CN110316736A - The preparation method of large-area nano film - Google Patents

The preparation method of large-area nano film Download PDF

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CN110316736A
CN110316736A CN201910561654.4A CN201910561654A CN110316736A CN 110316736 A CN110316736 A CN 110316736A CN 201910561654 A CN201910561654 A CN 201910561654A CN 110316736 A CN110316736 A CN 110316736A
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CN110316736B (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

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Abstract

The invention discloses the preparation methods of large-area nano film, belong to technical field of nano material, include the following steps: that surfactant, oily phase reaction precursor, alkaline organic and organic solvent 1) are added into reactor, and ultrasonic dissolution is used as oily phase under water bath condition；2) aqueous phase reactions precursor is dissolved in water, as water phase；3) it is mutually steadily contacted oily with water phase, forms flat oil-water interfaces between upper layer and lower layer liquid；4) it stands, the reaction for promoting reacting precursor object to design at interface generates large-area nano film.The preparation method of large-area nano film of the invention can prepare nanometer film with multi-layer structure, at least one layer of supporting layer, and functional layer is there are many selection, and structure is complicated, nanometer film vdiverse in function, having good mechanical properties.

Description

The preparation method of large-area nano film
Technical field
The invention belongs to technical field of nano material, and in particular to the preparation method of large-area nano film.
Background technique
In recent years, the very big emerging of people is caused using the preparation research that liquid-liquid (oil-water) interface carries out nano material Interest.Since unmixing two-phase always has a small amount of intersolubility in interface, liquid-liquid interface has certain thickness (about several to receive Rice).This very thin boundary layer possesses some unique macroscopic properties, such as higher viscosity and density etc..Two-phase is at interface Locate limited mixing and produces the dielectric constant with wider gradient.These characteristics, which are determined, prepares nano material in interface, The synthesis that its formation mechenism carries out nanostructure with conventional method is essentially different.Moreover, being received using liquid-liquid interface preparation Rice material also possesses an outstanding feature, i.e., it provides a kind of method for exploring liquid-liquid interface self performance and structure, The macrostructure of prepared sample reflects the structure at interface to a certain extent at liquid-liquid interface.In this way, during the reaction Liquid-liquid interface has double action: not only having adjusted transmission of the charge/ion in interface and also directs the structure of product.
Nano material is prepared using liquid-liquid interface, a kind of predecessor is usually dissolved in oily phase (organic solvent such as toluene, chlorine Imitate), another predecessor is soluble in the aqueous phase, and two is in contact later, and reaction is transmitted under the adjustment effect of liquid-liquid interface through ion And it goes on.Currently, having synthesized metal simple-substance, oxide, chalkogenide, polymer, heterogeneous two using liquid-liquid interface The nano materials such as aggressiveness and metal-organic framework material.
The synthesis of liquid-liquid (oil-water) interface has been achieved with certain progress in terms of nano material preparation, with the uniform liquid of tradition It is combined to and compares, have the advantage that i) has the characteristics that simple, cheap and convenient, and film in terms of film preparation The uniform adjustable zero defect of thickness；Ii) in terms of preparing nano particle, prepared product morphology is special, has excellent performance and can be with Accurate control；Iii) by changing temperature, reaction time, predecessor concentration, liquid phase viscosity, solvent polarity and upper phase liquid-column height Etc. conditions can adjust the thickness and microstructure of film；Iv the potentiality of film) is prepared with large area low energy consumption；v) Liquid-liquid interface synthesis reduces nucleation and rate of rise, is conducive to generate anisotropic nanostructure；Vi template) is not needed, It simplifies experimental procedure and reduces costs.Meanwhile liquid-liquid interface synthesis can also be with illumination, microwave, ultrasound, hydro-thermal and electricity The methods of chemistry is used in combination, and can also react under stirring conditions, selects high boiling unmixing two-phase, can also be The preparation research etc. of nano particle is carried out under higher temperature.
The prior art is all the nanometer film of single nanoparticle component, and the function of film is relatively simple, and interfacial property is difficult With regulation, it is difficult to prepare the film of large area, special mechanical performance is all excessively poor, it is very difficult to practical application.
