CN107265427A - Nano-particle of controllable appearance and preparation method thereof is prepared based on sandwich interface method - Google Patents
Nano-particle of controllable appearance and preparation method thereof is prepared based on sandwich interface method Download PDFInfo
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Abstract
The present invention relates to a kind of method that controllable appearance nano-particle is prepared based on sandwich interface method.This method is three-layer-liquid phase, abbreviation sandwich, including upper strata reverse microemulsion liquid phase, intermediate layer liquid phase and lower aqueous solution liquid phase by designing not miscible three-phase mixture；Their precipitation reaction are made to controllable appearance is different with size, nano-particles with different chemical property；Including noble metal, metal oxide, hydroxide, sulfide, the nano material such as metal-organic framework materials and biomedicine.The present invention, which is made, has uniform particle diameter, and structure is special, such as shell structurre, composite nanostructure and hollow-core construction novel nano particle.And technique is simple and convenient to operate, need not adjust pH；And it is high to equipment requirement；Meanwhile, product yield can be increased by improving the concentration of initial reactant on the premise of product pattern is not influenceed, it is easy to accomplish industrialized production.
Description
Technical field
It is to be related to a kind of sandwich interface method to prepare controllable shape specifically the present invention relates to nano material preparation technology
Nano-particle of looks and size and preparation method thereof, belongs to nanoscale materials engineering field.
Background technology
Nano material is due to being different from the special nature of block materials in numerous materials applications caused by dimensional effect
Field causes the extensive concern of researcher, and it is different just can to assign identical nano material by the regulation of nanocrystalline structure and pattern
Application field.Roughly reasonable construction nanocrystalline structure unit relates generally to two processes：Being to determine first to produce
The possibility chemical composition and its functional structure, such as shell layer nano structural and composite nanostructure of raw special nature；Next to that logical
The method for crossing nano material preparation, such as solid reaction process, mechanochemistry ball-milling method, solution deposit, hydro-thermal method, reverse micro emulsion
Method etc. realizes the preparation of designed nano material.In preparation process, generally by adding various additives, seed crystal nuclei
Deng；Or the growth of nanocrystal is adjusted by template auxiliary law, that is, realize by the manipulation of reaction environment to prevent nanometer
The random growth of crystal.The above-mentioned various methods for preparing nano material each tool in the size and Morphological control of nano material is special
Color, but again all in the presence of certain limitation in terms of the size and Morphological control of nano material.It is high for the solid reaction process
The diffusion of ion can make to generate out-phase impurity in course of reaction under temperature state；Precipitated for the mechanochemistry ball-milling method and solution
Method, easily produces agglomerate size and assembles；The nano material prepared for the hydro-thermal method, its nanocrystal easily occurs obvious
Preferential growth and be unfavorable for the regulation and control of nanocrystal pattern；For the reverse microemulsion process, it is more difficult to prepare suitable anti-
Phase microemulsion, and oil phase and the surfactant not easy-clear of nano grain surface.And for emerging interface method, due to
Not miscible two-phase interface is formd in the reaction, therefore there is the progressively transitional region by a phase to another phase, at this
Continuous graded is all presented in the structure of nano material, energy, composition etc. in one region.The atom of interface is in by institute
The interaction field of force being subject to is uneven, and can produce surface can be so as to stronger reactivity；And possess much not
It is same as the peculiar property of body phase.Therefore, the interface method prepares nano material and shows its great advantage.
In recent years, in the research of control nanocrystal size and its pattern, application interface method can prepare special knot
The nano material of structure, such as shell layer nano structural and composite nanostructure, because interface is with the non-flat of high surface energy
Weigh conversion zone, can influence the dynamic growth of nanocrystal as the passage of mass transfer, and then pass through complicated crystallization
Journey obtains preferable nanocrystal.Therefore, by the property of reactant in design interface method, such as precursor concentration, or change
The property at interface, such as changes solvent polarity, adds surfactant in a solvent, is beneficial to design and prepares novelty
Nanocrystalline structure unit, and can accurately control to generate the structure snd size of nano particle, this is increasingly becoming research in nanotechnology
Worker's focus of attention.Research points out that precursor concentration is lower, and the nanocrystal size of generation is smaller；Solvent polarity is lower,
The nanocrystal size of generation is smaller, and has slight deformation；The longer package action to nucleus of chain length of surfactant
Stronger, the nanocrystal size of generation is smaller；Vice versa.
