CN111876757B - Preparation method of inorganic two-dimensional nano material based on plane patterning polymer brush - Google Patents
Preparation method of inorganic two-dimensional nano material based on plane patterning polymer brush Download PDFInfo
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- CN111876757B CN111876757B CN202010595499.0A CN202010595499A CN111876757B CN 111876757 B CN111876757 B CN 111876757B CN 202010595499 A CN202010595499 A CN 202010595499A CN 111876757 B CN111876757 B CN 111876757B
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- ASVJFTFEDFWVRJ-UHFFFAOYSA-K thulium(3+);2,2,2-trifluoroacetate Chemical compound [Tm+3].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F ASVJFTFEDFWVRJ-UHFFFAOYSA-K 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- CURCMGVZNYCRNY-UHFFFAOYSA-N trimethylazanium;iodide Chemical compound I.CN(C)C CURCMGVZNYCRNY-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of an inorganic two-dimensional nano material based on a plane patterning polymer brush. The method comprises the following steps: (1) an ATRP initiator is connected on a smooth plane substrate, and then a patterned diblock copolymer brush is grown on the surface of the substrate by a method of combining photoinduction SI-ATRP and photomask patterning treatment; (2) soaking the patterned polymer brush into various inorganic nanometer precursor solutions for 0.5-240 hours, and selectively loading the inorganic precursors to the inner specific block layer of the block polymer brush through coordination and electrostatic action; (3) and finally preparing various inorganic two-dimensional nano materials on the surface of the substrate through in-situ reaction. The method can accurately control the size and the appearance of the material on a mesoscopic scale, can be processed and formed at one time, and can be suitable for preparing various inorganic two-dimensional materials. The prepared inorganic two-dimensional nano material can be widely applied to the fields of energy, catalysis, electronics and electric appliances.
Description
Technical Field
The invention belongs to the technical field of two-dimensional nanomaterials, and particularly relates to a preparation method of an inorganic two-dimensional nanomaterial based on a plane patterning polymer brush.
Background
Compared with a macroscopic body material, the two-dimensional nano material usually shows special electrical, optical, magnetic and catalytic properties and the like, so that the two-dimensional nano material has important application prospects in the fields of energy sources, ferroelectrics, catalysis, wave absorption, sensors, field effect transistors and the like. In recent decades, with the intensive research on two-dimensional nanomaterials, more two-dimensional nanomaterials with unique properties, such as insulators, semiconductors, and even superconductors, have been gradually discovered. The discovery of the advanced materials greatly promotes the progress of scientific research and industrial production, and simultaneously reveals the important significance of exploring a feasible and reliable two-dimensional nano-material preparation strategy. Particularly, in recent years, research on high-quality two-dimensional nanomaterials is increasing, and how to efficiently prepare the high-quality two-dimensional nanomaterials to explore the correlation between the parameters such as the nanometer components, the size, the morphology and the like and the performance of the nanomaterials is an important issue in the fields of chemistry and material science.
The synthesis of two-dimensional nano materials can be mainly divided into two strategies of top-down (chemical or mechanical stripping method and the like) and bottom-up (wet chemical method, chemical vapor deposition and the like). The basic idea of the top-down method is to strip the macroscopic material into a single-layer or several-layer nanosheet, i.e., to break the weak interaction force between the layers in the macroscopic crystal by means of external force. Correspondingly, the synthesis strategy of 'bottom-up' refers to that two-dimensional nano materials are directly synthesized from precursors by controlling kinetic parameters of material growth and chemical reaction. Patent application No. 201310424537.6 discloses a description of a method for the preparation of two-dimensional nanomaterials. The method for preparing the two-dimensional nano material by using the liquid ammonia/alkali metal solution has the advantage that the two-dimensional nano material can be produced in a large scale, but the method cannot be used for preparing a single-layer or thin two-dimensional nano material well. The patent application with the application number of 201410814100.8 discloses a preparation method of a thin two-dimensional nano titanium carbide material, which is only limited to preparing a single titanium carbide material and cannot prepare other two-dimensional nano materials.
