CN114887493B - Three-dimensional porous material and preparation method thereof - Google Patents

Three-dimensional porous material and preparation method thereof Download PDF

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CN114887493B
CN114887493B CN202210583113.3A CN202210583113A CN114887493B CN 114887493 B CN114887493 B CN 114887493B CN 202210583113 A CN202210583113 A CN 202210583113A CN 114887493 B CN114887493 B CN 114887493B
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photonic crystal
crystal template
porous material
particles
colloid particles
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CN114887493A (en
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刘国金
何文玉
樊莎
向娇娇
禹凡
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Zhejiang Sci Tech University ZSTU
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Zhejiang Sci Tech University ZSTU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/28—Polymers of vinyl aromatic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
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    • Y02A20/131—Reverse-osmosis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The embodiment of the application discloses a three-dimensional porous material and a preparation method thereof. The preparation method comprises the following steps: forming a first photonic crystal template, wherein the first photonic crystal template is formed by self-assembly of first colloid particles; mixing the second colloid particles and the polymer in an organic solvent to form a casting solution, applying the casting solution to the first photonic crystal template, and filling the polymer into the gaps of the first photonic crystal template; self-assembling the second colloid particles to form a second photonic crystal template stacked on the first photonic crystal template; removing the first colloid particles and the second colloid particles to obtain a three-dimensional porous material; wherein the particle size of the first colloid particles is smaller than the particle size of the second colloid particles. The preparation method realizes the accurate regulation and control of the microporous structure of the porous material, and can customize the pore size, the porosity and the film thickness of the porous material. And the multi-layer uniform pore layer can be simply and quickly prepared, the gradient separation of the porous material is realized, and the pollution resistance of the porous material is improved.

Description

Three-dimensional porous material and preparation method thereof
Technical Field
The application relates to the technical field of membrane separation, in particular to a three-dimensional porous material and a preparation method thereof.
Background
The three-dimensional porous material is mainly used as a separation membrane, common porous separation membranes comprise a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, a dialysis membrane, a gas separation membrane and the like, and the three-dimensional porous material is driven by a concentration gradient, a pressure gradient or a temperature gradient and the like to realize substance separation, and is commonly used in the fields of sea water desalination, oil-water separation, wastewater treatment and the like and is a key component in separation engineering.
The microporous structure is a key factor affecting the separation performance and effect of the three-dimensional porous material. The parameters of the microporous structure include the pore size, pore size distribution, porosity and thickness of the membrane, which are closely related to the preparation process. The existing method for preparing the three-dimensional porous material mainly comprises a stretching method and a phase inversion method. The stretching method can adjust the pore size, the porosity and the pore distribution of the membrane by changing the stretching rate, the stretching multiplying power and the stretching temperature, but because of certain difference of the internal structure of the polymer, the accurate regulation and control of the microporous structure of the membrane are difficult to realize in the stretching process. The phase inversion method can realize the adjustment of the microporous structure by changing the composition of the homogeneous solution or the rate of phase separation, but as in the stretching method, it is difficult to realize precise regulation.
In view of this, the present invention has been made.
Disclosure of Invention
An object of the present application is to provide a preparation method of a three-dimensional porous material, which realizes accurate regulation and control of a microporous structure of the porous material, and can customize the pore size, the porosity and the film thickness of the porous material. In addition, the preparation method can simply and rapidly prepare the multilayer uniform pore layer, realize gradient separation of the porous material and improve the pollution resistance of the porous material.
The objects of the present application are not limited to the above objects, and other objects and advantages of the present application not mentioned above can be understood from the following description and more clearly understood through embodiments of the present application. Furthermore, it is readily understood that the objects and advantages of the present application may be achieved by the features disclosed in the claims and combinations thereof.
In one aspect of the present application, the present application provides a method for preparing a three-dimensional porous material, including the steps of:
forming a first photonic crystal template, wherein the first photonic crystal template is formed by self-assembly of first colloid particles;
mixing second colloid particles and a polymer in an organic solvent to form a casting solution, applying the casting solution to the first photonic crystal template, and filling the polymer into gaps of the first photonic crystal template;
self-assembling the second colloidal particles to form a second photonic crystal template layered on the first photonic crystal template;
removing the first colloid particles and the second colloid particles to obtain the three-dimensional porous material;
wherein the particle size of the first colloidal particles is smaller than the particle size of the second colloidal particles.
