CN107265427B - Preparation of morphology-controllable nano particles based on sandwich interface method and preparation method thereof - Google Patents
Preparation of morphology-controllable nano particles based on sandwich interface method and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing morphology-controllable nanoparticles based on a sandwich interface method. The method designs an immiscible three-phase mixture, namely a three-layer liquid phase, which is called a sandwich for short, and comprises an upper-layer reversed-phase microemulsion liquid phase, a middle transition layer liquid phase and a lower-layer aqueous solution liquid phase; carrying out precipitation reaction on the raw materials to prepare nano particles with different controllable appearances and sizes and different chemical properties; comprises noble metal, metal oxide, hydroxide, sulfide, metal organic framework material, biomedicine and other nanometer materials. The invention can prepare novel nano particles with uniform particle size and special structure, such as shell structure, composite nano structure, hollow structure and the like. The process is simple, the operation is convenient, and the pH is not required to be adjusted; and the requirement on equipment is not high; meanwhile, the product yield can be increased by improving the concentration of the initial reactant on the premise of not influencing the appearance of the product, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to a nano material preparation technology, in particular to a sandwich interface method for preparing nano particles with controllable appearance and size and a preparation method thereof, belonging to the field of nano material engineering.
Background
The special properties of nanomaterials, different from bulk materials due to size effects, have attracted considerable attention from researchers in numerous material applications, where the same nanomaterials can be given different applications through the adjustment of nanocrystal structure and morphology. In general, the rational construction of nanocrystal building blocks involves two main processes: firstly, determining possible chemical compositions capable of generating special properties and functional structures thereof, such as shell layer nano structures, composite nano structures and the like; and secondly, the designed nano material is prepared by a nano material preparation method, such as a solid phase reaction method, a mechanochemical ball milling method, a solution precipitation method, a hydrothermal method, a reverse microemulsion method and the like. In the preparation process, various additives, seed crystal nuclei and the like are generally added; or the growth of the nano-crystal is adjusted by a template-assisted method, namely the disordered growth of the nano-crystal is prevented by controlling the reaction environment. The methods for preparing the nano material have various characteristics in the regulation and control of the size and the shape of the nano material, but have certain limitations in the regulation and control of the size and the shape of the nano material. For the solid phase reaction method, the diffusion of ions at a high temperature causes heterogeneous impurities to be generated during the reaction; for the mechanochemical ball milling method and the solution precipitation method, aggregation of the agglomerate size is easily generated; for the nano material prepared by the hydrothermal method, obvious preferential growth of nano crystals is easy to occur, so that the shape of the nano crystals is not favorably regulated; for the reverse microemulsion method, proper reverse microemulsion is difficult to prepare, and the oil phase and the surfactant on the surface of the nano particles are difficult to remove. For the emerging interface method, because two immiscible phase interfaces are formed in the reaction, a gradual transition region from one phase to another phase exists, and the structure, energy, composition and the like of the nano material in the region all present continuous gradient changes. Atoms at the interface are unbalanced due to the interaction force field, and surface energy is generated, so that the atoms have stronger reactivity; and possess many unique properties that differ from the bulk phase. Therefore, the interfacial method for preparing the nanomaterial shows great advantages.
In recent years, in the research of controlling the size and the morphology of the nanocrystal, the interface method can be applied to prepare nanomaterials with special structures, such as shell layer nanostructures, composite nanostructures and the like, because the interface is a non-equilibrium reaction region with high surface energy and can influence the dynamic growth of the nanocrystal as a material transmission channel, and further, the ideal nanocrystal can be obtained through a complex crystallization process. Therefore, by designing the properties of the reactants in the interfacial method, such as the concentration of the precursor, or by changing the properties of the interface, such as changing the polarity of the solvent, adding a surfactant to the solvent, etc., it is advantageous to design and prepare novel nanocrystal structural units, and to precisely control the structure and size of the generated nanoparticles, which is also becoming the focus of the nanometer researchers. Studies indicate that the lower the precursor concentration, the smaller the size of the nanocrystals produced; the lower the polarity of the solvent, the smaller the size of the generated nano crystal and the slight deformation; the longer the chain length of the surfactant is, the stronger the wrapping effect on crystal nuclei is, and the smaller the size of the generated nano crystal is; and vice versa.
