CN110316736B - Preparation method of large-area nano film - Google Patents

Preparation method of large-area nano film Download PDF

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CN110316736B
CN110316736B CN201910561654.4A CN201910561654A CN110316736B CN 110316736 B CN110316736 B CN 110316736B CN 201910561654 A CN201910561654 A CN 201910561654A CN 110316736 B CN110316736 B CN 110316736B
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oil phase
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CN110316736A (en
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祝建中
张欢
杨雪
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Hohai University HHU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides

Abstract

The invention discloses a preparation method of a large-area nano film, belonging to the technical field of nano materials and comprising the following steps: 1) adding a surfactant, an oil phase reaction precursor, an alkaline organic matter and an organic solvent into a reactor, and ultrasonically dissolving the mixture under a water bath condition to obtain an oil phase; 2) dissolving the water-phase reaction precursor in water to obtain a water phase; 3) the oil phase is stably contacted with the water phase, and a flat oil-water interface is formed between the upper layer of liquid and the lower layer of liquid; 4) standing to promote the reaction precursor to produce designed reaction in the interface and produce large area nanometer film. The preparation method of the large-area nano film can prepare the nano film with a multilayer structure, at least one supporting layer, various functional layers, complex structure, multiple functions and good mechanical property.

Description

Preparation method of large-area nano film
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a large-area nano film.
Background
In recent years, the research on the preparation of nanomaterials by using a liquid-liquid (oil-water) interface has attracted great interest. The liquid-liquid interface has a certain thickness (on the order of a few nanometers) because the immiscible two phases always have a small amount of miscibility at the interface. The very thin interfacial layer possesses some unique thermodynamic properties such as higher viscosity and density. The limited mixing of the two phases at the interface produces a dielectric constant with a wide gradient. These characteristics determine the preparation of nanomaterials at the interface, the mechanism of formation of which is substantially different from that of the synthesis of nanostructures by conventional methods. Moreover, the method for preparing the nano material by adopting the liquid-liquid interface also has a remarkable characteristic, namely, the method provides a method for exploring the self performance and the structure of the liquid-liquid interface, and the macroscopic structure of a sample prepared at the liquid-liquid interface reflects the structure of the interface to a certain extent. Thus, the liquid-liquid interface has a dual role during the reaction: not only is the transport of charge/ions at the interface regulated but the structure of the product is also guided.
The preparation of nano material by liquid-liquid interface is carried out by dissolving one precursor in oil phase (organic solvent such as toluene, chloroform, etc.) and another precursor in water phase, contacting two phases, and proceeding reaction by ion transmission under the regulation of liquid-liquid interface. At present, nano materials such as metal simple substances, oxides, chalcogenides, polymers, heterodimers, metal organic framework materials and the like have been synthesized by adopting a liquid-liquid interface.
Liquid-liquid (oil-water) interfacial synthesis has made some progress in the preparation of nanomaterials, which has the following advantages compared to the conventional homogeneous liquid phase synthesis: i) the method has the characteristics of simplicity, low cost and convenience in film preparation, and the film is uniform in thickness, adjustable and free of defects; ii) in the aspect of preparing nano particles, the prepared product has special appearance and excellent performance and can be accurately controlled; iii) the thickness and microstructure of the film can be adjusted by changing conditions such as temperature, reaction time, precursor concentration, liquid phase viscosity, solvent polarity and upper phase liquid column height; iv) the potential of large area and low energy consumption for preparing thin films; v) liquid-liquid interfacial synthesis reduces nucleation and growth rates, facilitating the production of anisotropic nanostructures; vi) no template is required, simplifying the experimental procedure and reducing the cost. Meanwhile, liquid-liquid interface synthesis can also be combined with methods such as illumination, microwave, ultrasound, hydrothermal method, electrochemical method and the like for use, can also be used for reaction under the condition of stirring, selects two immiscible phases with high boiling points, and can also be used for preparation research of nano particles at higher temperature and the like.