Preferably, in some of these embodiments, the polymer is filled into the void of the first photonic crystal template by vacuum negative pressure;
optionally, the vacuum negative pressure is 0.03-0.06 MPa.
Preferably, in some embodiments thereof, the first and second colloidal particles are removed by acid or alkali etching;
optionally, removing the first colloidal particles and the second colloidal particles with a highly corrosive solution;
optionally, the highly corrosive solution is an HF solution;
optionally, the mass concentration of the HF solution is 2-4%.
Preferably, in some embodiments, before applying the casting solution to the first photonic crystal template, the method further includes:
and calcining the first photonic crystal template, wherein the calcining temperature is 500-800 ℃ and the calcining time is 1-5 h.
Preferably, in some embodiments thereof, the first colloidal particle and the second colloidal particle are each independently selected from at least one of a silica microsphere, a zirconium dioxide microsphere, a calcium carbonate microsphere, a zinc sulfide microsphere, and a cadmium sulfide microsphere;
optionally, the first colloid particles and the second colloid particles are silicon dioxide microspheres, the particle size of the silicon dioxide microspheres is 220-320 nm, and the monodispersity index is not more than 0.08.
Preferably, in some embodiments, the mass concentration of the first colloidal particles is 0.1 to 5%, preferably 0.5 to 3%, more preferably 1%, which is dispersed in a dispersant selected from at least one of water, ethanol, absolute ethanol, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, in some embodiments thereof, the polymer is selected from at least one of polyvinylidene fluoride, polystyrene, polyacrylonitrile, polyethersulfone, polysulfone, polyvinylidene chloride, polyvinylidene fluoride-hexafluoropropylene, polyurethane, polystyrene-polyisoprene-polystyrene block copolymer, styrene-butadiene-styrene block copolymer, and poly (styrene-methyl methacrylate);
optionally, the mass concentration of the polymer in the casting solution is 7-15%;
optionally, the mass ratio of the polymer to the second colloid particles in the casting film liquid is 1 (1.5-2.5).
In another aspect of the present application, the present application provides a method for preparing a three-dimensional porous material, including the steps of:
1) Adopting a dispersion liquid of first colloid particles to form a first photonic crystal template through self-assembly and solidification;
2) Calcining the first photonic crystal template, wherein the calcining temperature is 500-800 ℃ and the calcining time is 1-5 h;
3) Mixing second colloid particles and a polymer in an organic solvent to form a casting solution, applying the casting solution to the first photonic crystal template, standing for 2-5 h, and filling the polymer into the gaps of the first photonic crystal template in a vacuum oven by adopting vacuum negative pressure of 0.03-0.06 MPa;
4) Evaporating to remove the organic solvent, so that the second colloid particles self-assemble to form a second photonic crystal template laminated on the first photonic crystal template;
5) Soaking the product obtained in the step 4) in an HF solution with the mass concentration of 2-4% for 8-12 h, removing the first colloid particles and the second colloid particles, and then cleaning and drying to obtain the three-dimensional porous material.
In yet another aspect of the present application, a three-dimensional porous material is provided, which is prepared by the preparation method as described above.
The technical scheme provided by the embodiment of the application can comprise the following beneficial effects:
according to the method, the pore size distribution, the pore size and the porosity of the porous material can be controlled by adjusting and controlling the particle size and the proportion of the colloid particles, so that the accurate adjustment and control of the microporous structure of the porous material are realized, and the pore size, the porosity and the film thickness of the porous material can be customized.
The porous material prepared by the method has the advantages of uniform pore size, high pore monodispersity, ordered pore distribution and the like, so that the flux of the porous material is increased, and the separation efficiency is improved. And the colloid particles are self-assembled, and gaps among the particles are smaller, so that the porous material has higher porosity.
The method provided by the application can simply and rapidly prepare the multilayer uniform pore layer, realize gradient separation of the porous material and improve the pollution resistance of the porous material.
The preparation method is simple and convenient, does not use expensive and complex instruments, and is easy to implement.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the following drawings, in which:
FIG. 1 is a flow chart of a method of preparing a three-dimensional porous material according to an embodiment of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a three-dimensional porous material according to an embodiment of the present application;
FIG. 3 is a schematic structural view of a three-dimensional porous material according to an embodiment of the present application;
FIG. 4 is a scanning electron microscope image of a three-dimensional porous material of example 1 of the present application;
fig. 5 is a graph showing the effect of the three-dimensional porous material of example 1 of the present application on filtering paint wastewater.
