CN110372022A - Macroscopical 3D multistage porous nanometer material one-step method for synthesizing - Google Patents
Macroscopical 3D multistage porous nanometer material one-step method for synthesizing Download PDFInfo
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Abstract
The invention discloses macroscopical 3D multistage porous nanometer material one-step method for synthesizing, belong to technical field of nano material, include the following steps: that surfactant and oily phase reaction precursor 1) are added into organic solvent, as oily phase；Aqueous phase reactions precursor is added in Xiang Shuizhong, as water phase；2) mixing is mutually contacted with water phase by oily, form the bicontinuous emulsion at grease two-arch tunnel interface；3) it stands, obtains macroscopical 3D multistage porous nanometer material.Macroscopical 3D multistage porous nanometer material one-step method for synthesizing of the invention, directly synthesize the integral macroscopic 3D nano material tangled and formed by continuous nanometer layer by liquid, continuous nanometer layer forms the multistage pore canal of co-continuous, from initial micron-sized duct nanoscale Kong Douyou, continuous nanometer layer is the composite nano materials for having nano material to synthesize.The structural strength that continuous nanometer layer provides can easily overcome the capillary pressure in removal liquid process, and volume contraction is less than 15% after dehydration.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to macroscopical 3D multistage porous nanometer material one-step synthesis side
Method.
Background technique
Porous material refers to a kind of material with a large amount of certain size pore structure and high specific surface area.It is opposite to connect
For continuous dielectric material, porous material generally have the absorption property that relative density is low, specific surface area is high, excellent and it is good every
The features such as sound, heat-insulated, permeability, and it is widely used to aerospace, environmental protection, telecommunications, atomic energy, medicine, traffic
The fields such as transport, metallurgy, building, mechanical, electrochemistry and petrochemical industry, be related to absorption, noise reduction, filtering, separation, circuits mask,
Heat-insulated, catalysis reaction, energy storage and all various purposes such as conversion and bioengineering, in science and technology and the development of the national economy
Play great function.
Sol-gal process refers to that one or more of components form colloidal sol in solution, converts colloidal sol using a series of processing
At gel, thus a kind of method for forming uniform almost non-crystalline solids.Progress of the colloidal sol with reaction, solid particle meeting
Crosslinking is grown up, and the gelation substance with network structure is become.Usually with metallo-organic compound, metal inorganic compound or
Both above-mentioned is the process that the mixture that raw material is formed passes through hydrolytie polycondensation, gradually gelation and the corresponding aging of progress and drying
Processing, and obtain oxide or the method for other compounds.
Two steps: the first step are broadly divided into based on the method that sol-gal process prepares porous material, by raw material and auxiliary honest material
It is dissolved in progress sol-gel process in solvent and ultimately forms gel；Second step obtains gel porous after being dried
Material.The state of gel and the pore structure of Drying Treatment Technology joint effect final product.
Macroscopical nano-porous materials Typical Representative is aeroge, and aerogel material typically refers to mutually interpolymerized with nano-scale particle
Collection forms nano-porous structure, and the three-dimensional porous lightweight solid material of gaseous state decentralized medium is full of in nano aperture.Airsetting
The distinctive three-dimensional network pore structure of glue, makes it have many unique properties, including high surface area, low refraction coefficient, low leads
Electrostrictive coefficient, low heat transfer coefficient, in a low voice spread speed, low-density etc..This makes aeroge have very extensive application field.Gas
Gel, due to the presence of surface tension, easily causes broken and pore structure the destruction of aerogel material in drying stage.Airsetting
The porosity of glue necessarily causes material brittleness itself big and frangible.
Generally speaking, aeroge has the disadvantage that: expensive preparation cost；It can be along with huge volume in drying process
It shrinks, cracking is easily caused, especially to larger-size colloid；Material itself is difficult to the low-intensity overcome, high crisp etc..These
Disadvantage, which becomes, restricts its widely applied bottleneck, therefore also becomes the key that scientists from all over the world's joint efforts from now on are broken through.It is existing
Technology is often to vibrate the application of the powder of nano material, such as forms powder consolidation, this actually reduces specific surface area
Multi-stage porous abundant can not be formed simultaneously, is highly detrimental to applications to nanostructures.