For example, the invention patent application with the patent publication number of CN105329938A of Zhongxing Ping et al is named as a method for preparing BaTiO3 nano-particles by an oil-water interface method; dissolving barium chloride, sodium oleate and tetrabutyl titanate in deionized water, and then adding cyclohexane to obtain an oil-soluble precursor; dissolving sodium hydroxide in deionized water to obtain a hydroxide precursor; and mixing the solutions to obtain a precursor solution, then reacting in a reaction kettle, washing, drying and calcining to obtain the barium titanate nano-particles. For example, Ni Yu-like patent publication No. CN104609433A entitled "method for preparing nano beta-calcium silicate hollow spheres by oil-water interface method" is similar to Yu et al, and sodium oleate and calcium chloride are added into a three-neck flask containing deionized water, absolute ethyl alcohol and n-hexane at room temperature, and after heating and refluxing in water bath for a certain time, calcium oleate is prepared by post-treatment; adding the prepared calcium oleate into a three-neck flask containing ethanol and an oil-soluble solvent to fully dissolve the calcium oleate, then adding an aqueous solution of sodium silicate, and heating and refluxing in a water bath for a certain time; and washing the prepared sample with deionized water and ethanol alternately, drying and calcining to obtain the nano beta-calcium silicate hollow sphere. The BaTiO3 nano particles and the nano beta-calcium silicate hollow spheres prepared by the two oil-water interface methods are not easy to regulate and control in the aspects of appearance and size, the diffusion of the nano particles in a liquid phase cannot be accurately regulated and controlled, the preparation process is complex, calcination is needed, and industrial production is not easy to realize.
Disclosure of Invention
The invention aims to provide a method for preparing nano particles with controllable morphology based on a sandwich interface method and a preparation method thereof aiming at the defects and the defects of the existing nano material preparation technology. The method utilizes a sandwich interface precipitation method to prepare the nano-crystals with different chemical properties, namely utilizes the advantage that the interface reaction has high surface energy to realize the regulation and control of the nucleation and the growth of nano-particles at the interface reaction position, thereby realizing the nano-particles with controllable appearance and size; finally, the novel nano material with uniform particle size and special structure, such as shell structure, composite nano structure, hollow structure and the like, is obtained.
The design concept and principle of the invention are as follows: designing immiscible three-phase mixtures, i.e. three liquid phases, herein referred to as sandwiches; the three liquid phases include an upper reversed-phase microemulsion liquid phase, a middle transition layer liquid phase and a lower aqueous solution liquid phase. The preparation process of the nano-particle mainly relates to the instability of the upper-layer reverse microemulsion, the ion diffusion regulated by the intermediate transition layer liquid phase and the precipitation reaction generated at the interface of the intermediate transition layer liquid phase and the lower-layer aqueous solution liquid phase. Before the reaction starts, the reactant in the upper-layer reversed-phase microemulsion phase and the reactant in the lower-layer aqueous solution phase are separated by the intermediate transition layer liquid phase, and the reactants cannot contact with each other, so that the reaction does not occur; when the temperature of the reactant rises to a certain temperature, the stability of the upper-layer reversed-phase microemulsion phase begins to be reduced, and the water core is broken to release the upper-layer reactant; and then the upper layer reactant is gradually diffused to the lower layer aqueous solution under the driving of gravity and concentration gradient, and is contacted with the reactants in the lower layer aqueous solution liquid phase through the intermediate transition layer liquid phase, so that a precipitation reaction is carried out at the interface of the intermediate transition layer liquid phase and the lower layer aqueous solution liquid phase, and finally the nano crystal is formed. Because the reaction space at the interface is limited and the ion supersaturation concentration is low, the growth of the nanocrystal is slow after nucleation, which is beneficial to controlling the size of the nanocrystal; and the time required by the free diffusion of the ions is longer, so that the crystal face is inoculated with sufficient time, and the integrity of the crystal is ensured. Therefore, as long as the reactants can be theoretically dissolved in the upper reversed phase microemulsion phase and the lower aqueous solution phase respectively, the morphology and the size of the prepared nano particles can be regulated and controlled.
Secondly, nanoparticles with different shapes and sizes can be prepared by adjusting the reaction time, the height of the liquid phase of the intermediate transition layer and the type of the surfactant used in the liquid phase of the lower aqueous solution. For the reaction time, the nucleation of diffusion control at the initial stage of the reaction is dominant, and the growth of the crystal grains is limited to a certain extent under the wrapping of the surfactant due to insufficient reactants at the interface; along with the extension of the reaction time, the reactants diffused to the interface are gradually increased, the crystal grains start to grow further under the environment with higher saturation, but when the crystal grains reach a certain size, the increase of the self gravity of the crystal grains causes the unbalance of the stress, the particles leave the interface layer and sink to the lower layer of the container, and the growth process of the nano crystals is also called as a paragraph.