Detailed Description
The present application is described in further detail below with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
It should be noted that endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and that such range or value should be understood to include values approaching such range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Referring to fig. 1 and 2, a method for preparing a three-dimensional porous material according to the present application is shown, which includes the following steps:
s101: and forming a first photonic crystal template, wherein the first photonic crystal template is formed by self-assembly of first colloid particles.
In the step, the first colloidal particles are dispersed in the dispersion liquid to form a first colloidal particle dispersion liquid, the first colloidal particle dispersion liquid is applied to a substrate, and the first photonic crystal template with ordered arrangement of the colloidal particles and in an opal structure is obtained through self-assembly and solidification.
Among them, the dispersion is not particularly limited, but is preferably at least one of water, ethanol, absolute ethanol, N-dimethylformamide and N, N-dimethylacetamide.
The assembly method includes, but is not limited to, a vertical deposition method, a dip-pull method, a dual-substrate self-assembly method, a heated horizontal self-assembly method, a spin-coating method, a vapor deposition method, or an electrodeposition method.
Curing methods include, but are not limited to, baking and uv curing.
S102: mixing second colloid particles and a polymer in an organic solvent to form a casting solution, applying the casting solution to the first photonic crystal template, and filling the polymer into the gaps of the first photonic crystal template.
In this step, the polymer is infiltrated from the upper surface of the first photonic crystal template and filled into the gaps between the first colloidal particles, and is fixed in the first photonic crystal template by curing or initiating polymerization. Wherein the filling can be by centrifugation, electrochemical deposition, filtration, etc.
S103: self-assembling the second colloidal particles to form a second photonic crystal template layered on the first photonic crystal template;
in this step, the second colloidal particles may be induced to self-assemble by, for example, evaporation, to form a second photonic crystal template in an opal structure laminated on the first photonic crystal template, thereby obtaining a porous material having a double film layer.
S104: removing the first colloid particles and the second colloid particles to obtain the three-dimensional porous material;
wherein the particle size of the first colloidal particles is smaller than the particle size of the second colloidal particles.
In this step, the porous material having a three-dimensional ordered pore structure, which is periodically arranged over a large area, is obtained after the first colloidal particles and the second colloidal particles are removed. Wherein, since the particle diameters of the first colloid particles and the second colloid particles are different from each other, the three-dimensional porous material has a double membrane layer with a gradient distribution of pore diameters, and the separation efficiency and the stain resistance of the three-dimensional porous material are thereby improved.
It can be seen that the preparation method not only realizes the accurate regulation and control of the microporous structure of the porous material, but also realizes the simple and rapid preparation of the separation membrane with the multilayer uniform pore layers. The method realizes the preparation of the first photonic crystal template and the second photonic crystal template through one-time filling, and has the advantages of simple process, high bonding compactness between each film layer, high uniformity degree of porous materials and the like compared with the traditional preparation of the first photonic crystal template and the second photonic crystal template step by step and then lamination.
It will be appreciated that a third photonic crystal template, a fourth photonic crystal template, etc. may be prepared in layers by reference to the above-described methods of the present application, to obtain a separation membrane having two or more uniform pore layers.
Further, in some embodiments of the present application, the polymer is filled into the void of the first photonic crystal template by vacuum negative pressure; optionally, the vacuum negative pressure is 0.03-0.06 MPa.
In this embodiment, the polymer is driven to fill the pores of the first photonic crystal template by the vacuum negative pressure acting force, so that the filling efficiency is obviously improved compared with the conventional centrifugal method and the like, and the stability of the first photonic crystal template is not affected. The vacuum negative pressure is too small, the filling rate of the polymer into the first photonic crystal template is too slow, the filling is incomplete, and the vacuum negative pressure is too large, so that the structure of the first photonic crystal template can be influenced.
Further, in some embodiments of the present application, the first and second colloidal particles are removed by an acid or alkali etching process;
optionally, removing the first colloidal particles and the second colloidal particles with a highly corrosive solution;
optionally, the highly corrosive solution is an HF solution;
optionally, the mass concentration of the HF solution is 2-4%.
The HF solution has extremely strong corrosiveness and can etch and remove the first colloid particles and the second colloid particles.