Summary of the invention
Goal of the invention: the purpose of the present invention is to provide macroscopical 3D multistage porous nanometer material one-step method for synthesizing, the materials
Material has nanostructure abundant, and specific surface area is very big；Shrinking percentage is very low during the preparation process, and the material prepared is opposite
Traditional aeroge has very high intensity.
Technical solution: to achieve the above object, the invention provides the following technical scheme:
Macroscopical 3D multistage porous nanometer material one-step method for synthesizing, includes the following steps:
1) surfactant and oily phase reaction precursor are added into organic solvent, as oily phase；Water phase is added in Xiang Shuizhong
Reacting precursor object, as water phase；
2) mixing is mutually contacted with water phase by oily, form the bicontinuous emulsion at grease two-arch tunnel interface；
3) it stands, obtains macroscopical 3D multistage porous nanometer material.
Macroscopical 3D multistage porous nanometer material is made of the two-dimensional curved surface that nano material forms, and curved surface is irregular
, including the channel being formed of curved surface；Curved surface is made of several layers of nano material, wherein at least includes supporting layer, binder course
And functional layer, supporting layer can be mainly fixed co-continuous interfaces, improve structural strength, binder course is functional layer and supporting layer
Binder course, functional layer assign some other corresponding specific functions of material；Has a multi-stage artery structure, including from micropore, mesoporous
To the nano aperture of macropore, maximum diameter of hole even can reach micron order, these ducts are interconnected.
Further, in step 1), the oily phase reaction precursor is alkaline organic, the aqueous phase reactions precursor
Object is metal salt；In step 2), after the oil mutually contacts mixing with water phase, the alkaline organic and metal salt are in oil-water interfaces
Hydroxide precipitating is generated, and is further self-assembly of the branch of nanostructure under the action of surfactant and surface tension
Support layer.
In step 2), including following reaction:
2.1) initiation reaction: alkaline organic generates OH with water on oil-water interfaces-；
2.2) supporting layer reacts: the OH that the cation of metal salt is generated in oil-water interfaces water side and initiation reaction in water phase-
Hydroxide precipitating is generated in oil-water interfaces, and is further self-assembled into nanometer under the action of surfactant and surface tension
Structural support layers.
Further, the hydroxide precipitated chemical molecular composition is
Wherein, X is 0~1, M2+、M3+For metal ion, An-For interlayer anion.
Further, in step 1), the oily phase reaction precursor further includes the metal alkoxide for being used to form functional layer
And/or macromolecular in organic polymer reaction.
Further, when the oily phase reaction precursor includes macromolecular in organic polymerization reaction, the water phase
Reacting precursor object further includes organic polymer reaction small molecular, and macromolecular reacts medium and small with organic polymer in organic polymer reaction
One of addition, condensation, polycondensation reaction or a variety of occur for molecule, generate resin.
It follows that functional layer reaction the following steps are included:
2.3) when oily phase reaction precursor further includes metal alkoxide, metal alkoxide is causing instead in the oily phase side at interface
The OH that should be generated-Catalytic action under, with water phase occur hydrolytic-polymeric reaction, formed nano structural material；
2.4) when oily phase reaction precursor further includes macromolecular in organic polymer reaction, the aqueous phase reactions precursor
It further include organic polymer reaction small molecular, macromolecular reacts small molecular with organic polymer and occurs to add in organic polymer reaction
At, condensation, one of polycondensation reaction or a variety of, resin is generated；
2.5) when oily phase reaction precursor also includes macromolecular in metal alkoxide and organic polymer reaction simultaneously, step
2.3) reaction -2.4) has generation.
Step 2.3) -2.5) reaction carried out on interface, it is multistage more to form macroscopical 3D along two-arch tunnel interface growth
Hole nano material；With the progress of reaction, the nanometer layer generated on interface is more and more finer and close, to limit water-oil phase and molten
The diffusion of the reacting precursor object of solution with contact, so that the reaction that suffocated, limits the thickness of nanometer layer.
Further, in step 1), Xiang Shuizhong is additionally added surfactant, as water phase.
Further, surfactant additive amount accounts for 50% or more of total surfactant additive amount in the oily phase,
The additive amount of surfactant accounts for 50% or less total surfactant additive amount in the water phase；The total surface activity
Agent additive amount concentration in the sum of oily phase and water phase volume is 10g/mL~0.01g/mL.
