Method and device for preparing micro/nano structure material
阅读说明：本技术 一种制备微/纳结构材料的方法及装置 (Method and device for preparing micro/nano structure material ) 是由 李彦 李逸坦 陈昱光 于 2019-08-15 设计创作，主要内容包括：本发明公开了一种制备微/纳结构和材料的方法与微/纳结构及装置,在本方法中,通过选择合适的本体液体和不同的异相溶液,异相溶液与本体液体接触时,通过调控异相溶液与本体液体界面上溶液行为来调控微纳结构的构建过程。这种方法具有良好的普适性,可以广泛应用于各种微/纳结构的构建。本发明工艺简单,不需要复杂的装置,对于微/纳结构的大范围和大规模制备具有应用前景。(The invention discloses a method for preparing a micro/nano structure and a material, the micro/nano structure and a device. The method has good universality and can be widely applied to the construction of various micro/nano structures. The method has simple process, does not need complex devices, and has application prospect for large-scale and large-scale preparation of the micro/nano structure.)
1. A method and a device for preparing a micro/nano structure material are characterized in that the method comprises the following steps:
step 1, selecting bulk liquid, placing the bulk liquid in a cavity/container, and optionally processing the bulk liquid;
step 2, selecting an out-phase solution, wherein a solute (a target material or a precursor thereof) is dispersed in the out-phase solution;
step 3, dropwise adding the heterogeneous solution on the surface of the bulk liquid to form a liquid-liquid system;
and 4, optionally regulating and controlling the liquid-liquid system, and collecting the micro/nano structure and the material with different shapes and structures.
2. The method of claim 1,
in step 1 and step 2, the bulk liquid and the heterogeneous solution are each independently selected from water or an organic solvent, for example from one or more of chlorobenzene, chloroform, o-dichlorobenzene, carbon tetrachloride, nitrobenzene, cyclohexane, alkanes (N-hexane, N-heptane, N-octane, isooctane, etc.), benzene and alkyl-substituted benzene (toluene, o-xylene, m-xylene, p-xylene, etc.), N-octanol, ethanol, ethyl acetate, N-dimethylformamide and N-methylpyrrolidone; and/or
In step 2, the solute (target material or precursor thereof) is selected from one or more of inorganic material, organic small molecule material and organic polymer.
3. The method of claim 1,
in the step 1, optionally carrying out preheating treatment on the bulk liquid, wherein the preheating treatment is carried out for 1 min-5 h at the temperature of 20-100 ℃; and/or
The heterogeneous solution is selected from volatile solvents which are not compatible or have poor compatibility with the bulk liquid; and/or
The concentration of the heterogeneous solution is 0.001-100 mg/mL.
4. The method according to any one of claims 1 to 3, wherein in step 4, the regulating comprises regulating the temperature of the bulk liquid and regulating the volatilization rate of the heterogeneous solution.
5. The method according to claim 4, wherein in step 4, the conditioning comprises a heating/cooling treatment and/or a purging treatment and optionally a pressure reduction treatment.
6. Micro/nano-structures obtained by the method according to one of claims 1 to 5.
7. An apparatus for carrying out the method according to one of claims 1 to 5, characterized in that the apparatus comprises a container (1) and a tank (2) for accommodating the container (1), wherein a bulk liquid (11) and a heterogeneous solution (12) are accommodated in the container (1), wherein the heterogeneous solution is located at the upper surface of the bulk liquid.
8. The apparatus of claim 7,
a heating/refrigerating device (3) is arranged below and/or above the container (1) and is used for respectively heating/refrigerating the upper end and the lower end of the body liquid in the container; and/or
The box body (2) is provided with a gas outlet (22) and a plurality of gas inlets (21).
9. The apparatus according to claim 8, wherein control valves (23) are provided between the gas inlet (21) and the tank (2), respectively, for controlling the rate of gas entry.
10. The device according to claim 9, wherein a solvent vapor generator (24) is arranged at least one of the gas inlets, preferably between the air inlet and the control valve.