In order to achieve the purpose of the invention, the invention is realized by adopting the technical scheme formed by the following technical measures.
The invention relates to a method for preparing nano particles with controllable morphology based on a sandwich interface method, which is characterized in that according to the method, an immiscible three-phase mixture, namely a three-layer liquid phase, namely a sandwich for short, is designed, the three-layer liquid phase comprises an upper-layer reversed-phase microemulsion liquid phase, a middle transition layer liquid phase and a lower-layer aqueous solution liquid phase, and the three-layer liquid phase and the sandwich are subjected to precipitation reaction to prepare the nano particles with controllable morphology and size, and the method comprises the following:
(1) preparation of upper-layer reversed-phase microemulsion phase
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper layer mixed solution, weighing an upper layer reactant raw material for preparing an upper layer reversed phase microemulsion phase, and dissolving the upper layer reactant raw material into 1mL of aqueous solution; then dropwise adding the mixture into the obtained upper-layer mixed solution by using a micro liquid inlet device, and fully dispersing the mixture by using a magnetic stirrer at room temperature until a clear and transparent upper-layer reversed-phase microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer liquid phase
Weighing lower layer reactant raw materials used for preparing the lower layer aqueous solution liquid phase, or the lower layer reactant raw materials and a surfactant, or the surfactant, and dissolving the lower layer reactant raw materials and the surfactant in 10mL of deionized water to prepare the lower layer aqueous solution liquid phase; the intermediate transition layer liquid phase adopts 2-15ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Slowly adding the lower aqueous solution liquid phase obtained in the step (2), 2-15ml of the middle transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a reaction tube in sequence, and placing the reaction tube in a constant-temperature water bath at 60-80 ℃ for reacting for 5-20 hours after two clear and stable interface layers are formed in the reaction tube respectively to obtain three layers of liquid phases, namely a sandwich mixed system;
(4) obtaining of nanoparticles
And (4) alternately washing the three-layer liquid phase obtained in the step (3) for multiple times by using absolute ethyl alcohol and deionized water through a centrifugal machine until the obtained product solution is clear and transparent, and then drying the clear and transparent product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the nano particles.
In the technical scheme, the upper layer reactant raw material is 0.1181-1.1810g of calcium nitrate; or 0.0366g cadmium chloride, or 0.1190g zinc nitrate, or 0.0605g ferric nitrate, or 0.0640g tetrachloroauric acid, or 0.0865g manganese acetate, or 0.0938g copper nitrate.
In the technical scheme, the lower layer reactant raw material is 0.1140-0.5700g of trisodium phosphate or 3.3200g of terephthalic acid.
In the technical scheme, the lower layer reactant raw materials are also 0.2280g of sodium carbonate and 0.0142g-0.5768g of sodium dodecyl sulfate surfactant, or 0.0480g of sodium sulfide and 0.0200g of polyvinyl pyrrole surfactant, or 0.0800g of sodium hydroxide and 0.0400g of polyvinyl pyrrole surfactant, or 2.3460g of vitamin C and 0.0600g of sodium citrate surfactant, or 0.0050g of ferric nitrate and 0.1141g of ammonium persulfate surfactant.
In the technical scheme, the used lower layer reactant raw materials are 0.1141g of ammonium persulfate surfactant and 0.1442g of sodium dodecyl sulfate surfactant, or 0.2500g of cetyltrimethylammonium bromide surfactant.
In the technical scheme, the reaction temperature of the reaction tube in the step (3) in a constant-temperature water bath is 60 ℃.
In the technical scheme, the reaction time of placing the reaction tube in the constant-temperature water bath in the step (3) is 20 hours.
In the technical scheme, the reaction tube uses a plug colorimetric reaction tube, the diameter of the reaction tube is between 1 and 5cm, and the length of the reaction tube is between 25 and 35 cm.
In the above technical scheme, the magnetic stirrer in the step (1) adopts a multi-head magnetic heating stirrer.
In the above technical scheme, the centrifuge in the step (4) adopts an electric centrifuge, and the use speed of the electric centrifuge is 4000 rpm.
The nano particles prepared by the method for preparing the nano particles with controllable morphology based on the sandwich interface method have hollow spherical particles, the size of the hollow spherical particles is about 50nm, the thickness of a shell layer is 5nm, and the hollow spherical particles have good crystallinity; the nano-particle has rod-shaped nano-particles with the average size of 10nm, good dispersion and good crystallinity; the nano-particles are solid spherical nano-particles with the size of 180-220nm, the surface is uneven, and the nano-particles are fine and have good crystallinity; the size of the spiked spherical particles is 400-500 nm; rod-shaped particles with the length of 500-700nm and good dispersibility; the particle has line shape, diameter of about 30nm, length of 1-2um, and good dispersibility.