Further, in some embodiments of the present application, before applying the casting solution to the first photonic crystal template, the method further includes:
and calcining the first photonic crystal template, wherein the calcining temperature is 500-800 ℃ and the calcining time is 1-5 h.
The structural stability of the first photonic crystal template can be improved through calcination, and the damage of the subsequent process to the ordered arrangement structure of the first photonic crystal template is prevented.
Further, in some embodiments of the present application, the first colloidal particle and the second colloidal particle are each independently selected from at least one of a silica microsphere, a zirconium dioxide microsphere, a calcium carbonate microsphere, a zinc sulfide microsphere, and a cadmium sulfide microsphere;
optionally, the first colloid particles and the second colloid particles are silicon dioxide microspheres, the particle size of the silicon dioxide microspheres is 220-320 nm, and the monodispersity index is not more than 0.08.
The silica microspheres are regular in shape, uniform in particle size, and excellent in stability, do not swell in organic solvents, and can be uniformly dispersed in water and organic solvents. The application adopts the silicon dioxide microsphere as the template particle, and can prepare the porous material with uniform pore size, high pore monodispersity and ordered pore distribution.
Further, in some embodiments of the present application, the mass concentration of the first colloidal particles is 0.1 to 5%, preferably 0.5 to 3%, more preferably 1%, which is dispersed in a dispersant selected from at least one of water, ethanol, absolute ethanol, N-dimethylformamide and N, N-dimethylacetamide.
Further, in some embodiments of the present application, the polymer is selected from at least one of polyvinylidene fluoride, polystyrene, polyacrylonitrile, polyethersulfone, polysulfone, polyvinylidene chloride, polyvinylidene fluoride-hexafluoropropylene, polyurethane, polystyrene-polyisoprene-polystyrene block copolymer, styrene-butadiene-styrene block copolymer, and poly (styrene-methyl methacrylate);
alternatively, the mass concentration of the polymer in the casting solution is 7-15%, the polymer concentration is too low to form a stable porous film, and too high concentration can lead to uneven filling and can not form a uniform porous film.
Optionally, the mass ratio of the polymer to the second colloid particles in the casting film liquid is 1 (1.5-2.5). The mass ratio of the polymer to the second colloid particles is controlled to be 1 (1.5-2.5), and the prepared porous material has higher pore dispersivity and more orderly pore distribution.
Wherein the organic solvent is a good solvent for the polymer, and the good solvent is a solvent capable of dissolving the polymer at a temperature not exceeding the melting point of the polymer, and comprises one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and Tetrahydrofuran (THF).
In some embodiments of the present application, the method for preparing the casting solution is as follows:
uniformly dispersing the second colloid particles in an organic solvent through ultrasonic vibration to obtain a first mixture;
mixing the first mixed solution with a polymer to obtain a second mixture;
stirring the second mixture at 50-80 ℃ for reaction for 10-24 hours to obtain the casting solution.
Further, in some embodiments of the present application, the preparation method of the three-dimensional porous material specifically includes the following steps:
1) Adopting a dispersion liquid of first colloid particles to form a first photonic crystal template through self-assembly and solidification;
2) Calcining the first photonic crystal template, wherein the calcining temperature is 500-800 ℃ and the calcining time is 1-5 h;
3) Mixing second colloid particles and a polymer in an organic solvent to form a casting solution, applying the casting solution to the first photonic crystal template, standing for 2-5 h, and filling the polymer into the gaps of the first photonic crystal template in a vacuum oven by adopting vacuum negative pressure of 0.03-0.06 MPa;
4) Evaporating to remove the organic solvent, so that the second colloid particles self-assemble to form a second photonic crystal template laminated on the first photonic crystal template;
5) Soaking the product obtained in the step 4) in an HF solution with the mass concentration of 2-4% for 8-12 h, removing the first colloid particles and the second colloid particles, and then cleaning and drying to obtain the three-dimensional porous material.
Wherein, in the step 1), the baking and curing are carried out by adopting an oven, and the temperature is 40-100 ℃, preferably 50-80 ℃, and more preferably 60 ℃.
Wherein the temperature of the oven in step 3) is 60-90 ℃, preferably 70 ℃.
Based on the same inventive concept, the application proposes a three-dimensional porous material, which is prepared by the preparation method as described above.