Technical Field
The invention relates to solution splitting behavior, in particular to a method and application of splitting of solutions with different types and different components on another interface, and specifically relates to a method and a device for preparing a micro/nano structure by utilizing the solution splitting behavior.
Background
In today's society, the development of energy, electronics and medical fields is on the rise. In the progress of these technologies, the application of various functional micro/nano structures has become inevitable. For example, how to simply and efficiently obtain high-quality micro/nano structures with characteristic sizes and specific shapes in the aspects of energy catalysis and drug delivery in medical treatment is a key problem to be solved in the development of the micro/nano structures. The micro-nano structure with uniform shape structure, clean surface and uniform size has very obvious effect on the further development of the fields.
Currently, methods for obtaining micro/nano structured particles include a Solvothermal method, a Hydrothermal method, a Precipitation method, an evaporative distillation method, a Mechanical pulverization method, and a Chemical vapor deposition method. The solvothermal method and the hydrothermal method are characterized in that under a certain temperature and the autogenous pressure of a solution (organic solvent or water), a plurality of precursors are dissolved in the solvent, so that reactants react in a liquid phase or supercritical state to slowly generate a product. This method often takes several hours or even days, and in the process, surfactants and stabilizers are usually added, which brings many limitations to the further application of the material. The mechanical pulverization method faces the problem that the obtained product is not uniform in size and shape. The chemical vapor deposition method, the evaporation distillation method and the like require a relatively complicated apparatus. It remains a great challenge to obtain micro/nano-structures on a large scale that are cost effective, have clean surfaces, and have specific dimensions.
Therefore, there is a need in the art for a method for mass production of micro/nano structures with clean surfaces, which has a simple process and low environmental dependence.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies by dropping a solution (heterogeneous solution) containing a volatile solvent onto another liquid interface (for example, dropping a solution of chlorobenzene, carbon tetrachloride, n-heptane, chloroform, etc. onto the surface of water), and the heterogeneous solution spontaneously undergoes splitting at the liquid interface, that is, a large droplet is split into a small droplet and the small droplet is further split, and this splitting process is continued until the small droplet has a certain micro/nano size, and the droplets having the certain micro/nano size can be used as a micro container for mass production of micro/nano particles of a specific size, thereby completing the present invention.
One aspect of the present invention is to provide a method for preparing micro/nano structures and materials, embodied in the following aspects:
(1) a method of making micro/nano structures and materials, wherein the method comprises the steps of:
step 2, selecting an out-phase solution, wherein a solute (a target material or a precursor thereof) is dispersed in the out-phase solution;
and 4, optionally regulating and controlling the liquid-liquid system, and collecting the micro/nano structure and the material with different shapes and structures.
(2) The method according to the above (1), wherein in
In step 2, the solute is selected from inorganic materials (e.g., C)60、C70、CdSO4、Cd(NO3)2、Cd(CH3CO2)2、ZnSO4、Zn(CH3COO)2Pb(NO3)2、Pb(CH3COO)2Etc.), organicOne or more of small molecule materials (phthalocyanine, rhodamine B, tetramethyl P-phenylenediamine, pyrene, P3HT, PCBM, thioacetamide and the like) and high molecule materials (such as polystyrene, polylactic acid, polyacetylene, polyvinyl chloride and the like).
(3) The method according to the above (1), wherein,
in the
The heterogeneous solution is selected from volatile solvents which are not compatible or have poor compatibility with the bulk liquid; and/or
The concentration of the heterogeneous solution is 0.001-100 mg/mL.
(4) The method according to the above (1), wherein, in the step 4, the regulating comprises regulating the temperature of the bulk liquid and regulating the volatilization rate of the heterogeneous solution.
(5) The method according to the above (4), wherein, in the step 4, the regulation comprises a heating/cooling treatment and/or a purging treatment and optionally a vacuum treatment.
(6) In a second aspect, the present invention provides micro/nano-structures and materials obtained by the method of the first aspect of the invention.