In the process of preparing the nano particles by the sandwich interface method, the growth of the nano crystals is limited by the quantity of reactants diffused to the interface, so that the growth of the crystals is inhibited within a certain range by the design of the interface, and the size of the nano particles can be effectively regulated and controlled. For the intermediate transition layer liquid phase, the higher the toluene level used in the intermediate transition layer liquid phase, the longer the diffusion distance of the ions in the upper reversed microemulsion phase, and the slower the diffusion rate, in the same diameter reaction tube, so the smaller the number of ions participating in the reaction near the interface layer. Therefore, the arrangement of the liquid phase of the intermediate transition layer not only can isolate two reactants participating in the reaction of the upper layer and the lower layer, but also can indirectly regulate the progress of the reaction by changing the diffusion rate, which is difficult to realize in other interface methods. For the surfactant, the interaction form with crystal nucleus is changed due to different types of the surfactant, so that the nucleation process of the crystal is influenced; the surfactant can also indirectly control the growth rate of crystal faces through the difference of the specific adsorption capacities of different crystal faces, change the inertial growth rule of crystals and realize the regulation and control of crystal growth, namely the regulation and control of the morphology and size of nanoparticles.
The method utilizes a sandwich interface precipitation method with good dispersibility to prepare nano crystals with different chemical properties, including noble metals, metal oxides, sulfides, metal organic framework Materials (MOFs), biomedicine and other nano particles; further controls the nucleation and growth of the nano-crystal through interface diffusion, and finally expands the range of the nano-material.
The synthesis of the nano particles with controllable morphology and size based on the sandwich interface method has the following advantages and beneficial technical effects:
1. the preparation method has simple process and convenient operation, and does not need to adjust the pH value; the reaction condition is mild, the production period is short, and the requirement on equipment is not high; meanwhile, the product yield can be increased by improving the concentration of the initial reactant on the premise of not influencing the appearance of the product, and the industrial production is easy to realize.
2. The reactants used in the preparation method are respectively solubilized into the upper reversed phase microemulsion phase and the lower aqueous solution phase, and the precipitation reaction can only occur at the interface of the intermediate transition layer liquid phase and the lower aqueous solution phase, so that the size of the nano particles is effectively limited.
3. The preparation method can effectively adjust the morphology of the nano-particles by changing the types of the surfactants in the lower aqueous solution liquid phase.
4. The nano particles prepared by the preparation method can be applied to the fields of electromagnetism, optics, catalytic chemistry, electronic information engineering, biomedicine and the like.
5. The preparation method disclosed by the invention utilizes a sandwich interface precipitation method with good dispersibility to prepare the nanocrystals with different chemical properties, including noble metals, metal oxides, hydroxides, sulfides, metal organic framework Materials (MOFs) and biomedical nanoparticles; further controls the nucleation and growth of the nano-crystal through interface diffusion, and finally expands the range of the nano-material.
Drawings
Fig. 1 is a scanning electron microscope picture of nano hydroxyapatite particles prepared in example 1 of the present invention;
fig. 2 is a scanning electron microscope picture of the nano-hydroxyapatite particles prepared in example 2 of the present invention;
fig. 3 is a scanning electron microscope picture of the nano-hydroxyapatite particles prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope picture of the nano calcium carbonate particles prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope picture of the nano calcium carbonate particles prepared in example 5 of the present invention;
FIG. 6 is a scanning electron microscope picture of the nano calcium carbonate particles prepared in example 6 of the present invention;
FIG. 7 is a scanning electron microscope picture of the nano calcium carbonate particles prepared in example 7 of the present invention;
FIG. 8 is a transmission electron microscope image of the nano cadmium sulfide particles prepared in example 8 of the present invention;
FIG. 9 is a transmission electron microscope image of nano zinc oxide particles prepared in example 9 of the present invention;
FIG. 10 is a scanning electron micrograph of nano-hydrated iron oxide particles prepared in example 10 of the present invention;
FIG. 11 is a TEM image of Au nanoparticles prepared in example 11 of the present invention;
FIG. 12 is a scanning electron micrograph of nano-manganese dioxide particles prepared according to example 12 of the present invention;
FIG. 13 is a scanning electron microscope image of the nano-manganous-manganic oxide particles prepared in example 13 of the present invention;
fig. 14 is a scanning electron microscope image of the nano metal organic framework material particles prepared in example 14 of the present invention.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the detailed description is only for further details of the present invention and should not be construed as limiting the scope of the present invention in any way.