The preparation methods of the two-dimensional nano materials reported at present are limited to a certain specific material component, and the preparation conditions need to be optimized according to the specific reaction efficiency and characteristics of the material component. Therefore, most of the methods lack universality, and the precise regulation and control of the composition, morphology and size of the two-dimensional nano material are difficult to carry out simultaneously.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a preparation method of an inorganic two-dimensional nanomaterial with wide applicability, namely a preparation method of an inorganic two-dimensional nanomaterial based on a plane patterning polymer brush, so as to solve the problems of poor universality, difficult adjustment of components, difficult control of size and difficult design of morphology of the existing preparation method of the inorganic two-dimensional nanomaterial.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an inorganic two-dimensional nano material based on a plane patterning polymer brush comprises the following steps:
(1) adding a photopolymerization catalyst, a monomer A and a solvent onto a planar substrate, carrying out photoinduced surface initiated atom transfer radical polymerization (SI-ATRP) reaction under a photoetching mask plate, and washing to obtain a patterned polymer A brush; adding a photopolymerization catalyst, a monomer B and a solvent onto the patterned polymer A brush, carrying out light-induced SI-ATRP reaction under the condition of illumination, and washing to obtain a patterned A-B type diblock copolymer brush;
wherein the planar substrate is connected with an Atom Transfer Radical Polymerization (ATRP) initiator, and the light-induced SI-ATRP reactions are all 0.1-10000 mu W/cm2Reacting for 0.1-24 hours at 10-50 ℃;
(2) and brushing the patterned A-B type diblock copolymer in an inorganic nano precursor solution, soaking for 0.5-240 hours, and reacting in situ at 0-200 ℃ for 1-120 hours to obtain the inorganic two-dimensional nano material on the surface of the substrate.
Preferably, the photopolymerization catalyst in the step (1) is at least one of CuBr, CuCl, CuI, 10-phenylphenothiazine, 5, 10-diphenyl-5, 10-dihydrophenazine and 5, 10-diphenyl-5, 10-dihydrophenazine derivatives.
Preferably, the monomer A in the step (1) is one of acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium iodide, acrylonitrile, vinyl pyrrolidone, 2-vinyl pyridine and 4-vinyl pyridine; more preferably at least one of vinylpyrrolidone, methacryloyloxyethyltrimethylammonium iodide and acrylic acid.
Preferably, the monomer B in the step (1) is one of methyl methacrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, butyl methacrylate, tert-butyl methacrylate, styrene and dodecafluoroheptyl methacrylate; more preferably at least one of butyl acrylate, styrene and methyl methacrylate.
Preferably, the molar ratio of the monomer A to the monomer B in the step (1) is 1: 100-100: 1, and more preferably 1: 10-10: 1; the molar ratio of the monomer A to the ATRP initiator grafted on the planar substrate is 10: 1-10000: 1, and more preferably 100: 1-5000: 1.
Preferably, in the step (1), the weight ratio of the photopolymerization catalyst to the monomer A is 0.0001: 1-0.1: 1, more preferably 0.005: 1-0.05: 1, the volume ratio of the monomer A to the solvent is 1: 50-50: 1; at the beginning of the SI-ATRP reaction in which the monomer B participates, the weight ratio of the photopolymerization catalyst to the monomer B is 0.0001: 1-0.1: 1, and more preferably 0.005: 1-0.05: 1, the volume ratio of the monomer B to the solvent is 1: 50-50: 1.
Preferably, the specific method for connecting the planar substrate with the Atom Transfer Radical Polymerization (ATRP) initiator in the step (1) is as follows: and (3) at normal temperature, placing the planar substrate in a mixed solution of an Atom Transfer Radical Polymerization (ATRP) initiator and triethylamine for reacting for 48-120 hours to obtain the planar substrate connected with the ATRP initiator.