Summary of the invention
Goal of the invention: the purpose of the present invention is to provide the preparation methods of large-area nano film, and it is multiple can to prepare structure Nanometer film that is miscellaneous, vdiverse in function, having good mechanical properties.
Technical solution: to achieve the above object, the invention provides the following technical scheme:
The preparation method of large-area nano film, includes the following steps:
1) surfactant, oily phase reaction precursor, alkaline organic and organic solvent are added into reactor, and in water Ultrasonic dissolution is as oily phase under the conditions of bath；
2) aqueous phase reactions precursor is dissolved in water, as water phase；
3) it is mutually steadily contacted oily with water phase, forms flat oil-water interfaces between upper layer and lower layer liquid；
4) it stands, the reaction for promoting reacting precursor object to design at interface generates large-area nano film.
Further, in step 1), in the oily phase, the concentration of surfactant is 0.01g/mL-0.05g/mL, oil The concentration of phase reaction precursor is 0.01ml/mL-0.1ml/mL, and the concentration of alkaline organic is 0.005ml/mL-0.01ml/ mL；Step 1-3) in, the ratio of the oily phase density and aqueous phase densities is less than or equal to 0.8 or more than or equal to 1.2.
Further, in step 2), the concentration of positive charge is 0.00006mol/mL-0.0001mol/ in the water phase mL。
Further, in step 1), the surfactant is selected from cation or nonionic surface active agent, HLB value is 2-7.
Further, in step 1), the surfactant is selected from cetyl trimethylammonium bromide, dodecyl three Methyl bromide ammonium, lecithin.
Further, in step 1), the alkaline organic is the organic matter that hydrolysis occurs and generates OH-；Step 2) in, the aqueous phase reactions precursor is the metal cation that precipitating is generated with hydroxyl.
The film of invention preparation is a kind of three layers or two layers of film, and wherein supporting layer and functional layer certainly exist, Organic layer is optional layer, and according to the demand of prepared film, the corresponding organic and inorganic precursor object of selection is generated corresponding organic Layer.
Further, the oily phase reaction precursor includes tetraethyl orthosilicate；The aqueous phase reactions precursor packet Include metal salt；When the oil is mutually contacted with water phase, oily phase reaction precursor and aqueous phase reactions precursor generate supporting layer；It is described Tetraethyl orthosilicate alkaline organic hydrolysis generate it is hydroxy under the conditions of, hydrolysis generate silica systematic function Layer.
Further, when the oily phase reaction precursor further includes organic reaction precursor, the aqueous phase reactions Precursor further includes alkaline oxidiser, and when the oil is mutually contacted with water phase, reaction generates organic layer in the functional layer, Form supporting layer-functional layer-organic layer layer structure.
Further, when the organic reaction precursor is aniline, the alkaline oxidiser is camphorsulfonic acid, institute The corresponding organic layer generated is polyaniline nano fiber, when the organic reaction precursor is aniline, the alkaline oxygen Agent is gold chloride, and the organic layer of corresponding generation is polyaniline/Au heterodimer.
Further, in step 1), the ultrasonic dissolution is ultrasonic dissolution under the conditions of 40-42 DEG C.
Nanometer film is made of three layers of nano material, wherein having one layer is supporting layer；Film two sides in preparation due to reacting Difference causes structure and main component also different, and the thickness of film is limited by reaction process；Nano material therein is mainly It is generated by the reaction on liquid-liquid interface, can according to need design regulation composition and pattern；The nano particle of component film and surface Activating agent and cosurfactant interaction combine, while rule very rich are formed during these nano-particles self assembles The nano-scale pore structure of rule, pore structure surface have many surfactant groups, and the mass transfer for forming basic selectivity is logical Road；There is one layer of relative tight layer among film, so that general substance is difficult to pass through mass transfer.