In the following examples of the invention, the apparatus and equipment used included: the reaction tube is a 50mL colorimetric reaction tube with a plug, the analytical balance is manufactured by Shanghai precision science instruments Inc. and is of a model DY200N, the centrifugal machine is an electric centrifugal machine of a model VitTG-6 manufactured by Sichuan Alco instruments Inc., the constant temperature water bath pot is manufactured by Jiangsu Jintani city and is of a model HH-8, the stirrer is a multi-head magnetic heating stirrer of a model HT-6 manufactured by Hezhou national Hua electric appliances Inc., the micro liquid feeder is a micro liquid feeder of a model TS2-60 manufactured by Baoding Lange constant flow pump Inc., the microscope is a scanning electron microscope of a model S-4800 manufactured by Japan electronic company, and the transmission electron microscope of a model Tecnai G2F20S-TWIN manufactured by the U.S.FEI company.
The method is operated according to the process steps of the method for preparing the nano particles with controllable morphology based on the sandwich interface method:
in the case of the example 1, the following examples are given,
(1) preparation of calcium nitrate upper-layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then dissolving 0.1181g of raw material calcium nitrate for preparing the upper-layer reverse microemulsion into 1mL of aqueous solution by balance, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer reverse microemulsion phase of the calcium nitrate is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer liquid phase
0.1140g of trisodium phosphate used as a raw material for preparing the lower-layer aqueous solution liquid phase is weighed by a balance and dissolved in 10mL of deionized water to obtain the lower-layer aqueous solution liquid phase; the intermediate transition layer liquid phase uses 15ml toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug in sequence, and placing the reaction tube into a constant-temperature water bath at 60 ℃ for reacting for 20 hours after two clear and stable interface layers are formed in the reaction tube respectively to obtain a three-phase mixture which is immiscible, namely a three-layer liquid phase, namely a sandwich for short;
(4) obtaining of nano hydroxyapatite particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the white nano hydroxyapatite particles.
Example 2
(1) Preparation of calcium nitrate upper-layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.5905g of raw material calcium nitrate for preparing the upper-layer reverse microemulsion by using a balance to dissolve the raw material calcium nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer reverse microemulsion phase of the calcium nitrate is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
0.5700g of trisodium phosphate used as a raw material for preparing the lower-layer aqueous solution liquid phase is weighed by a balance and dissolved in 10mL of deionized water to obtain the lower-layer aqueous solution liquid phase; the intermediate transition layer liquid phase is 10ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug in sequence, and placing the reaction tube into a 70 ℃ constant-temperature water bath for reaction for 10 hours after two clear and stable interface layers are formed in the reaction tube respectively to obtain a three-phase mixture which is immiscible, namely a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano hydroxyapatite particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the white nano hydroxyapatite particles.
Example 3
(1) Preparation of calcium nitrate upper-layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.2362g of calcium nitrate used as a raw material for preparing the upper-layer reverse microemulsion by using a balance to dissolve the calcium nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by adopting a multi-head magnetic heating stirrer until a clear and transparent upper-layer reverse microemulsion phase of the calcium nitrate is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
0.2280g of trisodium phosphate used as a lower-layer reactant for preparing the lower-layer aqueous solution liquid phase is weighed by a balance and dissolved in 10mL of deionized water to obtain the lower-layer aqueous solution liquid phase; 2ml of toluene intermediate transition layer liquid phase is used for the intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 80 ℃ for reacting for 5 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano hydroxyapatite particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product solution in a drying box at the temperature of 60 ℃ for 10 hours to obtain the white nano-hydroxyapatite particles.
Example 4
(1) Preparation of calcium nitrate upper-layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 1.1810g of raw material calcium nitrate for preparing the upper-layer reverse microemulsion by using a balance to dissolve the raw material calcium nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer reverse microemulsion phase of the calcium nitrate is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
0.2280g of raw material sodium carbonate and 0.0142g of surfactant sodium dodecyl sulfate which are used for preparing the lower aqueous solution liquid phase are dissolved in 10mL of deionized water to obtain the lower aqueous solution liquid phase; the intermediate transition layer liquid phase uses 15ml toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 60 ℃ for reacting for 20 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano calcium carbonate particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product solution in a drying box at the temperature of 60 ℃ for 10 hours to obtain the white nano calcium carbonate particles.