Such as Zhou Xingping patent publication No. is CN105329938A application for a patent for invention, a kind of entitled " oil
The method that water termination method prepares BaTiO3 nano particles "；By barium chloride, enuatrol, butyl titanate dissolving in deionized water,
Then add hexamethylene and obtain oil-soluble presoma；By sodium hydroxide dissolving in deionized water presoma hydroxy；
Solution is mixed into obtain precursor solution, then reacted in a kettle., washs, dry, calcine, obtain barium titanate nano particle.Again
Such as Ni is like the patent of invention that stupid patent publication No. is CN104609433A, and entitled " prepared by a kind of oil-water interfaces method
The method of nanometer β-calcium silicates hollow ball ", at room temperature, enuatrol and calcium chloride is added to and contain deionized water, anhydrous
In ethanol, the three-necked flask of n-hexane, after heating water bath backflow certain time, calcium oleate is made by post processing；Will be obtained
Calcium oleate is added to containing in ethanol, the three-necked flask of oil-dissolving solvent, it is fully dissolved, and is subsequently added the water-soluble of sodium metasilicate
Liquid, heating water bath backflow certain time；Obtained sample is alternately washed with deionized water, ethanol respectively, after drying, calcined
Nanometer β-calcium silicates hollow ball.BaTiO3 nano particles made from both oil-water interfaces methods and nanometer β-calcium silicates hollow ball exist
It is difficult to realize regulation and control in terms of pattern and size, it is impossible to realize the diffusion of nano particle in the liquid phase accuracy controlling, and prepare
Process is more complicated, it is necessary to calcine, and is difficult to realize industrialized production.
The content of the invention
There is provided a kind of base for defect and deficiency of the purpose of the present invention exactly present in existing nano material preparation technology
Nano-particle of controllable appearance and preparation method thereof is prepared in sandwich interface method.This method utilizes sandwich interphase precipitate legal system
The standby nanocrystal with different chemical property, i.e., have the advantage of high surface energy using interfacial reaction, realize that nano particle exists
The regulation and control of nucleation and growth at interfacial reaction, and then realize controllable pattern and the nano-particle of size；Finally obtain its particle diameter
It is homogeneous, with special construction, such as shell structurre, composite nanostructure and hollow-core construction novel nano-material.
The present invention Design Conception and principle be：The not miscible three-phase mixture of design is three-layer-liquid phase, here by three
Layer liquid phase is referred to as sandwich；Three-layer-liquid mutually includes upper strata reverse microemulsion liquid phase, intermediate layer liquid phase and lower aqueous solution liquid phase.
Unstability, the ion of intermediate layer liquid phase regulation of upper strata reverse micro emulsion are related generally to during nano-particle is prepared
Diffusion and the precipitation reaction produced at intermediate layer liquid phase and lower aqueous solution liquid interface.Before starting the reaction, on
The reactant in reactant and lower aqueous solution liquid phase in layer reverse microemulsion liquid phase is separated by intermediate layer liquid phase,
They can not contact with each other, and now reacting will not also occur；After reactant is increased to certain temperature, upper strata reverse microemulsion liquid phase
Stability begin to decline, water karyorrhexis discharges upper strata reactant；Drive of the subsequent upper strata reactant in gravity and concentration gradient
Layer aqueous solution liquid phase spreads gradually downward under making, and is connect by the reactant in intermediate layer liquid phase and lower aqueous solution liquid phase
Touch, precipitation reaction occurs at intermediate layer liquid phase and lower aqueous solution liquid interface, nanocrystal is ultimately formed.Because boundary
Reaction compartment at face is limited and ion supersaturation concentration is relatively low, thus it is slow-growing after nanocrystal nucleation, be conducive to control
The size of nanocrystal；And longer the time required to ion free diffusing, this causes crystal face to breed the time for having abundance, it is ensured that
The integrality of crystallization.As long as therefore reactant can be dissolved in upper strata reverse microemulsion liquid phase and lower aqueous solution liquid respectively in theory
Xiang Zhong, it is possible to the pattern and size of nano-particle prepared by regulation and control.
Secondly, by adjusting the surface used in reaction time, intermediate layer liquid phase height and lower aqueous solution liquid phase
Different-shape and the nano-particle of size can be made in active species.For the reaction time, initial reaction stage diffusion control
Nucleation is occupied an leading position, and crystal grain is under the parcel of surfactant, due to the insufficient reactant in interface, grain growth by
Certain limitation；With the extension in reaction time, the reactant for being diffused into interface gradually increases, and crystal grain is also therewith higher
Start further growth in the environment of saturation degree, but after crystal grain reaches certain size, the increase of its own gravity is led
The imbalance of stress is caused, particle will leave boundary layer and sink to container lower floor, and the growth course of nanocrystal also accuses one section
Fall.
To realize the purpose of the present invention, what the present invention was realized using the technical scheme being made up of following technical measures.