The supporting layer refers to the crystal for being capable of forming stratiform, sheet or band-like crystal form, by forming band-like, sheet Or layered nano-structure, form supporting layer；Supporting layer is a part of film, while playing limitation film thickness, increases whole material Expect intensity, improves porosity, reduce the effect of shrinking percentage；The film includes supporting layer and functional layer, and same ingredient can be both Supporting layer is also functional layer, and functional layer mainly assigns material special performance, such as catalytic, adsorptivity, selective penetrated property, parent Water hydrophobicity, high specific surface area etc.；The thickness of the film is uniform adjustable；
The reaction occurs on grease liquid-liquid interface, and is different in the reaction that oil is surveyed and water side occurs；Reaction What is generated is that nano-solid is attracted to interface, and combines with surfactant etc., and the nano particle of these generations is on interface Further growth and self assembly, ultimately form nanometer film；The surfactant can be single, be also possible to compound , it may include cosurfactant, and the by-product reacted can also be used as surfactant or cosurfactant； The pore structure is mainly the pore structure of the pore structure and interface part micelle forma-tion that are self-assembly of by nano material, Property of these scientific structures due to the nano-material surface itself of composition, such as surface charge, surface hydroxyl and nanometer material The organic matter of adsorption link, mainly surfactant and cosurfactant are expected, to impart the special selection of film Permeability；
The reaction includes: that 1, alkaline organic is dissolved in oily phase, reacts with water and generates OH-；2, metal soluble in water from Son, with OH- or other anion (by being dissolved in oily phase, reacting what hydrolysis generated with water) formation nano lamellars, sheet or With precipitating, supporting layer is formed；3, under the catalytic action of OH-, oily phase reaction precursor, such as positive tetrasilicic acid ethyl ester (TEOS), Hydrolysis-condensation reaction occurs and forms nano-solid substance；4, oxidisability metal cation and reductive organic matter are in interface generation oxygen Change reduction reaction, generates nano-metal particle；5, the precursor by addition, condensation, polycondensation reaction is dissolved separately in oily phase and water Xiang Zhong, then addition, condensation, polycondensation reaction occur on interface, generate target substance；The reaction includes above-mentioned 1 or multiple, And it can interact between differential responses, for example react catalyst or precipitating reagent that the OH- of generation is reacted as other, React template etc. of the nano material with special construction of 3-5 generation as reaction 6；
The surfactant dissolution mechanism includes: a. to be dissolved into water phase if the solubility in water phase is higher, B. dissolution enters oil mutually or in water phase to increase the solubility of reacting precursor object wherein dissolved as needed, and c. is by table agent It is separately dissolved with reacting precursor object, is such as dissolved in a small amount of oily phase, is initially formed interface with water phase, be re-introduced into before having dissolved reaction The oily phase of body object, reacts at interface；The standing can fix certain phase with low temperature, so that interface is relatively fixed, can also increase The condition for adding the promotions such as illumination, radiation, high temperature and pressure appropriate to react is reacted to control；
Reaction dominant mechanism: corresponding substance is dissolved in water phase and oily phase respectively (i.e. in two incompatible phases), is led to Liquid liquid two-arch tunnel Preparation equipment or method are crossed, the liquid-liquid interface of two-arch tunnel is formed, is the surface of dissolution first on interface Activating agent is diffused rapidly on interface, reduces the surface tension at interface, is maintained the stabilization of liquid-liquid interface to be formed, is dissolved in simultaneously Reaction initiator (by taking benzylamine as an example) in oily phase reacts in oil-water interfaces generates OH-, OH-It is quickly positive with the metal in water Hydroxide precipitation reaction occurs for ion, according to precipitating under the collective effect for being deposited in surfactant and interfacial tension of generation Heterogeneity, in oil-water interfaces Rapid self assembly at the supporting layer of different structure, while surfactant and nano particle are heavy Shallow lake interactive surfaces reactive nanoparticles will substantially reduce the surface tension of oil-water interfaces, with nanoparticles on interface Increase on the other hand make double so that the difficulty that reacting precursor object penetrates interface increases to limiting the thickness of nanometer layer Continuous phase is stablized even oil-water interfaces and is expanded automatically, and system is promoted to develop to interpenetrating composite, when metal cation consumes It is more, there is extra OH-When, in OH-Under catalytic action, the reacting precursor object (by taking TEOS as an example) in oily phase is dissolved in grease Hydrolysis condensation reaction occurs on interface, forms collosol and gel, and be self-assembly of nano-silica under the action of surfactant SiClx ball, and under interfacial tension, capillary force action, nano silica set is further self-assembly of on interface Body, when after reaction, forming stable two-arch tunnel emulsion gel, formd on two-arch tunnel interface one layer it is continuous complete Whole (including supporting layer, binder course, functional layer etc.) nanometer layer being made of nano material, not according to nano material composition It crosses, has different property.