The prior art is a nano film with a single nano particle component, the function of the film is single, the interface property is difficult to regulate and control, the film with a large area is difficult to prepare, the mechanical property is very poor, and the practical application is very difficult.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a large-area nano film, which can prepare the nano film with complex structure, multiple functions and good mechanical property.
The technical scheme is as follows: in order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the large-area nano film comprises the following steps:
1) adding a surfactant, an oil phase reaction precursor, an alkaline organic matter and an organic solvent into a reactor, and ultrasonically dissolving the mixture under a water bath condition to obtain an oil phase;
2) dissolving the water-phase reaction precursor in water to obtain a water phase;
3) the oil phase is stably contacted with the water phase, and a flat oil-water interface is formed between the upper layer of liquid and the lower layer of liquid;
4) standing to promote the reaction precursor to produce designed reaction in the interface and produce large area nanometer film.
Further, in the step 1), the concentration of the surfactant in the oil phase is 0.01g/mL-0.05g/mL, the concentration of the precursor of the oil phase reaction is 0.01mL/mL-0.1mL/mL, and the concentration of the basic organic matter is 0.005mL/mL-0.01 mL/mL; in the step 1-3), the ratio of the density of the oil phase to the density of the water phase is less than or equal to 0.8 or more than or equal to 1.2.
Further, in the step 2), the concentration of the positive charges in the aqueous phase is 0.00006mol/mL-0.0001 mol/mL.
Further, in step 1), the surfactant is selected from cationic or nonionic surfactants, and the HLB value of the surfactant is 2-7.
Further, in step 1), the surfactant is selected from cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide and lecithin.
Further, in the step 1), the basic organic matter is an organic matter which generates OH & lt- & gt through hydrolysis reaction; in the step 2), the precursor of the water phase reaction is metal cation which generates precipitate with hydroxide radical.
The membrane prepared by the invention is a three-layer or two-layer membrane, wherein a supporting layer and a functional layer are definitely existed, an organic layer is an optional layer, and corresponding organic and inorganic precursors are selected according to the requirement of the prepared membrane to generate the corresponding organic layer.
Further, the oil phase reaction precursor comprises tetraethyl orthosilicate; the water phase reaction precursor comprises metal salt; when the oil phase contacts with water, the oil phase reaction precursor and the water phase reaction precursor generate a supporting layer; and hydrolyzing the tetraethyl orthosilicate to generate a silicon dioxide generation functional layer under the condition of hydroxide radicals generated by hydrolysis of an alkaline organic matter.
Further, when the oil phase reaction precursor further comprises an organic reaction precursor, the water phase reaction precursor further comprises an alkaline oxidant, and when the oil phase is contacted with water, an organic layer is generated on the functional layer through reaction, so that a layered structure of a support layer-functional layer-organic layer is formed.
Further, when the organic reaction precursor is aniline, the alkaline oxidant is camphorsulfonic acid, the correspondingly generated organic layer is polyaniline nanofiber, when the organic reaction precursor is aniline, the alkaline oxidant is chloroauric acid, and the correspondingly generated organic layer is polyaniline/Au heterodimer.
Further, in the step 1), the ultrasonic dissolution is ultrasonic dissolution at the temperature of 40-42 ℃.
The nano film is composed of three layers of nano materials, wherein one layer is a supporting layer; the structure and the main components of the two sides of the membrane are different due to different reactions in the preparation, and the thickness of the membrane is limited by the reaction process; the nano material is mainly generated by reaction on a liquid-liquid interface, and the composition and the morphology can be designed and regulated according to needs; the nano particles composing the membrane are combined with the surfactant and the cosurfactant through interaction, meanwhile, the nano particles form a very rich regular nano-scale pore structure in the self-assembly process, and the surface of the pore structure is provided with a plurality of surfactant groups to form a basically selective mass transfer channel; there is a relatively dense layer in the middle of the membrane, making it difficult for general substances to pass through mass transfer.