The method of the nano-particle of the present invention that controllable appearance is prepared based on sandwich interface method, it is proposed, according to the invention, set
The not miscible three-phase mixture of meter is three-layer-liquid phase, abbreviation sandwich, including upper strata reverse microemulsion liquid phase, intermediate layer liquid
Mutually with lower aqueous solution liquid phase, they are subjected to precipitation reaction controllable appearances and the nano-particle of size, including following work is made
Skill step：
(1) preparation of upper strata reverse microemulsion liquid phase
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first, upper strata mixed solution is obtained,
The upper strata reactant feed used in preparation upper strata reverse microemulsion liquid phase is weighed, the 1mL aqueous solution is dissolved into；Then with it is micro enter
Liquid device is added dropwise in the mixed solution of gained upper strata, and makes its fully dispersed at room temperature using magnetic stirring apparatus, until
To the upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer liquid phase
Weigh and prepare lower floor's reactant feed used in lower aqueous solution liquid phase, or lower floor's reactant feed and surface-active
Agent, or surfactant are dissolved in 10mL deionized waters and lower aqueous solution liquid phase are made；The intermediate layer liquid phase is used
2-15ml toluene intermediate layer liquid phases；
(3) sandwich interfacial reaction
By lower aqueous solution liquid phase obtained by step (2), the upper strata that 2-15ml intermediate layers liquid phase and step (1) are prepared
Reverse micro emulsion is mutually slowly added into reaction tube successively, is formed respectively in question response pipe after two steady and audible boundary layers,
Reaction tube is placed in 60-80 DEG C of water bath with thermostatic control and reacted 5-20 hours, that is, it is mutually sandwich mixed system that three-layer-liquid, which is made,；
(4) acquisition of nano-particle
Step (3) resulting three-layer liquid phase absolute ethyl alcohol and deionized water are alternately washed multiple using centrifuge, until
Obtained reaction mixture clear, then the product of clear is placed in temperature to be dried in 60 DEG C of drying box, when drying
Between be 10 hours, that is, be made nano-particle.
In above-mentioned technical proposal, upper strata reactant feed used is 0.1181-1.1810g calcium nitrate；Or 0.0366g chlorinations
Cadmium, or 0.1190g zinc nitrates, or 0.0605g ferric nitrates, or 0.0640g tetra chlorauric acids, or 0.0865g manganese acetates, or
0.0938g copper nitrates.
In above-mentioned technical proposal, lower floor's reactant feed used is 0.1140-0.5700g tertiary sodium phosphates, or 3.3200g pairs
Phthalic acid.
In above-mentioned technical proposal, lower floor's reactant feed used is also 0.2280g sodium carbonate and 0.0142g-0.5768g ten
Sodium dialkyl sulfate surfactant, or 0.0480g vulcanized sodium and 0.0200g polyvinyl pyrrole surfactants, or 0.0800g
Sodium hydroxide and 0.0400g polyvinyl pyrrole surfactants, or 2.3460g vitamin Cs and 0.0600g sodium citrates surface are lived
Property agent, or 0.0050g ferric nitrates and 0.1141g ammonium persulfate surfactants.
In above-mentioned technical proposal, lower floor's reactant feed used also for 0.1141g ammonium persulfates surfactant and
0.1442g lauryl sodium sulfate surfactants, or 0.2500g cetyl trimethylammonium surfactants.
In above-mentioned technical proposal, the reaction temperature that reaction tube is placed in water bath with thermostatic control described in step (3) is 60 DEG C.
In above-mentioned technical proposal, the reaction time that reaction tube is placed in water bath with thermostatic control described in step (3) is 20 hours.
In above-mentioned technical proposal, the reaction tube is using tool plug chrominance response pipe, and its diameter is between 1-5cm, and length exists
Between 25-35cm.
In above-mentioned technical proposal, magnetic stirring apparatus described in step (1) uses bull magnetic force heating stirrer.
In above-mentioned technical proposal, centrifuge uses electric centrifuge described in step (4), its using rotating speed be 4000 turns/
Point.
According to receiving prepared by the method for the nano-particle of the present invention that controllable appearance is prepared based on sandwich interface method
Rice corpuscles, there is hollow spherical particles, and its size is in 50nm or so, and shell thickness is 5nm, with good crystallinity；Have bar-shaped
Nano-particle, average-size is 10nm, well dispersed, and crystallinity is good；There is solid spherical nano particle, its size is in 180-
220nm, surface is uneven, has tiny nano particle and crystallinity is good；Spinosity spherical particle, size is 400-500nm；Have
Rod-shpaed particle, length is in 500-700nm, favorable dispersibility；There is linear particle, diameter disperses in 30nm or so, length 1-2um
Property is good.
The present invention nano-particle is prepared by described sandwich interface method during, nanocrystal growth by
The limitation of the reactant quantity of interface is diffused into, therefore the design at interface makes growing up for crystal be pressed down within the specific limits
System, so that the Effective Regulation to nano-particles size can be realized.For intermediate layer liquid phase, in the anti-of identical diameter
Ying Guanzhong, the height of toluene is higher used in intermediate layer liquid phase, and the diffusion length of upper strata reverse microemulsion liquid phase intermediate ion is got over
Long, diffusion rate is slower, so the amount of ions that reaction is comparatively participated near boundary layer is fewer.Therefore, middle transition
The setting of layer liquid phase is not only able to two kinds of reactants that isolation participates in the upper and lower reaction, and can expand indirectly by changing
The process of speed regulation and control reaction is dissipated, this is difficult to realize in other interface methods.For surfactant, surface-active
Agent species is different, will be changed with the interaction type of nucleus, and then influences the nucleation process of crystal；Surfactant
Can also be by the growth rate of the difference indirect control crystal face of different crystal face specific adsorption abilities, changing the used of crystal has life
Long rule, realizes that the regulation and control of nano-particle pattern and size are realized in the regulation and control to crystal growth.