The reaction wraps but is not limited to following content:
1, alkaline organic is dissolved in oily phase, is reacted with water and is generated OH-, the alkaline organic includes but is not limited to: first Amine > urea (urea) > ethamine > ethanol amine > ethylenediamine > dimethylamine > trimethylamine > triethylamine > propylamine > isopropylamine > propane diamine > 1 1,3-, 2- propane diamine > tripropyl amine (TPA) > triethanolamine > butylamine > isobutyl amine > tert-butylamine > hexylamine > octylame > aniline > benzylamine > cyclohexylamine > pyridine > Hexa > 2-chlorophenol > 3- chlorophenol > 4- chlorophenol > o-aminophenol > m-aminophenol > para-aminophenol > ortho-aminotoluene > Meta-aminotoluene > para-totuidine > 8-hydroxyquinoline (20 DEG C) > diphenylamines > benzidine.
2, metal ion soluble in water, with OH-Or other anion (by being dissolved in oily phase, hydrolysis are reacted with water and is produced Raw) formation nano lamellar, sheet or zone precipitation etc., supporting layer is formed, including but not limited to: the chemical molecular composition of LDHs ForX is 0~1, M2+、M3+For metal ion, An-For interlayer anion, both Can modulation in a certain range, and then the functional material of a series of available different compositions, different structure, structure such as Fig. 1 institute Show.M on laminate2+Part is by M3+Some remaining positive charges, A can be generated when substitution, on neatly stone veneern-Then it is used to put down Weigh this part positive charge, makes entire LDHs material electroneutral.Common bivalent cation has Ca2+、Mg2+、Zn2+、Ni2+、Mn2 +、Co2+And Fe2+；Common Tricationic has Al3+、Cr3+、Mn3+、Fe3+、Ga3+、Co3+And Ni3+。
3, oxidisability metal cation and reductive organic matter generate nano metal in interface generation redox reaction Grain, including but not limited to: have various structures (monocrystalline, twin etc.) and various patterns (cube, truncated cube, octahedron, Rescinded angle is octahedra, rodlike, decahedron, icosahedron, plate-like etc.) metal nano material (Au, Ag, Pt, Pd, Rh, Cu, Fe, CO, Ni etc.) more than 50.
The utility model has the advantages that compared with prior art, the preparation method of large-area nano film of the invention, can prepare has The nanometer film of multilayered structure, at least one layer of supporting layer, functional layer there are many selection, structure is complicated, it is vdiverse in function, have good machine The nanometer film of tool performance.
Detailed description of the invention
Fig. 1 is TEOS+Al2(SO4)3*18H2400 times of optical microscope photographs of O；
Fig. 2 is CTAB+TEOS+Zn (NO3)2*6H2400 times of optical microscope photographs of O；
Fig. 3 is CTAB+TEOS+Zn (NO3)2*6H210000 times of SEM of O scheme；
Fig. 4 is CTAB+TEOS+Al2(SO4)3*18H2The SEM figure that 10000 times of O.
Specific embodiment
The present invention will be further explained in the following with reference to the drawings and specific embodiments.
The preparation method of large-area nano film, includes the following steps:
1) surfactant, oily phase reaction precursor, alkaline organic and organic solvent are added into reactor, and in water Ultrasonic dissolution is as oily phase under the conditions of bath；
2) aqueous phase reactions precursor is dissolved in water, as water phase；
3) it is mutually steadily contacted oily with water phase, forms flat oil-water interfaces between upper layer and lower layer liquid；
4) it stands, the reaction for promoting reacting precursor object to design at interface generates large-area nano film.