In a third aspect, the present invention provides an apparatus for implementing the method of the first aspect, which is embodied in the following aspects:
(7) an apparatus for carrying out the method of the first aspect of the invention, wherein the apparatus comprises a
(8) The apparatus according to the above (7), wherein,
a heating/refrigerating
The case 2 is provided with a gas outlet 22 and a plurality of gas inlets 21.
(9) The apparatus according to the above (8), wherein a control valve 23 is provided between each gas inlet 21 and the casing 2, respectively, for controlling the rate of gas entry.
(10) The apparatus according to the above (9), wherein a solvent vapor generator 24 is provided at least one of the gas inlets, preferably between the air inlet and the control valve.
Drawings
FIGS. 1-1 and 1-2 show schematic diagrams of liquid-liquid systems according to the present invention;
FIG. 2 shows several modes of bulk liquid interface solution behavior in a liquid-liquid system according to the present invention;
FIG. 3 shows the flow behavior of a solution in a liquid-liquid system according to the invention;
FIG. 4 shows the flow behaviour of a solution in an extended system according to the invention;
FIG. 5 is a schematic view of a temperature control device for a liquid-liquid system according to the present invention;
FIG. 6 shows a schematic view of the structure of the device according to the invention;
FIG. 7 shows C obtained in examples 1 to 260AFM images of micro/nano structures of polystyrene and polylactic acid.
Reference numerals
1-a container; 11-bulk liquid; 12-a heterogeneous solution; 2-a box body; 21-gas inlet; 22-gas outlet; 23-a control valve; 24-a solvent vapor generator; 3-heating/cooling device.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The invention provides a method for preparing micro/nano structures and materials by using solution behavior, wherein the method comprises the following steps:
According to a preferred embodiment of the present invention, in
In a further preferred embodiment, an inorganic salt or an organic compound is optionally dissolved in the bulk liquid, for example, an inorganic salt (such as cobalt nitrate, sodium chloride, lanthanum chloride, etc.) is dissolved in water, an organic small molecule material (phthalocyanine, rhodamine B, polyacetylene, tetramethyl-P-phenylenediamine, pyrene, P3HT, PCBM, thioacetamide, etc.) or an organic high molecule compound (such as polystyrene, polyvinyl chloride, polylactic acid, etc.) is dissolved in an organic solvent.
According to a preferred embodiment of the invention, in
Wherein the treatment is mainly used for increasing the temperature of a liquid-liquid system so as to improve the solution behavior of a liquid-liquid interface.
In a further preferred embodiment, the preheating treatment is performed at 20 to 100 ℃ for 1min to 5 h.
In a further preferred embodiment, the pre-heating treatment is carried out at 25 to 40 ℃ for 5min to 1h, for example 15 to 45 min.
And 2, selecting a heterogeneous solution in which a solute is dispersed.
According to a preferred embodiment of the present invention, in step 2, the heterogeneous solution is selected from water or organic solvents, for example from one or more of chlorobenzene, chloroform, o-dichlorobenzene, carbon tetrachloride, nitrobenzene, cyclohexane, alkanes (N-hexane, N-heptane, N-octane, isooctane, etc.), benzene and alkyl-substituted benzenes (toluene, o-xylene, m-xylene, p-xylene, etc.), N-octanol, ethanol, ethyl acetate, N-dimethylformamide and N-methylpyrrolidone; and/or
In a further preferred embodiment, the heterogeneous solution is selected from volatile organic solvents, preferably from one or more of chlorobenzene, chloroform, o-dichlorobenzene, carbon tetrachloride, nitrobenzene, cyclohexane, alkanes (N-hexane, N-heptane, N-octane, isooctane, etc.), benzene and alkyl-substituted benzenes (toluene, o-xylene, m-xylene, p-xylene, etc.), N-octanol, ethanol, ethyl acetate, N-dimethylformamide and N-methylpyrrolidone; and/or
In a further preferred embodiment, the heterogeneous solution of step 2 is selected from volatile solvents that are immiscible or poorly compatible with the bulk liquid of
Thus, the heterogeneous solution retains a liquid-liquid interface after contact with the bulk liquid.