The supporting layer is a crystal which can form a lamellar, flaky or banded crystal form, and the supporting layer is formed by forming a banded, flaky or layered nano structure; the supporting layer is a part of the membrane and plays a role in limiting the thickness of the membrane, increasing the strength of the whole material, improving the porosity and reducing the shrinkage; the membrane comprises a supporting layer and a functional layer, wherein the same component can be the supporting layer and the functional layer, and the functional layer mainly endows the material with special properties such as catalysis, adsorptivity, selective permeability, hydrophilicity and hydrophobicity, high specific surface area and the like; the thickness of the film is uniform and adjustable;
the reactions occur at the oil-water-liquid interface, and the reactions occurring at the oil side and the water side are different; the nano solid generated by the reaction is adsorbed on the interface and is combined with a surfactant and the like, and the generated nano particles further grow and self-assemble on the interface to finally form a nano film; the surfactant can be single or composite, can comprise cosurfactant, and can be used as a surfactant or a cosurfactant as a byproduct of the reaction; the pore structure is mainly formed by self-assembly of nano materials and is formed by interface local micelles, and the scientific structures are endowed with special selective permeability due to the self properties of the surface of the formed nano materials, such as surface charges, surface hydroxyl groups and the like, and organic matters adsorbed and linked on the surface of the nano materials, mainly surfactants and cosurfactants;
the reaction comprises the following steps: 1. dissolving alkaline organic matters in an oil phase, and reacting with water to generate OH-; 2. metal ions dissolved in water form nano-lamellar, flaky or precipitated with OH < - > or other anions (generated by hydrolysis reaction of water dissolved in oil phase) to form a supporting layer; 3. under the catalytic action of OH < - >, an oil phase reaction precursor, such as Tetraethoxysilane (TEOS), undergoes a hydrolytic condensation reaction to form a nano solid substance; 4. the oxidizing metal cations and the reducing organic matters undergo an oxidation-reduction reaction at an interface to generate nano metal particles; 5. respectively dissolving the precursor of the addition, condensation and polycondensation reaction in an oil phase and a water phase, and then carrying out the addition, condensation and polycondensation reaction on an interface to generate a target substance; the reaction comprises 1 or more than one of the above reactions, and different reactions can interact with each other, such as OH-generated by the reaction as a catalyst or a precipitant for other reactions, nano-materials with special structures generated by reactions 3-5 as a template for reaction 6, and the like;
the surfactant dissolving mode comprises the following steps: a. dissolving the surfactant and the reaction precursor into the oil phase or the water phase according to the requirement to increase the solubility of the reaction precursor dissolved in the surfactant, and c, dissolving the surfactant and the reaction precursor separately, for example, dissolving the surfactant and the reaction precursor into a small amount of oil phase, forming an interface with the water phase, introducing the oil phase in which the reaction precursor is dissolved, and reacting at the interface; the standing can fix a certain phase at low temperature so that an interface is relatively fixed, and can also increase reaction promoting conditions such as illumination, radiation, proper high temperature and pressure and the like to control the reaction;
the main reaction mechanism is as follows: respectively dissolving corresponding substances in a water phase and an oil phase (namely two incompatible phases), forming a liquid-liquid interface of the bicontinuous phase by liquid-liquid bicontinuous phase preparation equipment or method, quickly diffusing a dissolved surfactant on the interface to the interface, reducing the surface tension of the interface, maintaining the stability of the formed liquid-liquid interface, and simultaneously reacting a reaction initiator (for example, benzylamine) dissolved in the oil phase at the oil-water interface to generate OH-，OH-The method is characterized in that hydroxide precipitation reaction is rapidly carried out on the metal cations in water, generated precipitates are rapidly self-assembled into supporting layers with different structures at an oil-water interface under the combined action of a surfactant and interfacial tension according to different properties of the precipitates, the surfactant and nanoparticles precipitate surface active nanoparticles which interact with each other, the surface tension of the oil-water interface is greatly reduced, the increase of nanoparticles on the interface is realized, the difficulty of penetrating the interface of a reaction precursor is increased, so that the thickness of a nanolayer is limited, and the bicontinuous nanoparticle is enabled to be doubly connected on the other handThe continuous phase is stable and even the oil-water interface automatically expands, so that the system is promoted to develop into the bicontinuous phase microemulsion, when the metal cations are more consumed and have redundant OH-In OH when-Under the catalysis, a reaction precursor (TEOS for example) dissolved in an oil phase is subjected to hydrolytic polycondensation reaction on an oil-water interface to form sol-gel, self-assembled to form a nano-silica sphere under the action of a surfactant, further self-assembled to form a nano-silica aggregate on the interface under the action of interfacial tension and capillary force, and after the reaction is finished, a stable bicontinuous phase emulsion gel is formed, so that a continuous and complete nano-layer (comprising a supporting layer, a binding layer, a functional layer and the like) consisting of nano-materials is formed on the bicontinuous phase interface, and the nano-emulsion gel has different properties according to the composition of the nano-materials.