Example 5
(1) Preparation of calcium nitrate upper-layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 1.1810g of calcium nitrate used for preparing the upper-layer reverse microemulsion by using a balance to dissolve the calcium nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer reverse microemulsion phase of the calcium nitrate is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
0.2280g of sodium carbonate used for preparing the lower aqueous solution phase and 0.1442g of sodium dodecyl sulfate serving as a surfactant are weighed by balance and dissolved in 10mL of deionized water to obtain a lower aqueous solution phase; the intermediate transition layer liquid phase is 10ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 70 ℃ for reaction for 10 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano calcium carbonate particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product solution in a drying box at the temperature of 60 ℃ for 10 hours to obtain the white nano calcium carbonate particles.
Example 6
(1) Preparation of calcium nitrate upper-layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 1.1810g of calcium nitrate used for preparing the upper-layer reverse microemulsion by using a balance to dissolve the calcium nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer reverse microemulsion phase of the calcium nitrate is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
0.2280g of sodium carbonate used for preparing the lower-layer aqueous solution liquid phase and 0.2884g of surfactant lauryl sodium sulfate are weighed by a balance and dissolved in 10mL of deionized water to obtain the lower-layer aqueous solution liquid phase; the intermediate transition layer liquid phase uses 5ml toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 80 ℃ for reacting for 5 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano calcium carbonate particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the white nano calcium carbonate particles.
Example 7
(1) Preparation of calcium nitrate upper-layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 1.1810g of calcium nitrate used for preparing the upper-layer reverse microemulsion by using a balance to dissolve the calcium nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer reverse microemulsion phase of the calcium nitrate is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
0.2280g of sodium carbonate and 0.5768g of sodium dodecyl sulfate used for preparing the lower aqueous solution liquid phase are dissolved in 10mL of deionized water to obtain the lower aqueous solution liquid phase; the intermediate transition layer liquid phase is 10ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 60 ℃ for reacting for 20 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano calcium carbonate particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the white nano calcium carbonate particles.
Example 8
(1) Preparation of cadmium chloride upper layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.0366g of cadmium chloride used for preparing the upper-layer reversed-phase microemulsion by using a balance to dissolve the cadmium chloride into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer cadmium chloride reversed-phase microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
Dissolving 0.0480g of sodium sulfide and 0.0200g of surfactant polyvinylpyrrolidone in 10mL of deionized water by using a balance to prepare a lower aqueous solution liquid phase to obtain a lower aqueous solution liquid phase; the intermediate transition layer liquid phase is 10ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 60 ℃ for reacting for 20 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano cadmium sulfide particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the nano cadmium sulfide particles.
Example 9
(1) Preparation of zinc nitrate upper layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.1190g of zinc nitrate used for preparing the upper-layer reverse microemulsion by balance to dissolve the zinc nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer zinc nitrate reverse microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
Dissolving 0.0800g of sodium hydroxide and 0.0400g of surfactant polyvinylpyrrolidone in 10mL of deionized water by balance to obtain a lower aqueous solution phase; the intermediate transition layer liquid phase uses 15ml toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 60 ℃ for reacting for 20 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano zinc oxide particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the nano zinc oxide particles.
Example 10
(1) Preparation of ferric nitrate upper layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.0605g of ferric nitrate used for preparing the upper-layer reversed-phase microemulsion by using a balance to dissolve the ferric nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the ferric nitrate by adopting a multi-head magnetic heating stirrer at room temperature until a clear and transparent upper-layer ferric nitrate reversed-phase microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
Dissolving 0.2500g of lower-layer surfactant cetyl trimethylammonium bromide used for preparing the lower-layer aqueous solution liquid phase in 10mL of deionized water to obtain a lower-layer aqueous solution liquid phase; the intermediate transition layer liquid phase is 10ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 70 ℃ for reaction for 10 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano hydrated iron oxide particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the nano hydrated iron oxide particles.
Example 11
(1) Preparation of tetrachloroauric acid upper layer reverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then dissolving tetrachloroauric acid used for preparing the upper-layer reversed-phase microemulsion into 1mL of aqueous solution by using a balance, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer tetrachloroauric acid reversed-phase microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
2.3460g of lower layer reactant vitamin C and 0.0600g of surfactant sodium citrate used for preparing the lower layer aqueous solution liquid phase are dissolved in 10mL of deionized water to obtain the lower layer aqueous solution liquid phase; the intermediate transition layer liquid phase uses 5ml toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 80 ℃ for reacting for 5 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano gold particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product solution in a drying box at the temperature of 60 ℃ for 10 hours to obtain the nano gold particles.