Further, in step 1), the volume ratio that the organic solvent accounts for oily phase is 10%~80%；Step 1) and step
It is rapid 2) in, the oily phase density is 0.6~1.3 times of aqueous phase densities, and oil phase viscosity is 0.7~1.6 times of aqueous viscosity；Step
It is rapid 2) in, the water phase and the ratio that mixes of oil are 1:3~3:1, the oil mutually contact with water phase mix after, water phase is anti-
Answering cationic positive charge concentration in precursor is 0.00001~0.005mol/mL, and cationic positive changes and alkaline organic are managed
Molar ratio by the anion negative electrical charge number of generation is 0.5~0.8.
Further, the organic solvent is 1- heptyl bromide, 1- bromooctane, 1- bromononane, 1- bromo-n-11,1- bromine ten
Four alkane, chlorine hexamethylene, 1- bromine hexadecane, 4- methyl -3- ethyl heptane, 4- methylundecane, n-tridecane, n-eicosane, uncle
One or more kinds of combination in butyl benzene, 1,1- Diphenylheptane；The HLB of the surfactant is 2-7, the table
Face activating agent is didodecyldimethylammbromide bromide and/or lecithin.
Further, in step 3), the standing is 12~48h of standing under room temperature condition of normal pressure.
Reaction mechanism: corresponding substance is dissolved in water phase and oily phase respectively (i.e. in two incompatible phases), liquid is passed through
Liquid two-arch tunnel Preparation equipment or method form the liquid-liquid interface of two-arch tunnel, are the surface-active of dissolution first on interface
Agent is diffused rapidly on interface, reduces the surface tension at interface, maintains the stabilization of liquid-liquid interface to be formed, while being dissolved in oily phase
In reaction initiator (by taking benzylamine as an example) react in oil-water interfaces and generate OH-, OH-Quickly with the metal cation in water
Hydroxide precipitation reaction occurs, under the collective effect for being deposited in surfactant and interfacial tension of generation not according to precipitating
Congeniality, in oil-water interfaces Rapid self assembly at the supporting layer of different structure, while surfactant and nanoparticle precipitate phase
Interaction surface reactive nanoparticles will substantially reduce the surface tension of oil-water interfaces, with the increasing of nanoparticles on interface
Greatly, so that the difficulty that reacting precursor object penetrates interface increases to limit the thickness of nanometer layer, on the other hand make co-continuous
Mutually stablize even oil-water interfaces expand automatically, promote system to interpenetrating composite develop, when metal cation consume 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 on oil-water interfaces
Hydrolysis condensation reaction occurs, forms collosol and gel, and be self-assembly of nanometer titanium dioxide silicon ball under the action of surfactant,
And under interfacial tension, capillary force action, it is further self-assembly of nano silica aggregate on interface, works as reaction
After, stable two-arch tunnel emulsion gel is formed, one layer is formd on two-arch tunnel interface continuously completely by receiving
(including supporting layer, binder course, functional layer etc.) nanometer layer of rice material composition but according to nano material composition has not
Same property.
The utility model has the advantages that compared with prior art, macroscopical 3D multistage porous nanometer material one-step method for synthesizing of the invention, directly
It connected liquid and synthesizes the integral macroscopic 3D nano material tangled and formed by continuous nanometer layer, continuous nanometer layer forms doubly-linked
Continuous multistage pore canal, from initial micron-sized duct nanoscale Kong Douyou, continuous nanometer layer has nano material synthesis
Composite nano materials；Hydroxide supporting layer is formd in oil-water interfaces water side, the thickness for changing supporting layer is generally less than 2 microns,
And there is complicated nanostructure, particularly importantly supporting layer is one whole along the continuous macroscopic view of co-continuous interface growth
Body has formed and kept macroscopical 3D multistage porous structure under the action of supporting layer；The structural strength that continuous nanometer layer provides, energy
Enough capillary pressures easily overcome in removal liquid process, volume contraction is less than 15% after dehydration.
Detailed description of the invention
Fig. 1 is that macroscopic view 3D multistage porous nanometer material one-step method for synthesizing amplifies 100 times, the SEM figure not shaken；
Fig. 2 is that macroscopic view 3D multistage porous nanometer material one-step method for synthesizing amplifies 5000 times, the SEM figure not shaken；
Fig. 3 is macroscopic view 3D multistage porous nanometer material section structure；
Fig. 4 is the irregular continuous nanometer layer that irregular co-continuous solution interface is formed.
Specific embodiment
The present invention will be further explained in the following with reference to the drawings and specific embodiments.