More preferably, the solvent of the mixed solution of the ATRP initiator and the triethylamine is toluene, and the volume ratio of the ATRP initiator to the triethylamine in the mixed solution is (9-1): 1; the volume ratio of the ATRP initiator to the solvent is 1: 100-1: 400.
preferably, the planar substrate in step (1) is a smooth planar substrate, specifically at least one of a silicon wafer, a glass sheet, a mica sheet, a metal substrate and a polymer substrate.
Preferably, the Atom Transfer Radical Polymerization (ATRP) initiator in step (1) is at least one of an alkyl halide, benzyl halide, α -bromo ester, α -haloketone and α -halonitrile.
More preferably, the Atom Transfer Radical Polymerization (ATRP) initiator in the step (1) is at least one of 2-bromo-2-phenylacetic acid-6- (chlorodimethylsilyl) hexyl ester, 2-bromo-2-phenylacetic acid-6- (chlorodimethylsilyl) butyl ester and bromoisobutyric acid-6- (chlorodimethylsilyl) hexyl ester.
Preferably, the solvent in step (1) is at least one of toluene, anisole, benzyl alcohol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and N-methylpyrrolidone.
Preferably, the light-induced SI-ATRP reaction in the step (1) is carried out under ultraviolet irradiation, wherein the irradiation wavelength is at least one of 254nm, 365nm, 395nm and 405 nm.
Preferably, the light-induced SI-ATRP reaction in the step (1) is 0.8 μ W/cm2And reacting at 25 ℃ for 0.1-15 hours.
Preferably, the inorganic nano precursor in the inorganic nano precursor solution in step (2) is at least one of chloroauric acid, chloroplatinic acid, silver nitrate, silver acetate, ruthenium nitrate, rhodium chloride, rhodium nitrate, palladium nitrate, copper chloride, copper acetate, tetraisopropyl titanate, selenium, tellurium, cadmium acetylacetonate, lead acetylacetonate, zinc nitrate, ferric chloride, ferrous chloride, barium titanium isopropoxide, lead titanium isopropoxide, sodium trifluoroacetate, yttrium trifluoroacetate, ytterbium trifluoroacetate, erbium trifluoroacetate and thulium trifluoroacetate.
Preferably, the solvent of the inorganic nano precursor solution in step (2) is at least one of ethanol, methanol, chloroform, toluene, anisole, benzyl alcohol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and N-methylpyrrolidone.
Preferably, the inorganic nanophase former of the step (2)The concentration of the precursor solution is 10-310 g/mL; more preferably 0.01 to 0.25 g/mL.
Preferably, a reducing agent may be further added in the in-situ reaction in step (2), wherein the reducing agent is at least one of methanol, ethanol, propanol, ethylene glycol, oleylamine, sodium borohydride, potassium borohydride, lithium aluminum hydride, formaldehyde, acetaldehyde, glucose, aniline, phenol, formic acid and tetrabutylammonium bromide.
Preferably, a reducing agent can be further added in the in-situ reaction in the step (2), and the mass ratio of the reducing agent to the inorganic nano precursor is 50: 1-1: 50; more preferably 1: 2.5-1: 50.
preferably, the inorganic two-dimensional nanomaterial in step (2) is gold, platinum, silver, ruthenium, rhodium, palladium, copper oxide, cuprous oxide, titanium oxide, ferroferric oxide, ferrous oxide, zinc oxide, barium titanate, lead titanate, NaYF4:Yb/Er、NaYF4At least one of Yb/Tm, cadmium selenide and lead telluride.
Preferably, the thickness of the inorganic two-dimensional nano material in the step (2) is 0.1-500 nm, and the length and width dimensions are 0.1-150 μm.
Preferably, the temperature of the in-situ reaction in the step (2) is 60-180 ℃ and the time is 2-64 hours.