The reaction package is not limited to the following:
1. the alkaline organic matter is dissolved in the oil phase and reacts with water to generate OH-The basic organics include, but are not limited to: methylamine>Urea (Urea)>Ethylamine (ethylamine)>Ethanolamine>Ethylene diamine>Dimethylamine>Trimethylamine>Triethylamine>Propylamines>Isopropylamine>1, 3-propanediamine>1, 2-propanediamine>Tripropylamine>Triethanolamine>Butylamine>Isobutylamine>Tert-butylamine>Hexylamine>Octylamine>Aniline>Benzylamine>Cyclohexylamine>Pyridine compound>Hexamethylenetetramine>2-chlorophenol>3-chlorophenol>4-chlorophenol>Ortho-aminophenols>Meta-aminophenol>P-aminophenol>O-toluidine>M-toluidine>Para-toluidine>8-hydroxyquinoline (20 ℃ C.)>Diphenylamine>Benzidine.
2. Metal ions dissolved in water, with OH-Or other anions (resulting from hydrolysis by reaction with water, dissolved in the oil phase) form nano-lamellar, lamellar or ribbon-like precipitates, etc., forming a support layer, including but not limited to: the chemical molecular composition of LDHs is
Figure BDA0002108455080000051
X is 0 to 1, M2+、M3+Is a metal ion, An-Is an interlayer anion, both can be modulated within a certain range, and a series of different anions can be obtainedThe functional materials with different compositions and structures are shown in figure 1. M on a layer plate2+Partial quilt M3+During substitution, some residual positive charges are generated on the hydrotalcite laminate, An-It serves to balance this partial positive charge, making the overall LDHs material electrically neutral. A common divalent cation is Ca2+、Mg2+、Zn2+、Ni2+、Mn2 +、Co2+And Fe2+(ii) a A common trivalent cation is Al3+、Cr3+、Mn3+、Fe3+、Ga3+、Co3+And Ni3+。
3. The oxidative metal cations and the reducing organic matter undergo a redox reaction at the interface to generate nano-metal particles, including but not limited to: 50 or more kinds of metal nanomaterials (Au, Ag, Pt, Pd, Rh, Cu, Fe, CO, Ni, etc.) having various structures (single crystal, twin crystal, etc.) and morphologies (cube, truncated cube, octahedron, truncated octahedron, rod-like, decahedron, icosahedron, disk-like, etc.).
Has the advantages that: compared with the prior art, the preparation method of the large-area nano film can prepare the nano film with a multilayer structure, at least one supporting layer, various functional layers, complex structure, various functions and good mechanical property.
Drawings
FIG. 1 shows TEOS + Al2(SO4)3*18H2Optical micrograph of O at 400X;
FIG. 2 is CTAB + TEOS + Zn (NO)3)2*6H2Optical micrograph of O at 400X;
FIG. 3 is CTAB + TEOS + Zn (NO)3)2*6H210000 times SEM image of O;
FIG. 4 is CTAB + TEOS + Al2(SO4)3*18H2SEM image at O10000 times.