Macroscopical 3D multistage porous nanometer material one-step method for synthesizing, includes the following steps:
1) surfactant and oily phase reaction precursor are added into organic solvent, as oily phase；Water phase is added in Xiang Shuizhong
Reacting precursor object, as water phase；
2) mixing is mutually contacted with water phase by oily, form the bicontinuous emulsion at grease two-arch tunnel interface；
3) it stands, obtains macroscopical 3D multistage porous nanometer material.
Macroscopical 3D multistage porous nanometer material is made of the two-dimensional curved surface that nano material forms, and curved surface is irregular
, including the channel being formed of curved surface；Curved surface is made of several layers of nano material, and wherein at least having one layer is supporting layer；It is bent
Face two sides cause structure and main component also different due to the difference reacted in preparation, and the thickness of curved surface is by preparation reaction
Limitation；The nano particle of component film is combined with surfactant and cosurfactant interaction, while these nano particles
The nano-scale pore structure of rule very rich is formed in self assembling process, pore structure surface has many surfactants
Group forms the mass transfer channel of basic selectivity；Nano material therein is mainly to be generated by the reaction on liquid/liquid interface, can
With design as needed regulation；There is one layer of relative tight layer among curved surface, so that substance is difficult to pass through mass transfer；Have on curved surface very much
Fold and protrusion；Integral material has abundant duct, from nanoscale to micron order；The material shape that finally prepares and prepare precursor
The shape size of liquid is identical；Macroscopical 3D multistage porous nanometer material one-step method for synthesizing has a multi-stage artery structure, including from
Micropore, the mesoporous nano aperture to macropore, maximum diameter of hole even can reach micron order, these ducts are interconnected, and have very much
Conducive to liquid flowing and mass transfer, a step, which realizes, very big specific surface area, is provided simultaneously with higher mass transfer ability.
In step 1), oily phase reaction precursor is alkaline organic, and aqueous phase reactions precursor is metal salt；In step 2),
After oily phase contacts mixing with water phase, the alkaline organic and metal salt generate hydroxide in oil-water interfaces and precipitate, and on surface
The supporting layer of nanostructure is further self-assembly of under the action of activating agent and surface tension.
In step 2), including following reaction:
2.1) initiation reaction: alkaline organic generates OH with water on oil-water interfaces-；
2.2) supporting layer reacts: the OH that the cation of metal salt is generated in oil-water interfaces water side and initiation reaction in water phase-
Hydroxide precipitating is generated in oil-water interfaces, and is further self-assembled into nanometer under the action of surfactant and surface tension
Structural support layers.
Hydroxide precipitated chemical molecular composition isWherein, X is 0~1, M2 +、M3+For metal ion, An-For interlayer anion.
In step 1), oily phase reaction precursor further include be used to form functional layer metal alkoxide and/or organic polymer it is anti-
Answer middle macromolecular.
When oily phase reaction precursor includes macromolecular in organic polymerization reaction, aqueous phase reactions precursor further includes organic poly-
Reaction small molecular is closed, macromolecular reacts small molecular generation addition, condensation, polycondensation with organic polymer in organic polymer reaction
One of reaction is a variety of, generates resin.
It follows that functional layer reaction the following steps are included:
2.3) when oily phase reaction precursor further includes metal alkoxide, metal alkoxide is causing instead in the oily phase side at interface
The OH that should be generated-Catalytic action under, with water phase occur hydrolytic-polymeric reaction, formed nano structural material；
2.4) when oily phase reaction precursor further includes macromolecular in organic polymer reaction, aqueous phase reactions precursor further includes
Organic polymer reacts small molecular, and macromolecular reacts small molecular with organic polymer and addition occurs, contracts in organic polymer reaction
One of conjunction, polycondensation reaction are a variety of, generate resin；
2.5) when oily phase reaction precursor also includes macromolecular in metal alkoxide and organic polymer reaction simultaneously, step
2.3) reaction -2.4) has generation.
Step 2.3) -2.5) reaction carried out on interface, it is multistage more to form macroscopical 3D along two-arch tunnel interface growth
Hole nano material；With the progress of reaction, the nanometer layer generated on interface is more and more finer and close, to limit water-oil phase and molten
The diffusion of the reacting precursor object of solution with contact, so that the reaction that suffocated, limits the thickness of nanometer layer.