After an Atom Transfer Radical Polymerization (ATRP) initiator is connected to a planar substrate, a photopolymerization catalyst, a monomer and a solvent are added to the substrate, and a patterned double-block copolymer brush is grown on the surface of the substrate by a method of combining a photoinduced surface-initiated atom transfer radical polymerization (SI-ATRP) reaction with a patterning treatment of a photoetching mask plate; adding the patterned high-molecular brush and the inorganic nano precursor into a solvent, standing for a period of time, and selectively loading the inorganic precursor into a specific block layer of the inner layer of the block high-molecular brush, namely a polymer A block layer, through coordination and electrostatic action; and finally preparing various inorganic two-dimensional nano materials on the surface of the substrate through corresponding in-situ reaction.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method provides a preparation method of the inorganic two-dimensional nano material with wide applicability, and breaks through the limitation that the traditional preparation method of the two-dimensional nano material is usually limited to a certain specific material component.
(2) The method can independently regulate and control the two-dimensional nano material in three dimensions, and realizes the controllable regulation of the size and the appearance of the two-dimensional nano material.
(3) The inorganic two-dimensional nano material is directly prepared on a planar substrate, can be formed at one time to prepare various device products, and can be widely applied to the field of high and new technology products.
Drawings
FIG. 1 is a flow chart of the present invention for preparing inorganic two-dimensional nano-materials based on planar patterned polymer brushes.
Fig. 2 is an optical photograph of inorganic two-dimensional nanomaterial silver and gold nanosheets based on the planar patterned polymeric brush prepared in examples 1 and 2, respectively.
Fig. 3 is an atomic force microscope result of preparing inorganic two-dimensional nanomaterial silver nanosheets based on the planar patterned polymer brush prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Treating a smooth mica sheet substrate by using plasma, washing the mica sheet, putting the washed mica sheet into a halogenated alkane solution (a toluene solution of 2-bromo-2-phenylacetic acid-6- (chlorodimethylsilyl) hexyl ester and triethylamine, a toluene solution of 2-bromo-2-phenylacetic acid-6- (chlorodimethylsilyl) hexyl ester, triethylamine and toluene with the volume ratio of 18:2:5000) for reacting for 48 hours, connecting an ATRP initiator, then uniformly mixing CuBr, acrylic acid, N-dimethylformamide (the weight ratio of CuBr to acrylic acid is 0.5:100, the volume ratio of acrylic acid to N, N-dimethylformamide is 540:100), dropwise adding 100 microliters of the mixture on the mica sheet, covering the mica sheet with a glass sheet, covering the glass sheet with a light mask plate, opening an ultraviolet lamp (the wavelength of 365nm, the light intensity of 0.8 milliwatt/square centimeter), the reaction temperature is 25 ℃), the reaction is carried out for 0.1 hour, and the polyacrylic acid without grafting is washed out; continuously and uniformly mixing CuBr, methyl methacrylate and N, N-dimethylformamide (the weight ratio of CuBr to methyl methacrylate is 0.5:100, and the volume ratio of methyl methacrylate to N, N-dimethylformamide is 400:100), then dropwise adding 100 microliters of the mixture on a mica sheet, covering a glass sheet on the mica sheet, opening an ultraviolet lamp (the wavelength is 365nm, the light intensity is 0.8 milliwatt/square centimeter, the reaction temperature is 25 ℃), reacting for 0.2 hour, and finally cleaning to prepare the polyacrylic acid-b-polymethyl methacrylate double-block copolymer brush.
(2) The prepared polyacrylic acid-b-polymethyl methacrylate diblock copolymer is brushed in silver nitrate benzyl alcohol (the concentration of silver nitrate in benzyl alcohol is 0.01g/mL) solution, the solution stands for 2 days, silver ions fully enter a polyacrylic acid block layer of the diblock copolymer brush through coordination and electrostatic action, and the polymethyl methacrylate block layer plays a role in protection and isolation.
(3) Adding a reducing agent ethanol into the step (2), wherein the ratio of the ethanol to the silver nitrate is 100 microliters: 0.2g, reacting for 8 hours at 100 ℃, and finally taking out and washing with ethanol to obtain the two-dimensional inorganic silver nanosheet based on the planar patterning polymer brush.