Example 12
(1) Preparation of manganese acetate upper-layer inverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.0865g of manganese acetate used for preparing the upper-layer reverse microemulsion by using a balance to dissolve the manganese acetate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer manganese acetate reverse microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
Dissolving 0.0050g of lower-layer reactant ferric nitrate and 0.1141g of surfactant ammonium persulfate used for preparing the lower-layer aqueous solution liquid phase in 10mL of deionized water to obtain a lower-layer aqueous solution liquid phase; the intermediate transition layer liquid phase uses 15ml toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 60 ℃ for reacting for 20 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano manganese dioxide particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product solution in a drying box at the temperature of 60 ℃ for 10 hours to obtain the nano manganese dioxide particles.
Example 13
(1) Preparation of manganese acetate upper-layer inverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.0865g of manganese acetate used for preparing the upper-layer reverse microemulsion by using a balance to dissolve the manganese acetate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by using a multi-head magnetic heating stirrer until a clear and transparent upper-layer manganese acetate reverse microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
0.1141g of lower-layer surfactant ammonium persulfate and 0.1442g of surfactant sodium dodecyl sulfate used for preparing the lower-layer aqueous solution liquid phase are dissolved in 10mL of deionized water to obtain a lower-layer aqueous solution liquid phase; the intermediate transition layer liquid phase is 10ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 70 ℃ for reaction for 10 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) obtaining nano mangano manganic oxide particles
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product solution in a drying box at the temperature of 60 ℃ for 10 hours to obtain the nano mangano-manganic oxide particles.
Example 14
(1) Preparation of copper nitrate upper layer inverse microemulsion
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper-layer mixed solution, then weighing 0.0938g of copper nitrate used for preparing the upper-layer inverse microemulsion by balance to dissolve the copper nitrate into 1mL of aqueous solution, then dropwise adding the aqueous solution into the upper-layer mixed solution by using a trace liquid feeder, and fully dispersing the aqueous solution at room temperature by adopting a multi-head magnetic heating stirrer until a clear and transparent upper-layer copper nitrate inverse microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer
3.3200g of lower-layer reactant terephthalic acid for preparing the lower-layer aqueous solution liquid phase is dissolved in 10mL of deionized water to obtain the lower-layer aqueous solution liquid phase; the intermediate transition layer liquid phase uses 5ml toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Sequentially and slowly adding the lower aqueous solution liquid phase obtained in the step (2), the toluene intermediate transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a 50mL colorimetric reaction tube with a plug, and placing the reaction tube into a constant-temperature water bath at 80 ℃ for reacting for 5 hours after two clear and stable interface layers are respectively formed in the reaction tube to obtain a three-layer liquid phase, namely a sandwich for short;
(4) metal organic framework nanoparticle obtainment
And (4) alternately centrifuging and washing the three-layer liquid phase obtained in the step (3) for 3 times by using absolute ethyl alcohol and deionized water through a centrifugal machine at the rotating speed of 4000 rpm until the obtained product solution is clear and transparent, and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the metal organic framework nano particles.
The nano-hydroxyapatite prepared by the embodiment of the invention is needle-shaped, has the length of about 100nm and is well dispersed; the prepared calcium carbonate particles have regular shapes, the average size is about 500nm, the crystallinity is good, and the calcium carbonate particles are pure calcite crystals. Other nanoparticles have better crystallinity and can realize controllability of morphology and size. The method can realize the regulation and control of the size and the shape of the nanocrystal by adjusting the reaction time, the height of the transition layer and the type of the surfactant, and the product prepared by the method has high yield and high purity; the preparation method is simple, good in repeatability and low in cost. The nano cadmium sulfide synthesized by the method is hollow spherical, the size is about 50nm, the shell thickness is 5nm, and the nano cadmium sulfide has good crystallinity. The nano zinc oxide prepared by the invention is rod-shaped, the average size is 10nm, the dispersion is good, and the crystallinity is good. The gold nanoparticles prepared by the method are solid spherical, have the size of 180-220nm, are uneven in surface, have fine nanoparticles and are good in crystallinity. The manganese dioxide nano-particles prepared by the method are acanthosphere-shaped particles, the size is 400-500nm, and the dispersity is good. The manganous-manganic oxide nano-particles prepared by the method are acanthosphere-shaped particles, the average size is 250nm, and the dispersibility is good. The hydrated ferric oxide prepared by the invention is rod-shaped particles, the length is 500-700nm, and the dispersibility is good. The metal organic framework material prepared by the invention is linear particles, the diameter is about 30nm, the length is 1-2um, and the dispersibility is good.