Method of the present invention is prepared with different chemical property using the sandwich interphase precipitate method of good dispersion
Nanocrystal, including noble metal, metal oxide, sulfide, the nanometer such as metal-organic framework materials (MOFs) and biomedicine
Particle；Nucleation and the growth for controlling nanocrystal are further spread by interface, the model of nano material can be prepared by finally expanding
Enclose.
Nano-particle of the present invention based on sandwich interface method synthesis controllable appearance and size has the advantage that and had
The technique effect of benefit is as follows：
1st, preparation method technique of the present invention is simple and convenient to operate, need not adjust pH；Reaction condition is gentle, production
Cycle is short and not high to equipment requirement；Meanwhile, can be by improving initial reactant on the premise of product pattern is not influenceed
Concentration increases product yield, it is easy to accomplish industrialized production.
2nd, solubilising is water-soluble in upper strata reverse microemulsion liquid phase and lower floor respectively for reactant used in preparation method of the present invention
Liquid liquid phase, only could occur precipitation reaction at intermediate layer liquid phase and lower aqueous solution liquid interface, effectively limit
The size of nano particle.
3rd, preparation method of the present invention, can be effective by changing the kinds of surfactants in lower aqueous solution liquid phase
Adjust the pattern of nano particle.
4th, nano-particle prepared by preparation method of the present invention can be applicable to electromagnetism, optics, catalytic chemistry, electronics
In terms of the field such as information engineering and biomedicine.
5th, preparation method of the present invention is prepared using the sandwich interphase precipitate method of good dispersion has different chemistry
The nanocrystal of property, including noble metal, metal oxide, hydroxide, sulfide, metal-organic framework materials (MOFs) and
Biomedical nano-particle；Nucleation and the growth for controlling nanocrystal are further spread by interface, finally expanding to prepare
The scope of nano material.
Brief description of the drawings
Fig. 1 is the scanning electron microscopic picture of nanometer hydroxyapatite particle prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscopic picture of nanometer hydroxyapatite particle prepared by the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscopic picture of nanometer hydroxyapatite particle prepared by the embodiment of the present invention 3；
Fig. 4 is the scanning electron microscopic picture of Nano particles of calcium carbonate prepared by the embodiment of the present invention 4；
Fig. 5 is the scanning electron microscopic picture of Nano particles of calcium carbonate prepared by the embodiment of the present invention 5；
Fig. 6 is the scanning electron microscopic picture of Nano particles of calcium carbonate prepared by the embodiment of the present invention 6；
Fig. 7 is the scanning electron microscopic picture of Nano particles of calcium carbonate prepared by the embodiment of the present invention 7；
Fig. 8 is the transmission electron microscope picture of Nano cadmium sulphide particle prepared by the embodiment of the present invention 8；
Fig. 9 is the transmission electron microscope picture of nano zinc oxide particles prepared by the embodiment of the present invention 9；
Figure 10 is the scanning electron microscopic picture of nano hydrated ferric oxide particle prepared by the embodiment of the present invention 10；
Figure 11 is the transmission electron microscope picture of nano Au particle prepared by the embodiment of the present invention 11；
Figure 12 is the scanning electron microscopic picture of nano-manganese dioxide particle prepared by the embodiment of the present invention 12；
Figure 13 is the scanning electron microscopic picture of nano manganic manganous oxide particle prepared by the embodiment of the present invention 13；
Figure 14 is the scanning electron microscopic picture of nano metal organic framework material particle prepared by the embodiment of the present invention 14.
Embodiment
The present invention is specifically described below by specific embodiment, but the specific descriptions are simply in the present invention
Appearance is described in further detail, and should not be understood as any restriction to the scope of the present invention.
In the following examples of the present invention, instrument and equipment include：Reaction tube is 50mL tool plug chrominance response pipe,
The model DY200N of Shanghai Precision Scientific Apparatus Co., Ltd's production assay balance, centrifuge is that Sichuan another name for Sichuan Province section instrument is limited
The model of company's production ties up TG-6 electric centrifuge, the use of rotating speed is 4000 revs/min, and water bath with thermostatic control is that Community of Jin Tan County city is global
The model HH-8 of scientific instrument factory production thermostat water bath, agitator is the model that Changzhou Guohua Electric Appliance Co., Ltd. produces
For HT-6 bull magnetic force heating stirrer, micro liquid inlet device is the model TS2- that Baoding LanGe constant flow pump Co., Ltd produces
60 micro liquid inlet device, microscope is the SEM for the model S-4800 that NEC company produces, U.S. FEI
The model TecnaiG2F20S-TWIN of company's production transmission electron microscope.