FIG. 1 is a specific flow chart of the present invention for preparing an inorganic two-dimensional nanomaterial based on a planar patterned polymer brush. Fig. 2a is a corresponding optical microscope photograph of silver nanoplates. Fig. 3 is an atomic force microscope picture of silver nanoplates. The morphology of the silver nanosheet can be adjusted according to the pattern shape of the photomask, and the silver nanosheet has good optical reflection capability.
Example 2
(1) Treating a smooth copper sheet substrate by using plasma, washing the copper sheet, putting the copper sheet into an alpha-bromo-ester solution (a toluene solution of 2-bromo-2-phenylacetic acid 6- (chlorodimethylsilyl) butyl ester and triethylamine, wherein the volume ratio of 2-bromo-2-phenylacetic acid 6- (chlorodimethylsilyl) butyl ester, triethylamine and toluene is 10:10:1000) for reacting for 72 hours, connecting an ATRP initiator, then uniformly mixing 10-phenylphenothiazine, methacryloyloxyethyl trimethyl ammonium iodide, anisole (10-phenylphenothiazine, methacryloyloxyethyl trimethyl ammonium iodide with the weight ratio of 1:100, and methacryloyloxyethyl trimethyl ammonium iodide with the volume ratio of anisole of 400:100), dripping 100 microliters of the mixture on the copper sheet, opening an ultraviolet lamp (with the wavelength of 405nm, the light intensity is 0.8 milliwatt/square centimeter, the reaction temperature is 25 ℃) for 1 hour, and the polymethacryloxyethyl trimethyl ammonium iodide which is not grafted is washed clean; continuously and uniformly mixing 10-phenylphenothiazine, styrene and anisole (the weight ratio of 10-phenylphenothiazine to styrene is 2:100, and the volume ratio of styrene to anisole is 450:100), dripping 100 microliters of the mixture on a copper sheet, turning on an ultraviolet lamp (the wavelength is 365nm, the light intensity is 0.8 milliwatt/square centimeter, the reaction temperature is 25 ℃), reacting for 0.5 hour, and finally cleaning to prepare the polymethacryloxyethyl trimethyl ammonium iodide-b-polystyrene diblock copolymer brush.
(2) The prepared poly (methyl acryloyl oxyethyl trimethyl ammonium iodide-b-polystyrene) diblock copolymer brush is placed in an N, N-dimethylacetamide solution of chloroauric acid (the concentration of the chloroauric acid in the N, N-dimethylacetamide is 0.25g/mL), the poly (methyl methacrylate-b-polystyrene) diblock copolymer brush is stood for 2 days, gold ions fully enter a poly (methyl acryloyl oxyethyl trimethyl ammonium iodide) block layer of the diblock copolymer brush through coordination and electrostatic action, and the polystyrene block layer plays a role in protection and isolation.
(3) Adding a reducing agent sodium borohydride into the step (2), wherein the mass ratio of the sodium borohydride to the chloroauric acid is 1: and reacting 50 ℃ for 64 hours at 120 ℃, and finally taking out and washing with ethanol to obtain the two-dimensional inorganic gold nanosheet based on the planar patterned polymer brush.
FIG. 2b is the corresponding optical microscope photograph of the gold nanoplatelets. The morphology of the gold nanoplates can be adjusted according to the pattern shape of the photomask, and the gold nanoplates have good optical reflection capability.