Claims (4)
1. A method for preparing nano particles with controllable morphology based on a sandwich interface method is characterized in that an immiscible three-phase mixture, namely a three-layer liquid phase, namely a sandwich for short, is designed, the three-layer liquid phase comprises an upper-layer reversed-phase microemulsion liquid phase, a middle transition layer liquid phase and a lower-layer aqueous solution liquid phase, and the three-layer liquid phase and the middle transition layer liquid phase and the lower-layer aqueous solution liquid phase are subjected to precipitation reaction to prepare the nano particles with controllable morphology and size, and the:
(1) preparation of upper-layer reversed-phase microemulsion phase
Firstly, adding 3mL of emulsifier TX-100 and 1.5mL of n-amyl alcohol into 30mL of cyclohexane to obtain an upper layer mixed solution, weighing an upper layer reactant raw material for preparing an upper layer reversed phase microemulsion phase, and dissolving the upper layer reactant raw material into 1mL of aqueous solution; then dropwise adding the mixture into the obtained upper-layer mixed solution by using a micro liquid inlet device, and fully dispersing the mixture by using a magnetic stirrer at room temperature until a clear and transparent upper-layer reversed-phase microemulsion phase is obtained;
(2) preparation of lower aqueous liquid phase and intermediate transition layer liquid phase
Weighing lower layer reactant raw materials used for preparing the lower layer aqueous solution liquid phase, or the lower layer reactant raw materials and a surfactant, or the surfactant, and dissolving the lower layer reactant raw materials and the surfactant in 10mL of deionized water to prepare the lower layer aqueous solution liquid phase; the intermediate transition layer liquid phase adopts 2-15ml of toluene intermediate transition layer liquid phase;
(3) sandwich interface reaction
Slowly adding the lower aqueous solution liquid phase obtained in the step (2), 2-15ml of the middle transition layer liquid phase and the upper reversed-phase microemulsion liquid phase prepared in the step (1) into a reaction tube in sequence, and placing the reaction tube in a constant-temperature water bath at 60-80 ℃ for reacting for 5-20 hours after two clear and stable interface layers are formed in the reaction tube respectively to obtain three layers of liquid phases, namely a sandwich mixed system;
(4) nanoparticle obtaining
Alternately washing the three-layer liquid phase obtained in the step (3) for multiple times by using absolute ethyl alcohol and deionized water by using a centrifugal machine until the obtained product solution is clear and transparent, and then drying the clear and transparent product in a drying box at the temperature of 60 ℃ for 10 hours to obtain nano particles;
the raw material of the upper layer reactant is 0.1181-1.1810g of calcium nitrate; or 0.0366g cadmium chloride, or 0.1190g zinc nitrate, or 0.0605g ferric nitrate, or 0.0640g tetrachloroauric acid, or 0.0865g manganese acetate, or 0.0938g copper nitrate;
the raw material of the lower layer reactant is 0.1140-0.5700g of trisodium phosphate or 3.3200g of terephthalic acid.
2. The method for preparing morphology-controllable nanoparticles based on the sandwich interface method of claim 1, wherein the lower layer reactants are prepared from 0.2280g of sodium carbonate and 0.0142g to 0.5768g of sodium dodecyl sulfate surfactant, or 0.0480g of sodium sulfide and 0.0200g of polyvinylpyrrolidone surfactant, or 0.0800g of sodium hydroxide and 0.0400g of polyvinylpyrrolidone surfactant, or 2.3460g of vitamin C and 0.0600g of sodium citrate surfactant, or 0.0050g of ferric nitrate and 0.1141g of ammonium persulfate surfactant.
3. The method for preparing nanoparticles with controllable morphology according to claim 1 or 2, characterized in that the raw materials used for the lower layer reactants are 0.1141g ammonium persulfate surfactant and 0.1442g sodium dodecyl sulfate surfactant, or 0.2500g cetyltrimethylammonium bromide surfactant.
4. The method for preparing nanoparticles with controllable morphology according to claim 1, wherein the reaction temperature of the reaction tube in the step (3) in a constant-temperature water bath is 60 ℃; the reaction time was 20 hours.
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| JP2002137910A (en) * | 2000-10-31 | 2002-05-14 | Japan Science & Technology Corp | Hydroxy-apatite nano particle and its manufacturing method |
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| Ordering of Disordered Nanowires：Spontaneous Formation of Highly Aligned，Ultralong Ag Nanowire Films at Oil-Water-Air Interface;Hong-Yan Shi et al.;《advanced functional materials》;20101231;第20卷;全文 * |
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