Detailed Description
The invention will be further described with reference to the following drawings and specific embodiments.
The preparation method of the large-area nano film comprises the following steps:
1) adding a surfactant, an oil phase reaction precursor, an alkaline organic matter and an organic solvent into a reactor, and ultrasonically dissolving the mixture under a water bath condition to obtain an oil phase;
2) dissolving the water-phase reaction precursor in water to obtain a water phase;
3) the oil phase is stably contacted with the water phase, and a flat oil-water interface is formed between the upper layer of liquid and the lower layer of liquid;
4) standing to promote the reaction precursor to produce designed reaction in the interface and produce large area nanometer film.
In the step 1), the concentration of the surfactant in the oil phase is 0.01-0.05 g/mL, the concentration of the precursor of the oil phase reaction is 0.01-0.1 mL/mL, and the concentration of the alkaline organic matter is 0.005-0.01 mL/mL; in the step 1-3), the ratio of the density of the oil phase to the density of the water phase is not more than 0.8 or not more than 1.2.
In the step 2), the concentration of positive charges in the aqueous phase is 0.00006mol/mL-0.0001 mol/mL.
In step 1), the surfactant is selected from cationic or nonionic surfactants, and the HLB value of the surfactant is 2-7.
In step 1), the surfactant is selected from cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide and lecithin.
In the step 1), the alkaline organic matter is an organic matter which generates OH < - > through hydrolysis reaction; in step 2), the metal salt is a metal cation which generates a precipitate with hydroxide.
The membrane prepared by the invention is a three-layer or two-layer membrane, wherein a supporting layer and a functional layer are definitely existed, an organic layer is an optional layer, and corresponding organic and inorganic precursors are selected according to the requirement of the prepared membrane to generate the corresponding organic layer.
The oil phase reaction precursor comprises tetraethyl orthosilicate; the aqueous phase reaction precursor comprises a metal salt; when the oil phase contacts with the water phase, the oil phase reaction precursor and the water phase reaction precursor generate a supporting layer; and hydrolyzing tetraethyl orthosilicate to generate a silicon dioxide generation functional layer under the condition of hydroxide radicals generated by hydrolysis of alkaline organic matters.
When the oil phase reaction precursor also comprises an organic reaction precursor, the water phase reaction precursor also comprises an alkaline oxidant, and when the oil phase is contacted with water, an organic layer is generated on the functional layer by reaction to form a layered structure of a supporting layer-functional layer-organic layer.
When the organic reaction precursor is aniline, the alkaline oxidant is camphorsulfonic acid, the correspondingly generated organic layer is polyaniline nanofiber, when the organic reaction precursor is aniline, the alkaline oxidant is chloroauric acid, and the correspondingly generated organic layer is polyaniline/Au heterodimer.
Example 1
The preparation method of the large-area nano film comprises the following steps:
1. weighing 2ml of tetraethyl orthosilicate (0.089 ml/ml in the oil phase);
2. weighing 0.5ml benzylamine (0.0222 ml/ml in oil phase);
3. measuring 20ml of CHCl3The density was 1500kg/m3；
4. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
5. weighing a small amount of Al2(SO4)3*18H20.05g of O was added to 5ml of distilled water and dissolved so that the positive charge concentration was 0.0002252 mol/ml;
6. slowly pouring the water phase into the oil phase;
7. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
8. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M1. As shown in fig. 1, the formed film is a dense film on which formed silica is supported.
Example 2
The preparation method of the large-area nano film comprises the following steps:
1. 0.021g of cetyltrimethylammonium bromide (CTAB) (0.003 g/ml in the oil phase) was weighed;
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. 7ml CHCl was measured3The density was 1500kg/m3；
5. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
6. weighing small amount of Zn (NO)3)2·6H2O0.008925 g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
7. slowly pouring the water phase into the oil phase;
8. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
9. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M2. The microstructure was microscopically observed, and a relatively dense film was formed as shown in FIG. 2. The dots attached to the top are silica and the flakes are metal hydroxides, and as can be seen from a comparison of fig. 1, the surfactant changes the structure of the material. And the more refined layer structure can be seen in fig. 3, the upper granular is silica particles, and the lower loose layer is zinc hydroxide as a support layer.