In step 1), in oily phase, the concentration of surfactant is 0.01g/mL-0.05g/mL, oily phase reaction precursor Concentration is 0.01ml/mL-0.1ml/mL, and the concentration of alkaline organic is 0.005ml/mL-0.01ml/mL；Step 1-3) in, oil The ratio of phase density and aqueous phase densities is less than or equal to 0.8 or more than or equal to 1.2.
In step 2), the concentration of positive charge is 0.00006mol/mL-0.0001mol/mL in water phase.
In step 1), surfactant is selected from cation or nonionic surface active agent, HLB value 2-7.
In step 1), surfactant is selected from cetyl trimethylammonium bromide, dodecyl trimethyl ammonium bromide, lecithin Rouge.
In step 1), alkaline organic is the organic matter that hydrolysis occurs and generates OH-；In step 2), metal salt be with Hydroxyl generates the metal cation of precipitating.
The film of invention preparation is a kind of three layers or two layers of film, and wherein supporting layer and functional layer certainly exist, Organic layer is optional layer, and according to the demand of prepared film, the corresponding organic and inorganic precursor object of selection is generated corresponding organic Layer.
Oily phase reaction precursor includes tetraethyl orthosilicate；Aqueous phase reactions precursor includes metal salt；It is oily mutually to be connect with water phase When touching, oily phase reaction precursor and aqueous phase reactions precursor generate supporting layer；Tetraethyl orthosilicate is hydrolyzed in alkaline organic and is given birth to At it is hydroxy under the conditions of, hydrolysis generate silica systematic function layer.
When oily phase reaction precursor further includes organic reaction precursor, aqueous phase reactions precursor further includes alkaline oxygenated Agent, when oil is mutually contacted with water phase, reaction generates organic layer on a functional, forms supporting layer-functional layer-organic layer stratiform knot Structure.
When the organic reaction precursor is aniline, the alkaline oxidiser is camphorsulfonic acid, corresponding generation Organic layer be polyaniline nano fiber, when the organic reaction precursor be aniline when, the alkaline oxidiser be chlorine Auric acid, the organic layer of corresponding generation are polyaniline/Au heterodimer.
Embodiment 1
The preparation method of large-area nano film, includes the following steps:
1, tetraethyl orthosilicate 2ml (0.089ml/ml in oily phase) is weighed；
2, benzylamine 0.5ml is weighed, (0.0222ml/ml in oily phase)；
3,20mlCHCl is measured3Density is 1500kg/m3；
4,40-42 DEG C of ultrasonic dissolution is as oily phase；
5, a small amount of Al is weighed2(SO4)3*18H2O 0.05g is added in distilled water in 5ml, dissolution so that positive charge it is dense Degree is 0.0002252mol/ml；
6, water phase is poured slowly into oily phase；
7, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
8, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M1.As shown in Figure 1, formed Film is fine and close film, and what is loaded above is the silica to be formed.
Embodiment 2
The preparation method of large-area nano film, includes the following steps:
1,0.021g cetyl trimethylammonium bromide (CTAB) (0.003g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4,7mlCHCl is measured3Density is 1500kg/m3；
5,40-42 DEG C of ultrasonic dissolution is as oily phase；
6, a small amount of Zn (NO is weighed3)2·6H2O 0.008925g is added in distilled water, dissolves the concentration so that positive charge For 0.00006mol/ml；
7, water phase is poured slowly into oily phase；
8, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
9, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M2.Its microstructure is micro- State under mirror, layer as shown in Figure 2 form the fine and close film of comparison.The pointing object being attached to above is silica, sheet For metal hydroxides, comparison diagram 1 is as can be seen that surfactant changes the structure of material.And the layer structure more refined In Fig. 3 as can be seen that granular above is silica dioxide granule, below loose stratiform be zinc hydroxide be supporting layer.