Preferably, when the bulk liquid is water, the heterogeneous solution is preferably selected from chlorobenzene, chloroform, o-dichlorobenzene, carbon tetrachloride, nitrobenzene, cyclohexane, alkanes (n-hexane, n-heptane, n-octane, isooctane, etc.), benzene and alkyl-substituted benzenes (toluene, o-xylene, m-xylene, p-xylene, etc.).
According to a preferred embodiment of the present invention, the solute is selected from one or more of inorganic materials, organic materials and polymers in step 2.
In a further preferred embodiment, in step 2, the solute is an inorganic material (e.g., C)60、C70、CdSO4、Cd(NO3)2、Cd(CH3CO2)2、ZnSO4、Zn(CH3COO)2Pb(NO3)2Or Pb (CH)3COO)2Etc.), organic small molecular materials (phthalocyanine, rhodamine B, tetramethyl P-phenylenediamine, pyrene, P3HT, PCBM, thioacetamide, etc.) and high molecular materials (e.g., polystyrene, polylactic acid, polyacetylene, polyvinyl chloride, etc.).
In the present invention, different solvents may be selected to form products of different morphologies based on the same solute.
According to a preferred embodiment of the present invention, in step 2, the concentration of the heterogeneous solution is 0.001 to 100 mg/mL.
In a further preferred embodiment, in step 2, the concentration of the heterogeneous solution is 0.01 to 5 mg/mL.
In a further preferred embodiment, in step 2, the concentration of the heterogeneous solution is 0.1 to 3mg/mL, such as 0.5 to 2 mg/mL.
And 3, dropwise adding the heterogeneous solution on the surface of the bulk liquid to form a liquid-liquid system.
Wherein the heterogeneous solution floats on the bulk liquid when a small amount of the heterogeneous solution is dropped at the interface of the bulk liquid (as shown in fig. 1-1); when the amount of heterogeneous solution is large, it will settle inside the bulk liquid (as shown in FIGS. 1-2). When the heterogeneous solution is dripped close to the edge of the container and the dripped heterogeneous solution is more, the heterogeneous solution can sink to the bottom of the container and is 'pinned' at the bottom end of the container, so that the heterogeneous solution is fixed at a specific position, and a relatively stable liquid drop splitting process is further obtained. This process is shown in figure 4 as an expanded system.
In the present invention, by using a specific combination of the heterogeneous solution and the bulk liquid having a large difference in solubility, a liquid-liquid interface is constructed when the heterogeneous solution is dropped on the interface of the bulk liquid, and the heterogeneous solution preferably has two modes of bulk splitting and tip splitting (as shown in FIG. 2).
And 4, optionally regulating and controlling a liquid-liquid system to realize the splitting of the heterogeneous solution on another liquid interface (bulk liquid), and collecting the micro/nano structure and material with different appearances and structures.
According to a preferred embodiment of the present invention, in step 4, the regulating comprises regulating the temperature of the bulk liquid and regulating the volatilization rate of the heterogeneous solution.
In a further preferred embodiment, in step 4, the conditioning comprises a heating/cooling treatment and/or a purging treatment and optionally a vacuum treatment.
In the present invention, the behaviour of the heterogeneous solution is controlled by heating/cooling and/or purging and optionally vacuum treatment, thus enabling a large scale build-up of micro/nanostructures based on the splitting behaviour of the heterogeneous solution at the liquid interface. Meanwhile, the product appearance can be changed by regulation and control, and different shapes can be obtainedFeatures of the sheet, e.g. C60Presents different morphologies at different temperatures, such as dumbbell-shaped, annular or flaky single crystal structures and the like.
According to a preferred embodiment of the invention, the heating/cooling treatment is carried out as follows: the heating/cooling treatment is performed above or below the bulk liquid, preferably above the bulk liquid.