Example 3
The preparation method of the large-area nano film comprises the following steps:
1. 0.07g of cetyltrimethylammonium bromide (CTAB) (0.01 g/ml in the oil phase) was weighed out;
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. 7ml CHCl was measured3(density 1500 kg/m)3)；
5. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
6. weighing small amount of Zn (NO)3)2·6H2O0.008925 g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
7. slowly pouring the water phase into the oil phase;
8. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
9. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M3.
Example 4
The preparation method of the large-area nano film comprises the following steps:
1. 0.07g of cetyltrimethylammonium bromide (CTAB) (0.01 g/ml in the oil phase) was weighed out;
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. 7ml CHCl was measured3(density 1500 kg/m)3)；
5. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
6. weighing a small amount of Al2(SO4)3*18H2O0.09324 g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
7. slowly pouring the water phase into the oil phase;
8. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
9. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M4. The structure of the membrane is shown in fig. 4, and it can be seen that unlike fig. 3, the supporting layer is aluminum hydroxide, the structure is more dense, and the upper granular is silicon dioxide.
Example 5
The preparation method of the large-area nano film comprises the following steps:
1. 0.07g of cetyltrimethylammonium bromide (CTAB) (0.01 g/ml in the oil phase) was weighed out;
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. 7ml CHCl was measured3(density 1500 kg/m)3)；
5. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
6. weighing a small amount of Al2(SO4)3*18H2O 0.04662g，Zn(NO3)2·6H2O0.0313g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
7. slowly pouring the water phase into the oil phase;
8. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
9. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M5.
Example 6
The preparation method of the large-area nano film comprises the following steps:
1. 0.35g of cetyltrimethylammonium bromide (CTAB) (0.05 g/ml in the oil phase) was weighed out;
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. 7ml CHCl was measured3(density 1500 kg/m)3)；
5. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
6. weighing small amount of Zn (NO)3)2·6H2O0.008925 g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
7. slowly pouring the water phase into the oil phase;
8. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
9. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M6.
Example 7
The preparation method of the large-area nano film comprises the following steps:
1. weighing 0.07g lecithin (0.01 g/ml in oil phase);
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. 7ml CHCl was measured3(density 1500 kg/m)3)；
5. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
6. weighing small amount of Zn (NO)3)2·6H2O0.008925 g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
7. slowly pouring the water phase into the oil phase;
8. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
9. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M7.
Example 8
The preparation method of the large-area nano film comprises the following steps:
1. 0.07g of cetyltrimethylammonium bromide (CTAB) (0.01 g/ml in the oil phase) was weighed out;
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. weighing 1ml (1.02g) of aniline in the oil phase, wherein the concentration of aniline in the oil phase is 0.143 ml/ml;
5. 6ml of hexane (density 660 kg/m) were measured3)；
6. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
7. weighing small amount of Zn (NO)3)2·6H2O0.008925 g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
8. weighing 0.1g of camphorsulfonic acid, wherein the concentration of the camphorsulfonic acid in a water phase is 0.0143 g/ml;
9. slowly pouring the water phase into the oil phase;
10. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
11. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M8.