Embodiment 3
The preparation method of large-area nano film, includes the following steps:
1,0.07g cetyl trimethylammonium bromide (CTAB) (0.01g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4,7mlCHCl is measured3(density 1500kg/m3)；
5,40-42 DEG C of ultrasonic dissolution is as oily phase；
6, a small amount of Zn (NO is weighed3)2·6H2O 0.008925g is added in distilled water, dissolves the concentration so that positive charge For 0.00006mol/ml；
7, water phase is poured slowly into oily phase；
8, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
9, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M3.
Embodiment 4
The preparation method of large-area nano film, includes the following steps:
1,0.07g cetyl trimethylammonium bromide (CTAB) (0.01g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4,7mlCHCl is measured3(density 1500kg/m3)；
5,40-42 DEG C of ultrasonic dissolution is as oily phase；
6, a small amount of Al is weighed2(SO4)3*18H2O 0.09324g is added in distilled water, dissolves the concentration so that positive charge For 0.00006mol/ml；
7, water phase is poured slowly into oily phase；
8, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
9, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M4.The structure of film such as Fig. 4 table Show, it can be seen that different from Fig. 3, supporting layer is aluminium hydroxide, and structure is finer and close, above it is granular be silica.
Embodiment 5
The preparation method of large-area nano film, includes the following steps:
1,0.07g cetyl trimethylammonium bromide (CTAB) (0.01g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4,7mlCHCl is measured3(density 1500kg/m3)；
5,40-42 DEG C of ultrasonic dissolution is as oily phase；
6, a small amount of Al is weighed2(SO4)3*18H2O 0.04662g, Zn (NO3)2·6H2O0.0313g is added in distilled water, Dissolution is so that the concentration of positive charge is 0.00006mol/ml；
7, water phase is poured slowly into oily phase；
8, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
9, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M5.
Embodiment 6
The preparation method of large-area nano film, includes the following steps:
1,0.35g cetyl trimethylammonium bromide (CTAB) (0.05g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4,7mlCHCl is measured3(density 1500kg/m3)；
5,40-42 DEG C of ultrasonic dissolution is as oily phase；
6, a small amount of Zn (NO is weighed3)2·6H2O 0.008925g is added in distilled water, dissolves the concentration so that positive charge For 0.00006mol/ml；
7, water phase is poured slowly into oily phase；
8, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
9, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M6.
Embodiment 7
The preparation method of large-area nano film, includes the following steps:
1,0.07g lecithin (0.01g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4,7mlCHCl is measured3(density 1500kg/m3)；
5,40-42 DEG C of ultrasonic dissolution is as oily phase；
6, a small amount of Zn (NO is weighed3)2·6H2O 0.008925g is added in distilled water, dissolves the concentration so that positive charge For 0.00006mol/ml；
7, water phase is poured slowly into oily phase；
8, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
9, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M7.
Embodiment 8
The preparation method of large-area nano film, includes the following steps:
1,0.07g cetyl trimethylammonium bromide (CTAB) (0.01g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4, aniline 1ml (1.02g) concentration 0.143ml/ml in oily phase is weighed；
5,6ml hexane (density 660kg/m is measured3)；
6,40-42 DEG C of ultrasonic dissolution is as oily phase；
7, a small amount of Zn (NO is weighed3)2·6H2O 0.008925g is added in distilled water, dissolves the concentration so that positive charge For 0.00006mol/ml；
8, camphorsulfonic acid 0.1g is weighed, concentration is 0.0143g/ml in water phase；
9, water phase is poured slowly into oily phase；
10, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
11, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M8.
Embodiment 9
The preparation method of large-area nano film, includes the following steps:
1,0.07g cetyl trimethylammonium bromide (CTAB) (0.01g/ml in oily phase) is weighed；
2, tetraethyl orthosilicate 0.07ml (0.01ml/ml in oily phase) is weighed；
3, benzylamine 0.035ml is weighed, (0.005ml/ml in oily phase)；
4, aniline 1ml (1.02g) concentration 0.143ml/ml in oily phase is weighed；
5,6ml hexane (density 660kg/m is measured3)；
6,40-42 DEG C of ultrasonic dissolution is as oily phase；
7, a small amount of Zn (NO is weighed3)2·6H2O 0.008925g is added in distilled water, dissolves the concentration so that positive charge For 0.00006mol/ml；
8, HAuCl is weighed3·HCl·4H2O 0.1g, concentration is 0.0143g/ml in water phase；
9, water phase is poured slowly into oily phase；
10, in prefabricated reactor, oil is mutually steadily contacted with water phase, forms smooth flat oil-water interfaces；
11, it stands, the reaction for promoting reacting precursor object to design at interface；Membrane marker is M9.