Example 3
(1) Treating a smooth silicon wafer substrate by using plasma, washing the silicon wafer, putting the silicon wafer into a benzyl halide solution (a toluene solution of 6- (chlorodimethylsilyl) hexyl bromoisobutyrate and triethylamine, wherein the volume ratio of 6- (chlorodimethylsilyl) hexyl bromoisobutyrate to triethylamine to toluene is 15:5:5000) for reacting for 48 hours, connecting an ATRP (atom transfer radical polymerization) initiator, then uniformly mixing 10-phenylphenothiazine, 5, 10-diphenyl-5, 10-dihydrophenazine, vinylpyrrolidone, dimethyl sulfoxide and tetrahydrofuran (10-phenylphenothiazine, 5, 10-diphenyl-5, 10-dihydrophenazine and vinylpyrrolidone), wherein the weight ratio of the vinylpyrrolidone to the dimethyl sulfoxide to the tetrahydrofuran is 1:1:100, and the volume ratio of the vinylpyrrolidone to the tetrahydrofuran is 200:200:100), then dropwise adding 100 microlitres onto the silicon wafer, turning on an ultraviolet lamp (wavelength of 405nm, light intensity of 0.8 milliwatt/square centimeter and reaction temperature of 25 ℃) to react for 10 hours, and washing out the polyvinylpyrrolidone without grafting; CuCl, CuI, butyl acrylate styrene, benzyl alcohol and N, N-dimethylformamide (the weight ratio of CuCl, CuI and butyl acrylate is 0.5:0.5:100, and the volume ratio of butyl acrylate, benzyl alcohol and N, N-dimethylformamide is 400:10:90) are uniformly mixed, 100 microliters of the mixture is dripped on a silicon wafer, an ultraviolet lamp (the wavelength is 365nm, the light intensity is 0.8 milliwatt/square centimeter, and the reaction temperature is 25 ℃) is turned on for reaction for 15 hours, and finally, the polyvinylpyrrolidone-b-polybutyl acrylate diblock copolymer brush is prepared by cleaning.
(2) The prepared polyvinylpyrrolidone-b-polybutyl acrylate diblock copolymer brush is placed in a mixed solution of ferric chloride and ferrous chloride (the mass ratio of the ferric chloride to the ferrous chloride is 1: 1), the solvent is dimethyl sulfoxide and tetrahydrofuran solution, the volume ratio of the dimethyl sulfoxide to the tetrahydrofuran solution is 4:1, the total concentration of the ferric chloride and the ferrous chloride added in the solvent is 0.01g/mL, the mixture stands for 2 days, iron ions fully enter a polyvinylpyrrolidone block layer of the diblock copolymer brush through coordination and electrostatic action, and the polybutyl acrylate block layer plays a role in protection and isolation.
(3) And (3) reacting for 24 hours at 120 ℃, finally taking out and washing with ethanol to obtain the two-dimensional inorganic ferroferric oxide nano sheet based on the planar patterned polymer brush.
The morphology of the ferroferric oxide nano-sheet can be adjusted according to the pattern shape of the photomask.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of an inorganic two-dimensional nano material based on a plane patterning polymer brush is characterized by comprising the following steps:
(1) adding a photopolymerization catalyst, a monomer A and a solvent onto a planar substrate, carrying out photoinduced SI-ATRP reaction under a photoetching mask plate, and flushing to obtain a patterned polymer A brush; adding a photopolymerization catalyst, a monomer B and a solvent onto the patterned polymer A brush, carrying out light-induced SI-ATRP reaction under the condition of illumination, and washing to obtain a patterned A-B type diblock copolymer brush;
wherein the planar substrate is connected with an ATRP initiator, and the light-induced SI-ATRP reactions are all 0.1-800 muW/cm2Reacting for 0.1-15 hours at 25-50 ℃;
(2) brushing the patterned A-B type diblock copolymer in an inorganic nano precursor solution, soaking for 48 hours, and reacting in situ at 100-120 ℃ for 8-64 hours to obtain an inorganic two-dimensional nano material on the surface of the substrate;
the monomer A in the step (1) is at least one of vinyl pyrrolidone, methacryloyloxyethyl trimethyl ammonium iodide and acrylic acid;
the monomer B in the step (1) is at least one of butyl acrylate, styrene and methyl methacrylate;
the ATRP initiator in the step (1) is at least one of 2-bromo-2-phenylacetic acid-6- (chlorodimethylsilyl) hexyl ester, 2-bromo-2-phenylacetic acid-6- (chlorodimethylsilyl) butyl ester and bromoisobutyric acid-6- (chlorodimethylsilyl) hexyl ester;
the photopolymerization catalyst in the step (1) is one of CuBr, 10-phenylphenothiazine and 5, 10-diphenyl-5, 10-dihydrophenazine;
the specific method for connecting the plane substrate with the atom transfer radical polymerization initiator in the step (1) comprises the following steps: and (3) at normal temperature, placing the planar substrate in a mixed solution of an atom transfer radical polymerization initiator and triethylamine to react for 48-72 hours to obtain the planar substrate connected with the ATRP initiator.