Example 9
The preparation method of the large-area nano film comprises the following steps:
1. 0.07g of cetyltrimethylammonium bromide (CTAB) (0.01 g/ml in the oil phase) was weighed out;
2. weighing 0.07ml of tetraethyl orthosilicate (0.01 ml/ml in the oil phase);
3. weighing 0.035ml benzylamine (0.005 ml/ml in oil phase);
4. weighing 1ml (1.02g) of aniline in the oil phase, wherein the concentration of aniline in the oil phase is 0.143 ml/ml;
5. 6ml of hexane (density 660 kg/m) were measured3)；
6. Ultrasonic dissolving at 40-42 deg.C to obtain oil phase;
7. weighing small amount of Zn (NO)3)2·6H2O0.008925 g was added to distilled water and dissolved so that the concentration of positive charges was 0.00006 mol/ml;
8. weighing HAuCl3·HCl·4H20.1g of O, and the concentration of the water phase is 0.0143 g/ml;
9. slowly pouring the water phase into the oil phase;
10. in a prefabricated reactor, an oil phase is stably contacted with a water phase to form a smooth and flat oil-water interface;
11. standing to promote the reaction precursor to generate designed reaction on the interface; the membrane is labeled M9.
Example 10 test example
As shown in Table 1 below, the thickness can be directly measured by SEM for the results of the film thickness tests of the films M1-M9 obtained in examples 1-9.
TABLE 1 film thickness test results for films M1-M9
M1 M2 M3 M4 M5 M6 M7 M8 M9
Film thickness (nm) 2057 3319 3142 2516 2899 3095 3541 4658 4875
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. The preparation method of the large-area nano film is characterized by comprising the following steps: the method comprises the following steps:
1) adding a surfactant, an oil phase reaction precursor, an alkaline organic matter and an organic solvent into a reactor, and ultrasonically dissolving the mixture under a water bath condition to obtain an oil phase;
2) dissolving the water-phase reaction precursor in water to obtain a water phase;
3) the oil phase is stably contacted with the water phase, and a flat oil-water interface is formed between the upper layer of liquid and the lower layer of liquid;
4) standing to promote the designed reaction of the reaction precursor on the interface to generate a large-area nano film;
wherein, in the step 1), the oil phase reaction precursor comprises tetraethyl orthosilicate; in the step 2), the water-phase reaction precursor is a metal salt which is dissolved in water and can generate precipitate by metal cations and hydroxide radicals; when the oil phase contacts with water, the oil phase reaction precursor and the water phase reaction precursor generate a supporting layer; and hydrolyzing the tetraethyl orthosilicate to generate a silicon dioxide generation functional layer under the condition of hydroxide radicals generated by hydrolysis of an alkaline organic matter.
2. The method of preparing a large-area nanomembrane according to claim 1, wherein: in the step 1), in the oil phase, the concentration of the surfactant is 0.01-0.05 g/mL, the concentration of the precursor of the oil phase reaction is 0.01-0.1 mL/mL, and the concentration of the alkaline organic matter is 0.005-0.01 mL/mL; in the step 1-3), the ratio of the density of the oil phase to the density of the water phase is less than or equal to 0.8 or more than or equal to 1.2.
3. The method of preparing a large-area nanomembrane according to claim 1, wherein: in the step 2), the concentration of positive charges in the water phase is 0.00006mol/mL-0.0001 mol/mL.
4. The method of preparing a large-area nanomembrane according to claim 1, wherein: in the step 1), the surfactant is selected from cationic or nonionic surfactants, and the HLB value of the surfactant is 2-7.
5. The method of claim 4, wherein the nano-film is prepared by: in step 1), the surfactant is selected from cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide and lecithin.
6. The method of preparing a large-area nanomembrane according to claim 1, wherein: when the oil phase reaction precursor further comprises an organic reaction precursor, the water phase reaction precursor further comprises an alkaline oxidant, and when the oil phase contacts with water, the oil phase reacts on the functional layer to generate an organic layer, so that a layered structure of a support layer-functional layer-organic layer is formed, and the organic reaction precursor is aniline; the alkaline oxidant is camphorsulfonic acid, and the corresponding generated organic layer is polyaniline nanofiber; the alkaline oxidant is chloroauric acid, and the corresponding generated organic layer is polyaniline/Au heterodimer.
7. The method of preparing a large-area nanomembrane according to claim 1, wherein: in the step 1), the ultrasonic dissolution is ultrasonic dissolution at the temperature of 40-42 ℃.
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