10 test case of embodiment
It as shown in table 1 below, is the film thickness test result of the obtained film M1-M9 of embodiment 1-9, it can be direct by SEM Measure thickness.
The film thickness test result of 1 film M1-M9 of table
M1 M2 M3 M4 M5 M6 M7 M8 M9
Film thickness (nm) 2057 3319 3142 2516 2899 3095 3541 4658 4875
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims (10)

1. the preparation method of large-area nano film, characterized by the following steps:
1) surfactant, oily phase reaction precursor, alkaline organic and organic solvent are added into reactor, and in water-bath item Ultrasonic dissolution is as oily phase under part；
2) aqueous phase reactions precursor is dissolved in water, as water phase；
3) it is mutually steadily contacted oily with water phase, forms flat oil-water interfaces between upper layer and lower layer liquid；
4) it stands, the reaction for promoting reacting precursor object to design at interface generates large-area nano film.
2. the preparation method of large-area nano film according to claim 1, it is characterised in that: in step 1), the oil Xiang Zhong, the concentration of surfactant are 0.01g/mL-0.05g/mL, and the concentration of oily phase reaction precursor is 0.01ml/mL- 0.1ml/mL, the concentration of alkaline organic are 0.005ml/mL-0.01ml/mL；Step 1-3) in, the oily phase density and water The ratio of phase density is less than or equal to 0.8 or more than or equal to 1.2.
3. the preparation method of large-area nano film according to claim 1, it is characterised in that: in step 2), the water The concentration of positive charge is 0.00006mol/mL-0.0001mol/mL in phase.
4. the preparation method of large-area nano film according to claim 1, it is characterised in that: in step 1), the table Face activating agent is selected from cation or nonionic surface active agent, HLB value 2-7.
5. the preparation method of large-area nano film according to claim 4, it is characterised in that: in step 1), the table Face activating agent is selected from cetyl trimethylammonium bromide, dodecyl trimethyl ammonium bromide and lecithin.
6. the preparation method of large-area nano film according to claim 1, it is characterised in that: in step 1), the alkali Property organic matter be occur hydrolysis generate OH- organic matter；In step 2), the aqueous phase reactions precursor is and hydroxyl Generate the metal cation of precipitating.
7. the preparation method of large-area nano film according to claim 6, it is characterised in that: the oily phase reaction precursor Object includes tetraethyl orthosilicate；The aqueous phase reactions precursor includes metal salt；When the oil is mutually contacted with water phase, oily phase Reacting precursor object and aqueous phase reactions precursor generate supporting layer；The tetraethyl orthosilicate is generated in alkaline organic hydrolysis Under the conditions of hydroxy, hydrolysis generates silica systematic function layer.
8. the preparation method of large-area nano film according to claim 7, it is characterised in that: before the oily phase reaction When body object further includes organic reaction precursor, the aqueous phase reactions precursor further includes alkaline oxidiser, the described oil mutually with When water phase contacts, reaction generates organic layer in the functional layer, forms supporting layer-functional layer-organic layer layer structure.
9. the preparation method of large-area nano film according to claim 8, it is characterised in that: before the organic reaction When body object is aniline, the alkaline oxidiser is camphorsulfonic acid, and the organic layer of corresponding generation is polyaniline nano fiber, when When the organic reaction precursor is aniline, the alkaline oxidiser is gold chloride, and the organic layer of corresponding generation is poly- Aniline/Au heterodimer.
10. the preparation method of large-area nano film according to claim 1, it is characterised in that: in step 1), described is super Sound dissolution is ultrasonic dissolution under the conditions of 40-42 DEG C.
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