The processing step for being prepared the method for the nano-particle of controllable appearance based on sandwich interface method as described above is entered
Row operation：
Embodiment 1,
(1) preparation of calcium nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The raw material calcium nitrate prepared used in the reverse micro emulsion of upper strata is weighed in the balance to the aqueous solution for taking 0.1181g to be dissolved into 1mL, Ran Houyong
The aqueous solution is added dropwise in the mixed solution of upper strata by micro liquid inlet device, and makes it at room temperature with bull magnetic force heating stirrer
It is fully dispersed, until obtaining the calcium nitrate upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer liquid phase
The raw material tertiary sodium phosphate prepared used in lower aqueous solution liquid phase is weighed in the balance take 0.1140g be dissolved in 10mL go from
Lower aqueous solution liquid phase is produced in sub- water；Intermediate layer liquid phase 15ml toluene intermediate layer liquid phases；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 60 DEG C of waters bath with thermostatic control and reacted 20 hours, that is, obtains not miscible three-phase mixture i.e. three
Layer liquid phase, abbreviation sandwich；
(4) acquisition of nanometer hydroxyapatite particle
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the product is placed in temperature for 60 DEG C
Drying box in dry 10 hours, that is, obtain white nanometer hydroxyapatite particle.
Embodiment 2
(1) preparation of calcium nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The raw material calcium nitrate prepared used in the reverse micro emulsion of upper strata is weighed in the balance to the aqueous solution for taking 0.5905g to be dissolved into 1mL, Ran Houyong
The aqueous solution is added dropwise in the mixed solution of upper strata by micro liquid inlet device, and is made at room temperature using bull magnetic force heating stirrer
Its is fully dispersed, until obtaining the calcium nitrate upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The raw material tertiary sodium phosphate prepared used in lower aqueous solution liquid phase is weighed in the balance take 0.5700g be dissolved in 10mL go from
Lower aqueous solution liquid phase is produced in sub- water；Intermediate layer liquid phase 10ml toluene intermediate layer liquid phases；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 70 DEG C of waters bath with thermostatic control and reacted 10 hours, that is, obtains not miscible three-phase mixture i.e. three
Layer liquid phase, abbreviation sandwich；
(4) nanometer hydroxyapatite particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the product is placed in temperature for 60 DEG C
Drying box in dry 10 hours, that is, obtain white nanometer hydroxyapatite particle.
Embodiment 3
(1) preparation of calcium nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The raw material calcium nitrate prepared used in the reverse micro emulsion of upper strata is weighed in the balance to the aqueous solution for taking 0.2362g to be dissolved into 1mL, Ran Houyong
The aqueous solution is added dropwise in the mixed solution of upper strata by micro liquid inlet device, and is made at room temperature using bull magnetic force heating stirrer
Its is fully dispersed, until obtaining the calcium nitrate upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The lower floor's reactant tertiary sodium phosphate prepared used in lower aqueous solution liquid phase, which is weighed in the balance, takes 0.2280g to be dissolved in
Lower aqueous solution liquid phase is produced in 10mL deionized waters；Intermediate layer liquid phase 2ml toluene intermediate layer liquid phases；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 80 DEG C of waters bath with thermostatic control and reacted 5 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) nanometer hydroxyapatite particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the reaction mixture is placed in into temperature is
Dried 10 hours in 60 DEG C of drying box, that is, obtain white nanometer hydroxyapatite particle.
Embodiment 4
(1) preparation of calcium nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The raw material calcium nitrate prepared used in the reverse micro emulsion of upper strata is weighed in the balance to the aqueous solution for taking 1.1810g to be dissolved into 1mL, Ran Houyong
The aqueous solution is added dropwise in the mixed solution of upper strata by micro liquid inlet device, and is made at room temperature using bull magnetic force heating stirrer
Its is fully dispersed, until obtaining the calcium nitrate upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
Oxide spinel sodium 0.2280g and Surfactant SDS used in lower aqueous solution liquid phase will be prepared
0.0142g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase is with 15ml toluene
Between transition zone liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 60 DEG C of waters bath with thermostatic control and reacted 20 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) Nano particles of calcium carbonate is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the reaction mixture is placed in into temperature is
Dried 10 hours in 60 DEG C of drying box, that is, obtain white Nano particles of calcium carbonate.
Embodiment 5
(1) preparation of calcium nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The calcium nitrate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 1.1810g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the calcium nitrate upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The sodium carbonate prepared used in lower aqueous solution liquid phase is weighed in the balance and takes 0.2280g and surfactant sodium dodecyl base
Sodium sulphate 0.1442g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase 10ml
Toluene intermediate layer liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 70 DEG C of waters bath with thermostatic control and reacted 10 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) Nano particles of calcium carbonate is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the reaction mixture is placed in into temperature is
Dried 10 hours in 60 DEG C of drying box, that is, obtain white Nano particles of calcium carbonate.