2. The preparation method of the inorganic two-dimensional nanomaterial based on the planar patterning polymer brush according to claim 1, wherein the molar ratio of the monomer A to the monomer B in the step (1) is 1: 100-100: 1; the molar ratio of the monomer A to the ATRP initiator grafted on the planar substrate is 10: 1-10000: 1.
3. The preparation method of the inorganic two-dimensional nanomaterial based on the planar patterning polymer brush according to claim 1, wherein in the step (1), the weight ratio of the photopolymerization catalyst to the monomer A is 0.005-0.02: 1, the volume ratio of the monomer A to the solvent is 1: 1.5-5.4: 1; at the beginning of the SI-ATRP reaction in which the monomer B participates, the weight ratio of the photopolymerization catalyst to the monomer B is 0.005-0.02: 1, the volume ratio of the monomer B to the solvent is 4: 1-4.5: 1.
4. the method for preparing the inorganic two-dimensional nanomaterial based on the planar patterning polymer brush according to claim 1, wherein the inorganic nano precursor in the inorganic nano precursor solution in the step (2) is one of silver nitrate, chloroauric acid, ferric chloride and ferrous chloride;
and (3) the inorganic two-dimensional nano material in the step (2) is one of gold, silver and ferroferric oxide.
5. The method for preparing the inorganic two-dimensional nanomaterial based on the planar patterning polymer brush according to claim 1, wherein the concentration of the inorganic nano precursor solution in the step (2) is 0.01-0.25 g/mL; and (3) adding a reducing agent into the in-situ reaction in the step (2), wherein the reducing agent is one of ethanol and sodium borohydride, and the mass ratio of the reducing agent to the inorganic nano precursor is 50: 1-1: 50.
6. the method for preparing the inorganic two-dimensional nanomaterial based on the planar patterned polymer brush according to claim 1, wherein the light-induced SI-ATRP reaction in step (1) is performed under ultraviolet irradiation, wherein the irradiation wavelength is at least one of 365nm, 395nm and 405 nm.
7. The preparation method of the inorganic two-dimensional nanomaterial based on the planar patterning polymer brush according to claim 1, wherein in the specific method in which the planar substrate is connected with the atom transfer radical polymerization initiator, the volume ratio of the ATRP initiator to triethylamine in the mixed solution is (9-1): 1, volume ratio of ATRP initiator to solvent is 1: 100-15: 5000, wherein the solvent is a solvent in a mixed solution of an atom transfer radical polymerization initiator and triethylamine;
the planar substrate in the step (1) is a smooth planar substrate, and specifically is at least one of a silicon wafer, a glass sheet, a mica sheet, a metal substrate and a polymer substrate;
the solvent in the step (1) is at least one of toluene, anisole, benzyl alcohol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and N-methylpyrrolidone;
and (3) the solvent of the inorganic nano precursor solution in the step (2) is at least one of ethanol, methanol, chloroform, toluene, anisole, benzyl alcohol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and N-methylpyrrolidone.
8. The preparation method of the inorganic two-dimensional nanomaterial based on the planar patterned polymer brush according to claim 1, wherein the thickness of the inorganic two-dimensional nanomaterial obtained in the step (2) is 0.1-500 nm, and the length and width dimensions are 0.1-150 μm.
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