In step 1), Xiang Shuizhong is additionally added surfactant, as water phase.
In step 1), the volume ratio that organic solvent accounts for oily phase is 10%~80%, and surfactant additive amount accounts in oily phase
50% or more of total surfactant additive amount, the additive amount of surfactant accounts for total surfactant additive amount in water phase
50% or less；Total surfactant additive amount concentration in the sum of oily phase and water phase volume is 1g/mL~0.001g/mL；Step
1) and in step 2), oily phase density is 0.6~1.3 times of aqueous phase densities, and oil phase viscosity is 0.7~1.6 times of aqueous viscosity；Step
It is rapid 2) in, water phase and the ratio that mixes of oil are 1:3~3:1；After oily phase contacts mixing with water phase, aqueous phase reactions precursor middle-jiao yang, function of the spleen and stomach
Ion positive charge concentration is 0.00001~0.005mol/mL, the yin that cationic positive changes and alkaline organic theory generate from
The molar ratio of sub- negative electrical charge number is 0.5~0.8.
Organic solvent be 1- heptyl bromide, 1- bromooctane, 1- bromononane, 1- bromo-n-11,1- bromo-tetradecane, chlorine hexamethylene,
1- bromine hexadecane, 4- methyl -3- ethyl heptane, 4- methylundecane, n-tridecane, n-eicosane, tert-butyl benzene, 1,1- hexichol
One or more kinds of combination in base heptane；The HLB of surfactant is 2-7, and surfactant is double dodecyl dimethyls
Ammonium bromide and/or lecithin.
In step 3), the standing is 12~48h of standing under room temperature condition of normal pressure.
Supporting layer, which refers to, to be capable of forming stratiform, sheet perhaps the crystal of band-like crystal form passes through and forms band-like, sheet or layer
Shape nanostructure forms supporting layer；Supporting layer is a part of curved surface, while playing restricted curved surface thickness, increases integral material
Intensity improves porosity, reduces the effect of shrinking percentage；Curved surface includes supporting layer and functional layer, and same ingredient can be both support
Layer is also functional layer, and functional layer mainly assigns material special performance, such as catalytic, adsorptivity, selective, high specific surface
Product etc.；It can according to need design and prepare special structure and ingredient, so that nano material has catalytic, adsorptivity, selection
Property and electric conductivity, different layers can be provided simultaneously with one or several so that curved surface and whole nano material have spy
Different performance is applied to corresponding occasion.
There is material property at the co-continuous interface that initial mixing is formed and obviously influences；Reaction occurs in liquid-liquid interface
On, and be different in the reaction that oil is surveyed and water side occurs；It is that nano-solid is attracted to interface, and and surface that reaction, which generates,
Activating agent combines, to further decrease interfacial tension, interfacial area is forced further to increase, interface increases to form new oil
Water termination, to form the structures such as fold, protrusion；With the progress of reaction, oily phase (or water phase) can constantly be reduced, thus
Force the interface newly formed mutually recessed to oil, to form the structures such as regular fold, protrusion；Co-continuous interface is initially by surface
Activating agent is constituted, and is then constantly constituted together with the nano-solid of generation later；Surfactant can be single, can also be with
It is compound, may include cosurfactant, and the by-product reacted can also be used as surfactant or help surface
Activating agent.
Embodiment 1
The preparation method of macroscopical 3D multistage porous nanometer material one-step method for synthesizing, step are as follows:
1, weighing the bis- dodecyl dimethyl bromine ammoniums (DDAB) of 0.7g, (concentration 0.05g/mL, 100% is dissolved in oily phase
In), it is put into reactor (25mL beaker)；
2,3.5mL ethyl orthosilicate (TEOS) is taken to pour into reactor；
3,3.5mL n-dodecane is taken to pour into reactor (organic solvent account for oil make an appointment 50%)；
4,0.7mL benzylamine is taken to pour into reactor (about 0.0063mol)；
5, ultrasonic dissolution is as oily phase；
6、Al2(SO4)3*18H2O is soluble in water, concentration 0.000112049mol/mL, as water phase；
7,7mL water phase is taken to be rapidly injected (very crucial, it is to be ensured that entire liquid is mixed after injection in above-mentioned oily phase reaction device
Close milky white, be not layered, without bubble, no clear liquid is stopped over) (the yin that cationic positive changes and alkaline organic theory generate
0.7) molar ratio of ion negative electrical charge number is about；
8, after ten minutes to oily mutually injection water phase, concussion shakes up (very crucial, it is to be ensured that entire liquid is mixing after injection
It is milky white, be not layered, without bubble, no clear liquid is stopped over), then stand under normal temperature conditions for 24 hours；
9, it is dried for 24 hours under 80 DEG C of aerobic conditions；
Drying is an entirety, shrinking percentage 6.9% afterwards for 24 hours under 80 DEG C of aerobic conditions；Structure such as Fig. 1 and Fig. 2.