Embodiment 6
(1) preparation of calcium nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The calcium nitrate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 1.1810g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the calcium nitrate upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The sodium carbonate prepared used in lower aqueous solution liquid phase is weighed in the balance and takes 0.2280g and surfactant sodium dodecyl base
Sodium sulphate 0.2884g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase 5ml first
Benzene intermediate layer liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 80 DEG C of waters bath with thermostatic control and reacted 5 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) Nano particles of calcium carbonate is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the product is placed in temperature for 60 DEG C
Drying box in dry 10 hours, that is, obtain white Nano particles of calcium carbonate.
Embodiment 7
(1) preparation of calcium nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The calcium nitrate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 1.1810g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the calcium nitrate upper strata reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
Sodium carbonate 0.2280g and Surfactant SDS used in lower aqueous solution liquid phase will be prepared
0.5768g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase is with 10ml toluene
Between transition zone liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 60 DEG C of waters bath with thermostatic control and reacted 20 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) Nano particles of calcium carbonate is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the product is placed in temperature for 60 DEG C
Drying box in dry 10 hours, that is, obtain white Nano particles of calcium carbonate.
Embodiment 8
(1) preparation of caddy upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The caddy prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 0.0366g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the upper strata caddy reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The vulcanized sodium prepared used in lower aqueous solution liquid phase is weighed in the balance and takes 0.0480g and surfactant polyethylene pyrrole
Cough up ketone 0.0200g and be dissolved in 10mL deionized waters and produce lower aqueous solution liquid phase；The intermediate layer liquid phase 10ml first
Benzene intermediate layer liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 60 DEG C of waters bath with thermostatic control and reacted 20 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) Nano cadmium sulphide particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the product is placed in temperature for 60 DEG C
Drying box in dry 10 hours, that is, obtain Nano cadmium sulphide particle.
Embodiment 9
(1) preparation of zinc nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The zinc nitrate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 0.1190g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the upper strata zinc nitrate reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The sodium hydroxide prepared used in lower aqueous solution liquid phase is weighed in the balance and takes 0.0800g and surfactant polyethylene
Pyrrolones 0.0400g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase 15ml
Toluene intermediate layer liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 60 DEG C of waters bath with thermostatic control and reacted 20 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) nano zinc oxide particles are obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the product is placed in temperature for 60 DEG C
Drying box in dry 10 hours, that is, obtain nano zinc oxide particles.
Embodiment 10
(1) preparation of ferric nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The ferric nitrate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 0.0605g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the upper strata ferric nitrate reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The underlying surfaces activating agent cetyl trimethyl ammonium 0.2500g dissolvings used in lower aqueous solution liquid phase will be prepared
Lower aqueous solution liquid phase is produced in 10mL deionized waters；Intermediate layer liquid phase 10ml toluene intermediate layer liquid
Phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 70 DEG C of waters bath with thermostatic control and reacted 10 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) nano hydrated ferric oxide particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the product is placed in temperature for 60 DEG C
Drying box in dry 10 hours, that is, obtain nano hydrated ferric oxide particle.
Embodiment 11
(1) preparation of tetra chlorauric acid upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The tetra chlorauric acid prepared used in the reverse micro emulsion of upper strata is weighed in the balance and takes 0.0640 aqueous solution for being dissolved into 1mL, then with micro-
The aqueous solution is added dropwise in the mixed solution of upper strata by amount liquid inlet device, and makes it at room temperature using bull magnetic force heating stirrer
It is fully dispersed, until obtaining the upper strata tetra chlorauric acid reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
Lower floor reactant vitamin C 2.3460g and surfactant citric acid used in lower aqueous solution liquid phase will be prepared
Sodium 0.0600g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase is with 5ml toluene
Between transition zone liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 80 DEG C of waters bath with thermostatic control and reacted 5 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) nano Au particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the reaction mixture is placed in into temperature is
Dried 10 hours in 60 DEG C of drying box, that is, obtain nano Au particle.
Embodiment 12
(1) preparation of manganese acetate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The manganese acetate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 0.0865g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the upper strata manganese acetate reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
Lower floor reactant ferric nitrate 0.0050g and surfactant ammonium persulfate used in lower aqueous solution liquid phase will be prepared
0.1141g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase is with 15ml toluene
Between transition zone liquid phase；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 60 DEG C of waters bath with thermostatic control and reacted 20 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) nano-manganese dioxide particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the reaction mixture is placed in into temperature is
Dried 10 hours in 60 DEG C of drying box, that is, obtain nano-manganese dioxide particle.
Embodiment 13
(1) preparation of manganese acetate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The manganese acetate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 0.0865g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the upper strata manganese acetate reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
Underlying surfaces activating agent ammonium persulfate 0.1141g and surfactant ten used in lower aqueous solution liquid phase will be prepared
Sodium dialkyl sulfate 0.1442g, which is dissolved in 10mL deionized waters, produces lower aqueous solution liquid phase；The intermediate layer liquid phase
With 10ml toluene intermediate layer liquid phases；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 70 DEG C of waters bath with thermostatic control and reacted 10 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) nano manganic manganous oxide particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then the reaction mixture is placed in into temperature is
Dried 10 hours in 60 DEG C of drying box, that is, obtain nano manganic manganous oxide particle.