The temperature of the system is changed by changing the temperature of the bulk liquid, the volatilization rate and the surface tension of the solution are changed, and the behavior of heterogeneous solution droplets on the interface of the bulk liquid is further regulated and controlled. For the regulation and control of the system temperature and the temperature gradient, the optimized heating/refrigerating direction has universality, and the system can be used for heating/refrigerating below, heating/refrigerating above, heating by a unidirectional heat source/cold source or heating/refrigerating in multiple directions by multiple heat sources/cold sources, so that the temperature of the whole system is improved. Wherein, when heating/refrigerating above the bulk liquid, the heating/refrigerating treatment is realized from top to bottom; when heating/cooling is performed below the bulk liquid, a bottom-up heating/cooling process is achieved.
In a further preferred embodiment, the temperature of the heating/cooling treatment is 20 to 90 ℃, for example 20 to 50 ℃.
Wherein an applied temperature is used to influence the flow inside the solution, i.e. a temperature field is applied to the liquid-liquid system according to the invention. The heat source can be heating/cooling from top to bottom or from bottom to top (as shown in fig. 5), and the heating/cooling process can accelerate/slow volatilization, enhance/reduce disturbance of flow to liquid-liquid system, and promote/inhibit droplet splitting process, which is very important for obtaining micro/nano structure.
Therefore, by applying a temperature field so that the applied temperature affects the internal flow of the solution, the desired micro/nano structure can be obtained by controlling the flow of the entire solution.
According to a preferred embodiment of the present invention, the reduced pressure treatment is performed as follows: the liquid-liquid system is subjected to a pressure reduction treatment so that the degree of vacuum of the liquid-liquid system reaches 0.1 to 1 standard atmospheric pressure.
Wherein the evaporation of the heterogeneous solution is promoted by controlling the vacuum degree, the evaporation takes away heat, the temperature at the top end of the heterogeneous solution is lower than that of the bulk liquid below the heterogeneous solution at the upper layer, a temperature gradient is formed, and Marangoni flow in a liquid-liquid system is shown in figure 3. The flow process in the liquid-liquid system disturbs the droplet behavior, further promoting the splitting behavior of the droplets.
Marangoni flow refers to the flow of a surface of a liquid under the influence of a surface tension gradient when there is a temperature or concentration gradient, due to the temperature or concentration dependence of the surface tension. Also known as marangoni flow, which causes surface liquid to flow from a region of low surface tension to a region of high surface tension. It is called Marangoni Effect (Marangoni Effect) in thermophysics.
According to a preferred embodiment of the present invention, the purge treatment is performed as follows: air and/or solvent vapor is blown into the liquid-liquid system.
Wherein, the air blowing can promote the evaporation of heterogeneous solution, and the evaporation takes away heat, further forms temperature gradient, promotes the split action of liquid drop.
In a further preferred embodiment, the solvent vapor is a vapor containing at least one solvent component of the heterogeneous solution.
Wherein, the method of blowing in solvent vapor is mainly suitable for heterogeneous solution containing two or more volatile solvents, thus, blowing in one solvent vapor can inhibit evaporation of the corresponding solvent in heterogeneous solution without affecting volatilization of other solvents.
In a further preferred embodiment, the purge rate is controlled to be 100 to 1000sccm, preferably 200 to 500 sccm.
Specifically, in the preparation of particles having a micro/nano structure, a composite structure similar to a core-shell structure can be obtained by controlling the solvent vapor blown in step 4. For example, when the heterogeneous solution contains A, B two solvents, wherein A solvent has A solute dissolved therein and B solvent has B solute dissolved therein, if one solvent vapor (e.g., vapor of A solvent) is purged into the liquid-liquid system, volatilization of A solvent in the system can be suppressed without affecting volatilization of B solvent, and precipitation of B solute is formed in the heterogeneous solution, and at this time, precipitated particles are in A solution. At this time, air or other solvent component (preferably air) is blown into the system to promote the volatilization of the B solvent, and further to precipitate the A solute, wherein the precipitation takes the B solute precipitation particles as cores, and the B particles are coated and precipitated to form an A/B compound, which is similar to a core-shell structure. This is also an application where the method of the invention is very clever.