Embodiment 2
The preparation method of macroscopical 3D multistage porous nanometer material one-step method for synthesizing, step are as follows:
1, the bis- dodecyl dimethyl bromine ammoniums of 0.7g (DDAB concentration is 0.05g/mL, and 100% is dissolved in oily phase) is weighed,
It is put into reactor (25mL beaker)；
2,3.5mL ethyl orthosilicate (TEOS) is taken to pour into reactor；
3, mono- bromo-tetradecane of 3.5mL is taken to pour into reactor (organic solvent account for oil make an appointment 50%)；
4,0.7mL benzylamine is taken to pour into reactor (about 0.0063mol)；
5, ultrasonic dissolution is as oily phase；
6、Zn(NO3)2*6H2O is soluble in water, concentration 0.000336146mol/mL, as water phase；
7,7mL water phase is taken to be rapidly injected (very crucial, it is to be ensured that entire liquid is mixed after injection in above-mentioned oily phase reaction device
Close milky white, be not layered, without bubble, no clear liquid is stopped over) (the yin that cationic positive changes and alkaline organic theory generate
0.7) molar ratio of ion negative electrical charge number is about；
8, it stands under normal temperature conditions for 24 hours；
9, it is dried for 24 hours under 70 DEG C of aerobic conditions；
Fig. 3, drying is whole, shrinking percentage 2.9% afterwards for 24 hours under 70 DEG C of aerobic conditions.
Embodiment 3
Macroscopical 3D multistage porous nanometer material one-step method for synthesizing, step are as follows:
1,0.5g lecithin (concentration 0.035g/mL, 100% is dissolved in oily phase) is weighed, being put into reactor, (25mL is burnt
Cup) in；
2,2.5mL ethyl orthosilicate (TEOS) is taken to pour into reactor；
3,0.2g dicetyl peroxydicarbonate diisopropyl rouge；
4,5mL heptane is taken to be put into reactor (organic solvent account for oil make an appointment 60%)；
5,0.5mL benzylamine is taken to pour into reactor (about 0.0004mol)；
6, under 40-42 DEG C of water-bath, ultrasonic dissolution is as oily phase；
7,2g vinyl chloride is taken；
8,0.5g polyvinyl alcohol is taken；
9,10mL deionized water is added；
10、Al2(SO4)3*18H2During O is soluble in the aqueous phase, concentration 0.000112049mol/mL, as water phase；
11, by heated aqueous to 95 DEG C；
12,7mL water phase is taken to be rapidly injected in above-mentioned 7mL oil phase reaction device (very crucial, it is to be ensured that entire liquid after injection
It is that mixing is milky white, is not layered, without bubble, no clear liquid is stopped over) (cationic positive changes and alkaline organic theory generate
The molar ratio of anion negative electrical charge number be about 0.8)；
13,95 DEG C of holding 12h；
14, dry 10h is cooled under 60 DEG C of aerobic conditions；
15, thermal polymerization 2h under the conditions of 100 DEG C.
It is whole, shrinking percentage 14.3% after dry 2h under 100 DEG C of aerobic conditions.