Embodiment 14
(1) preparation of copper nitrate upper strata reverse micro emulsion
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first and obtain upper strata mixed solution, then
The copper nitrate prepared used in the reverse micro emulsion of upper strata is weighed to the aqueous solution for taking 0.0938g to be dissolved into 1mL in the balance, then with micro
The aqueous solution is added dropwise in the mixed solution of upper strata by liquid inlet device, and fills it at room temperature using bull magnetic force heating stirrer
It is scattered, until obtaining the upper strata copper nitrate reverse microemulsion liquid phase of clear；
(2) preparation of lower aqueous solution liquid phase and intermediate layer
The lower floor reactant terephthalic acid (TPA) 3.3200g prepared used in lower aqueous solution liquid phase is dissolved in 10mL deionizations
Lower aqueous solution liquid phase is produced in water；Intermediate layer liquid phase 5ml toluene intermediate layer liquid phases；
(3) sandwich interfacial reaction
The upper strata that lower aqueous solution liquid phase, toluene intermediate layer liquid phase and step (1) obtained by step (2) are prepared is anti-
Phase microemulsion is mutually slowly added into 50mL tool plug chrominance response pipes successively, formed respectively in question response pipe two it is steady and audible
After boundary layer, reaction tube is placed in 80 DEG C of waters bath with thermostatic control and reacted 5 hours, that is, obtains three-layer-liquid phase, abbreviation sandwich；
(4) metal organic framework nano-particle is obtained
Step (3) resulting three-layer liquid phase is subjected to alternating centrifugal using centrifuge with absolute ethyl alcohol and deionized water and washs 3
Secondary, centrifuge speed is 4000 revs/min, until obtained reaction mixture clear, then by the product in drying box temperature
Dried 10 hours for 60 DEG C, that is, obtain metal organic framework nano-particle.
The present invention is in needle-like by the nanometer hydroxyapatite prepared by embodiment, is about 100nm, well dispersed；It is made
Standby calcium carbonate granule regular appearance, average-size is in 500nm or so, and crystallinity is good, is pure calcite crystal.It is other
Nano particle is respectively provided with preferable crystallinity and can realize the controllability of pattern and size.When the inventive method is reacted by adjusting
Between, transition layer height and kinds of surfactants can realize the regulation and control to nanocrystal size and pattern, and the inventive method system
Product yields are big, purity is high；Preparation method is simple, reproducible, cost is low.The Nano cadmium sulphide that the present invention is synthesized is sky
Bulbus cordis shape, size is in 50nm or so, and shell thickness is 5nm, with good crystallinity.Nano zine oxide prepared by the present invention into
Bar-shaped, average-size is 10nm, well dispersed, and crystallinity is good.Gold nano grain prepared by the present invention is solid spherical, size
In 180-220nm, surface is uneven, has tiny nano particle and crystallinity is good.Manganese dioxide nano prepared by the present invention
Particle is thorn spherical particle, and size is 400-500nm, favorable dispersibility.Trimanganese tetroxide nano particle prepared by the present invention is
Spherical particle is pierced, average-size is 250nm, favorable dispersibility.Hydrated ferric oxide prepared by the present invention is rod-shpaed particle, and length exists
500-700nm, favorable dispersibility.Metal-organic framework materials prepared by the present invention are linear particle, and diameter is long in 30nm or so
Spend 1-2um, favorable dispersibility.
Claims (9)
1. a kind of method for the nano-particle that controllable appearance is prepared based on sandwich interface method, it is characterised in that design is not miscible
Three-phase mixture be three-layer-liquid phase, abbreviation sandwich, including upper strata reverse microemulsion liquid phase, intermediate layer liquid phase and lower floor's water
They are carried out precipitation reaction and controllable appearance and the nano-particle of size are made, comprised the following steps that by solution liquid phase：
(1) preparation of upper strata reverse microemulsion liquid phase
3mL emulsifying agent TX-100 and 1.5mL n-amyl alcohols are added in 30mL hexamethylenes first, upper strata mixed solution is obtained, weighs
The upper strata reactant feed used in the reverse microemulsion liquid phase of upper strata is prepared, the 1mL aqueous solution is dissolved into；Then micro liquid inlet device is used
It is added dropwise in the mixed solution of gained upper strata, and makes its fully dispersed at room temperature using magnetic stirring apparatus, it is clear until obtaining
Clear bright upper strata reverse microemulsion liquid phase；
(2) preparation of lower aqueous solution liquid phase and intermediate layer liquid phase
Weigh and prepare lower floor's reactant feed used in lower aqueous solution liquid phase, or lower floor's reactant feed and surfactant,
Or surfactant is dissolved in 10mL deionized waters and lower aqueous solution liquid phase is made；The intermediate layer liquid phase uses 2-
15ml toluene intermediate layer liquid phases；
(3) sandwich interfacial reaction
By lower aqueous solution liquid phase obtained by step (2), the upper strata that 2-15ml intermediate layers liquid phase and step (1) are prepared is anti-phase
Microemulsion is mutually slowly added into reaction tube successively, is formed respectively in question response pipe after two steady and audible boundary layers, will be anti-
Should pipe be placed in 60-80 DEG C of water bath with thermostatic control react 5-20 hour, that is, be made three-layer-liquid mutually i.e. sandwich mixed system；
(4) nano-particle is obtained
Step (3) resulting three-layer liquid phase absolute ethyl alcohol and deionized water are alternately washed multiple using centrifuge, until obtaining
Reaction mixture clear, then the product of clear is placed in temperature to be dried in 60 DEG C of drying boxes, drying time is 10
Hour, that is, nano-particle is made.