The evaporation rate of the liquid-liquid system is changed integrally by using a blowing and vacuum device, so that the internal fluid behavior of the solution and the overall behavior (splitting and movement) of the solution are changed.
In the present invention, a bulk liquid capable of supporting the upper layer solution (heterogeneous solution) is first selected, and then the upper layer heterogeneous solution is introduced. Different combinations are selected according to the parameters of surface tension, interfacial tension and evaporation latent heat between the bulk liquid and the solvent of the heterogeneous solution. Furthermore, the behavior of the upper-layer heterogeneous solution is regulated, and the behavior of the upper-layer solution is controlled through heating/refrigeration, purging and vacuum treatment, so that the large-scale construction of the micro/nano structure based on the splitting behavior of the heterogeneous solution on a liquid interface is realized, and the liquid drops with certain micro/nano size can be used as a micro-reaction cavity for large-scale preparation of the micro/nano structure with specific size.
In the present invention, step 4 is optional, and if the heterogeneous solution is not regulated, the splitting can be realized on the bulk liquid to form small liquid. But the regulation can promote the division and can realize the acquisition of products with different morphologies.
In a second aspect, the present invention provides a micro/nanoparticle obtained by the method of the first aspect of the present invention.
In a third aspect, the present invention provides an apparatus for carrying out the method of the first aspect of the invention, as shown in fig. 5 to 6, the apparatus comprising a
Wherein, a liquid-liquid system is formed in the container, and then the container is transferred into the box body for regulation and control treatment to promote heterogeneous division.
According to a preferred embodiment of the present invention, the container has at least one cavity capable of holding the bulk liquid, and the bulk liquid is exposed so as to be able to carry the heterogeneous solution.
In a further preferred embodiment, the container may be any one of a culture dish, an evaporation dish, a beaker, a liquid bath, and the like liquid container.
According to a preferred embodiment of the present invention, as shown in fig. 5, a heating/
When the upper heating device is used for heating/refrigerating, the top-down heating/refrigerating is realized, when the lower device is used for heating/refrigerating, the bottom-up heating/refrigerating is realized, and the upper heating device and the lower heating/refrigerating can be simultaneously used.
According to a preferred embodiment of the present invention, as shown in fig. 6, a gas outlet 22 and a plurality of gas inlets 21 are opened in the case 2.
Wherein, the gas inlet 21 is used for introducing air into the box body, and the gas outlet 22 is used for leading out air, solvent vapor and a solvent volatilized by heterogeneous solution
In a further preferred embodiment, a control valve 23 is provided between each gas inlet 21 and the tank 2, respectively, for controlling the rate of gas entry.
In a further preferred embodiment, a solvent vapor generator 24 is provided at least one of the gas inlets, preferably between the air inlet and the control valve.
The solvent vapor generator 24 is configured to generate solvent vapor, and may be a sub-container containing solvent, and performs heating/cooling treatment on the sub-container to generate solvent vapor. The solvent steam generator is connected with the air inlet, and then the solvent steam can be brought into the box body.
In the present invention, the control valve 23 may also be connected to a vacuum-pumping device for performing vacuum treatment on the box body.
The invention has the following beneficial effects:
(1) according to the method, proper bulk liquid, upper-layer solvent and solute are selected, so that the liquid behavior on a liquid-liquid interface can be controlled, and a large-scale micro/nano structure with a specific shape and uniform size is finally obtained;
(2) the device is adopted to carry out the process of constructing the micro/nano structure based on the splitting of the heterogeneous solution on the splitting liquid interface of the heterogeneous solution on the liquid interface, and the solution behavior (namely the splitting behavior based on the heterogeneous solution on the liquid interface) generated in the device can be accurately predicted, adjusted and controlled;
(3) the method has universality and very simple process, and does not need any complicated mechanical device;
(4) the method for preparing the micro/nano structure and the material by using the solution behavior can also be applied to the preparation of the micro/nano structure with a special core-shell structure.
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