Embodiment 4
Macroscopical 3D multistage porous nanometer material one-step method for synthesizing, step are as follows:
1, weighing 1.5g cetyl trimethyl bromine ammonium (CTAB), (concentration 0.105g/mL, 100% is dissolved in oily phase
In), it is put into reactor (25mL beaker)；
2,0.5g phenol is weighed to be put into reactor；
3,1.0mL metatitanic acid methyl esters ethyl orthosilicate (TEOS) is taken to pour into reactor；
4, mono- bromo-tetradecane of 5mL is taken to pour into reactor (organic solvent account for oil make an appointment 70%)；
5,0.5mL benzylamine is taken to pour into reactor (about 0.0004mol)；
6, under 40-42 DEG C of water-bath, ultrasonic dissolution is as oily phase；
7, formaldehyde is soluble in water, concentration 0.05g/mL, as water phase；
8、Al2(SO4)3*18H2During O is soluble in the aqueous phase, concentration 0.000112049mol/mL, as water phase；
9,7mL water phase is taken to be rapidly injected in above-mentioned 7mL oil phase reaction device (very crucial, it is to be ensured that entire liquid after injection
It is that mixing is milky white, is not layered, without bubble, no clear liquid is stopped over) (cationic positive changes and alkaline organic theory generate
The molar ratio of anion negative electrical charge number be about 0.8)；
10, it stands under normal temperature conditions for 24 hours；
11, dry 10h under 60 DEG C of aerobic conditions；
12, thermal polymerization is for 24 hours under the conditions of 100 DEG C；
Drying is whole, shrinking percentage 14% afterwards for 24 hours under 100 DEG C of aerobic conditions.
Embodiment 5
Macroscopical 3D multistage porous nanometer material one-step method for synthesizing, step are as follows:
1,0.7g lecithin (concentration 0.05g/mL, 100% is dissolved in oily phase) is weighed, being put into reactor, (25mL is burnt
Cup) in；
2,2.5mL ethyl orthosilicate (TEOS) is taken to pour into reactor；
3, mono- bromo-tetradecane of 3.5mL is taken to pour into reactor (organic solvent account for oil make an appointment 50%)；
4,1.0mL phenol is taken to pour into reactor；
5,0.7mL propylamine is taken to pour into reactor (about 0.0085mol)；
6, ultrasonic dissolution is as oily phase；
7、Zn(NO3)2*6H2O is soluble in water, concentration 0.0001mol/mL, Al2(SO4)3*18H2O is soluble in water, concentration
For 0.00008mol/mL, formaldehyde is soluble in water, concentration 0.0014mol/mL, as water phase；
8,7mL water phase and 7mL oil phase are taken, is rapidly injected by two-arch tunnel preparation facilities (non-in above-mentioned oily phase reaction device
Chang Guanjian, it is to be ensured that entire liquid is that mixing is milky white after injection, is not layered, without bubble, no clear liquid is stopped over) (cation
0.55) molar ratio for the anion negative electrical charge number that positive changes and alkaline organic theory generate is about；
9, it stands under normal temperature conditions for 24 hours；
10, it is dried for 24 hours under 60 DEG C of aerobic conditions；
11, thermal polymerization is for 24 hours under the conditions of 100 DEG C；
Drying is whole, shrinking percentage 10% afterwards for 24 hours under 100 DEG C of aerobic conditions.
Embodiment 6
1, macroscopic view 3D multistage porous nanometer material one-step method for synthesizing, step are as follows:
2, weighing the bis- dodecyl dimethyl bromine ammoniums (DDAB) of 0.7g, (concentration 0.05g/mL, 100% is dissolved in oily phase
In), it is put into reactor (25mL beaker)；
3,3.5mL ethyl orthosilicate (TEOS) is taken to pour into reactor；
4,3.5mL dodecane is taken to pour into reactor (organic solvent account for oil make an appointment 50%)；
5,0.7mL benzylamine is taken to pour into reactor (about 0.0063mol)；
6, ultrasonic dissolution is as oily phase；
7、Zn(NO3)2*6H2O is soluble in water, concentration 0.000336146mol/mL, as water phase；
8,7mL water phase is taken to be rapidly injected (very crucial, it is to be ensured that entire liquid is mixed after injection in above-mentioned oily phase reaction device
Close milky white, be not layered, without bubble, no clear liquid is stopped over) (the yin that cationic positive changes and alkaline organic theory generate
0.7) molar ratio of ion negative electrical charge number is about；
9, it stands under normal temperature conditions for 24 hours；
10, it is dried for 24 hours under 70 DEG C of aerobic conditions；
Drying is whole, shrinking percentage 5.6% afterwards for 24 hours under 70 DEG C of aerobic conditions.