2. preparing the method for the nano-particle of controllable appearance based on sandwich interface method according to claim 1, its feature exists
Raw materials used in the upper strata reactant is 0.1181-1.1810g calcium nitrate；Or 0.0366g caddies, or 0.1190g nitric acid
Zinc, or 0.0605g ferric nitrates, or 0.0640g tetra chlorauric acids, or 0.0865g manganese acetates, or 0.0938g copper nitrates.
3. preparing the method for the nano-particle of controllable appearance based on sandwich interface method according to claim 1, its feature exists
It is raw materials used for 0.1140-0.5700g tertiary sodium phosphates, or 3.3200g terephthalic acid (TPA)s in lower floor's reactant.
4. the method for the nano-particle of controllable appearance is prepared based on sandwich interface method according to claim 1 or 3, its feature
Be lower floor's reactant it is raw materials used also be 0.2280g sodium carbonate and 0.0142g-0.5768g lauryl sodium sulfate tables
Face activating agent, or 0.0480g vulcanized sodium and 0.0200g polyvinyl pyrrole surfactants, or 0.0800g sodium hydroxides and
0.0400g polyvinyl pyrrole surfactants, or 2.3460g vitamin Cs and 0.0600g sodium citrate surfactants, or
0.0050g ferric nitrates and 0.1141g ammonium persulfate surfactants.
5. the method for the nano-particle of controllable appearance is prepared based on sandwich interface method according to claim 1 or 3, its feature
Be lower floor's reactant it is raw materials used also be 0.1141g ammonium persulfates surfactant and 0.1442g dodecyl sulphates
Natrium surfactant, or 0.2500g cetyl trimethylammonium surfactants.
6. preparing the method for the nano-particle of controllable appearance based on sandwich interface method according to claim 1, its feature exists
The reaction temperature that reaction tube is placed in water bath with thermostatic control described in step (3) is 60 DEG C；Reaction time is 20 hours.
7. preparing the method for the nano-particle of controllable appearance based on sandwich interface method according to claim 1, its feature exists
The reaction tube described in step (3) is using tool plug chrominance response pipe, and its diameter is between 1-5cm, and length is between 25-35cm.
8. preparing the method for the nano-particle of controllable appearance based on sandwich interface method according to claim 1, its feature exists
The magnetic stirring apparatus described in step (1) uses bull magnetic force heating stirrer.
9. preparing the method for the nano-particle of controllable appearance based on sandwich interface method according to claim 1, its feature exists
Centrifuge uses electric centrifuge described in step (4), and it is 4000 revs/min using rotating speed.
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| CN107638878A (en) * | 2017-11-14 | 2018-01-30 | 济南大学 | A kind of preparation method of sandwich structure nano-tube composite catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002137910A (en) * | 2000-10-31 | 2002-05-14 | Japan Science & Technology Corp | Hydroxy-apatite nano particle and its manufacturing method |
| CN103319733A (en) * | 2013-06-13 | 2013-09-25 | 广东药学院 | Method for preparing glycan-negative ion polysaccharide compound nanoparticles from micro-emulsions |
| CN104439277A (en) * | 2014-11-28 | 2015-03-25 | 江南大学 | Preparation method of Au nanometer particles |
-
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- 2017-05-16 CN CN201710344962.2A patent/CN107265427B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002137910A (en) * | 2000-10-31 | 2002-05-14 | Japan Science & Technology Corp | Hydroxy-apatite nano particle and its manufacturing method |
| CN103319733A (en) * | 2013-06-13 | 2013-09-25 | 广东药学院 | Method for preparing glycan-negative ion polysaccharide compound nanoparticles from micro-emulsions |
| CN104439277A (en) * | 2014-11-28 | 2015-03-25 | 江南大学 | Preparation method of Au nanometer particles |
Non-Patent Citations (1)
| Title |
|---|
| HONG-YAN SHI ET AL.: "Ordering of Disordered Nanowires：Spontaneous Formation of Highly Aligned，Ultralong Ag Nanowire Films at Oil-Water-Air Interface", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107638878A (en) * | 2017-11-14 | 2018-01-30 | 济南大学 | A kind of preparation method of sandwich structure nano-tube composite catalyst |
| CN107638878B (en) * | 2017-11-14 | 2020-02-04 | 济南大学 | Preparation method of nanotube composite catalyst with sandwich structure |
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