of 100℃ for 1-3 hours, and then the surface of the substrate is cleaned with anhydrous ethanol to obtain an amino group treated substrate.

7. The method of claim 1, wherein: the substrate comprises any one of silicon wafer, aluminum sheet, iron sheet, copper sheet, glass and polyacrylonitrile.

8. The method of claim 1, wherein The method further comprises: After the Schiff base reaction and the aldol polymerization reaction are completed, the sp 2 - Carbon conjugated two-dimensional polymer thin film.

9. sp2 produced by the production method according to any one of claims 1 to 8 2 - carbon conjugated two-dimensional polymer film characterized by: The sp 2 The carbon conjugated two-dimensional polymer thin film has a porous structure. 2 The carbon conjugated two-dimensional polymer thin film has a thickness of 50 nm to 1 μm.

10. The sp of claim 9 2 - Use of carbon conjugated two-dimensional polymer thin films in the field of energy conversion or optoelectronic devices.

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