Embodiment 7
Macroscopical 3D multistage porous nanometer material one-step method for synthesizing, step are as follows:
1, weighing the bis- dodecyl dimethyl bromine ammoniums (DDAB) of 0.7g, (concentration 0.05g/mL, 100% is dissolved in oily phase
In), it is put into reactor (25mL beaker)；
2,3.5mL ethyl orthosilicate (TEOS) is taken to pour into reactor；
3, mono- bromo-tetradecane of 3.5mL is taken to pour into reactor (organic solvent account for oil make an appointment 50%)；
4,0.7mL benzylamine is taken to pour into reactor (about 0.0063mol)；
5, ultrasonic dissolution is as oily phase；
6、MgSO4·7H2O of 0.000168073mol/mL and Al2(SO4)3*18H2O of 5.60243E-05mol/
ML, as water phase；
7,7mL water phase is taken to be rapidly injected in above-mentioned oily phase reaction device；(cationic positive changes and alkaline organic theory are raw
At the molar ratio of anion negative electrical charge number be about 0.7)
8, it stands under normal temperature conditions for 24 hours；
9, it is dried for 24 hours under 70 DEG C of aerobic conditions；
Fig. 4, drying is whole, shrinking percentage 6.6% afterwards for 24 hours under 70 DEG C of aerobic conditions.
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. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing, characterized by the following steps:
1) surfactant and oily phase reaction precursor are added into organic solvent, as oily phase；Aqueous phase reactions are added in Xiang Shuizhong
Precursor, as water phase；
2) mixing is mutually contacted with water phase by oily, form the bicontinuous emulsion at grease two-arch tunnel interface；
3) it stands, obtains macroscopical 3D multistage porous nanometer material.
2. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to claim 1, it is characterised in that: step 1)
In, the oily phase reaction precursor is alkaline organic, and the aqueous phase reactions precursor is metal salt；In step 2), institute
After the oil stated mutually contacts mixing with water phase, the alkaline organic and metal salt generate hydroxide in oil-water interfaces and precipitate, and
The supporting layer of nanostructure is further self-assembly of under the action of surfactant and surface tension.
3. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to claim 2, it is characterised in that: described
Hydroxide precipitated chemical molecular composition isWherein, X is 0~1, M2+、M3+For gold
Belong to ion, An-For interlayer anion.
4. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to claim 2, it is characterised in that: step 1)
In, the oily phase reaction precursor further includes dividing greatly in the metal alkoxide and/or organic polymer reaction for be used to form functional layer
Son.
5. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to claim 4, it is characterised in that: when described
Oily phase reaction precursor when including macromolecular in organic polymerization reaction, the aqueous phase reactions precursor further includes organic polymer
Small molecular is reacted, it is anti-to react small molecular generation addition, condensation, polycondensation with organic polymer for macromolecular in organic polymer reaction
It one of answers or a variety of, generates resin.
6. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to claim 1, it is characterised in that: step 1)
In, Xiang Shuizhong is additionally added surfactant, as water phase.
7. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to claim 6, it is characterised in that: described
Surfactant additive amount accounts for 50% or more of total surfactant additive amount in oily phase, surfactant in the water phase
Additive amount accounts for 50% or less total surfactant additive amount；The total surfactant additive amount is oily mutually overall with water phase
The ratio between product, concentration are 1g/mL~0.001g/mL.
8. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to any one of claims 1-7, special
Sign is: in step 1), the volume ratio that the organic solvent accounts for oily phase is 10%~80%；In step 1) and step 2), institute
The oily phase density stated is 0.6~1.3 times of aqueous phase densities, and oil phase viscosity is 0.7~1.6 times of aqueous viscosity；In step 2), institute
The ratio that the water phase and oil stated mix is 1:3~3:1, after the oil mutually contacts mixing with water phase, aqueous phase reactions precursor
Middle cation positive charge concentration is 0.00001~0.005mol/mL, what cationic positive changes and alkaline organic theory generated
The molar ratio of anion negative electrical charge number is 0.5~0.8.
9. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to any one of claims 1-7, special
Sign is: the organic solvent is 1- heptyl bromide, 1- bromooctane, 1- bromononane, 1- bromo-n-11,1- bromo-tetradecane, chlorine ring
Hexane, 1- bromine hexadecane, 4- methyl -3- ethyl heptane, 4- methylundecane, n-tridecane, n-eicosane, tert-butyl benzene, 1,
One or more kinds of combination in 1- Diphenylheptane；The HLB of the surfactant is 2-7, the surfactant
For didodecyldimethylammbromide bromide and/or lecithin.
10. macroscopic view 3D multistage porous nanometer material one-step method for synthesizing according to any one of claims 1-7, special
Sign is: in step 3), the standing is 12~48h of standing under room temperature condition of normal pressure.
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