Referring to fig. 3, the three-dimensional porous material at least has two stacked membrane layers, a first membrane layer and a second membrane layer, wherein the size of the filtration micropores of the same membrane layer is uniform and easy to regulate, and the pore size between the two membrane layers has gradient change, so that the three-dimensional porous material has higher stain resistance.
Example 1
The three-dimensional porous material is prepared by the following steps:
(1) 0.6g of monodisperse SiO was weighed out 2 Colloidal microspheres (particle size: 260 nm) and the same were mixed with59.4g of ethanol was mixed and uniformly dispersed by ultrasonic vibration to obtain a first colloidal particle dispersion having a mass fraction of 1%.
(2) And (3) placing the dispersion liquid obtained in the step (1) in an oven, and preparing a first photonic crystal template on the glass sheet by adopting a vertical deposition method.
(3) And (3) placing the first photonic crystal template obtained in the step (2) in a muffle furnace for calcination (600 ℃ for 3 h).
(4) Preparing a casting solution: weighing 0.8g PVDF powder (molecular weight 120 w) and 2g SiO respectively 2 Colloidal microspheres (particle size 300nm, monodisperse coefficient)<0.08 8g DMF; firstly, making SiO implement ultrasonic vibration 2 The colloidal microspheres are uniformly dispersed in DMF solution (denoted as first mixture); then adding PVDF powder into the first mixture to obtain a second mixture; finally, the second mixture is placed into a water bath kettle with the temperature of 50 ℃ for heating and stirring for 12 hours, so that PVDF is completely dissolved in DMF, and uniform casting solution is obtained.
(5) 1ml of the casting solution obtained in the step (4) is taken and dripped into the first photonic crystal template obtained in the step (3), and after standing for 2 hours, the casting solution is placed into a vacuum oven at 60 ℃. Under the condition of negative pressure of 0.05MPa, the casting solution is completely infiltrated into the first photonic crystal template, and simultaneously DMF is evaporated and monodisperse SiO is induced 2 Colloidal microspheres (300 nm particle size) were assembled on a first photonic crystal template. After the solvent is completely evaporated, the SiO-containing material is obtained 2 Composite material of colloid microsphere double assembled layer.
(6) Immersing the composite material obtained in the step (5) in 4wt% hydrofluoric acid for 8 hours to sufficiently remove SiO 2 And cleaning and drying the microspheres to obtain the three-dimensional porous material with the double-uniform-pore layers.
The three-dimensional porous material obtained by observation has obvious double uniform pore layers (shown in fig. 3 and 4), the porosity is as high as 80.8%, and the pure water flux is 1137 and 1137L m -2 h -1 . The retention rate of carbon black particles in the coating wastewater can reach 100% (figure 5), after 3 times of coating wastewater separation, the retention rate of the three-dimensional porous material on the carbon black particles can still reach 100%, the pure water flux recovery rate is as high as 96%, and the pollution resistance is higher.
Example 2
The three-dimensional porous material is prepared by the following steps:
(1) 0.6g of monodisperse SiO was weighed out 2 Colloidal microspheres (particle size 220 nm) were mixed with 59.4g of ethanol and dispersed uniformly by ultrasonic vibration to a first colloidal particle dispersion having a mass fraction of 1%.
(2) And (3) placing the dispersion liquid obtained in the step (1) in an oven, and preparing a first photonic crystal template on the glass sheet by adopting a vertical deposition method.
(3) And (3) placing the first photonic crystal template obtained in the step (2) in a muffle furnace for calcination (500 ℃ for 5 h).
(4) Preparing a casting solution: 1.2g of PAN powder (molecular weight 15 w) and 3g of SiO were weighed out respectively 2 Colloidal microspheres (particle size about 270nm, monodisperse coefficient)<0.08 9g DMF; firstly, making SiO implement ultrasonic vibration 2 The colloidal microspheres are uniformly dispersed in DMF solution (denoted as first mixture); then adding PAN powder into the first mixture to obtain a second mixture; finally, the second mixture is placed into a water bath kettle with the temperature of 80 ℃ for heating and stirring for 12 hours, so that PAN is completely dissolved in DMF, and uniform casting solution is obtained.
(5) 1ml of the casting solution obtained in the step (4) is taken and dripped into the first photonic crystal template obtained in the step (3), and after standing for 2 hours, the casting solution is placed into a vacuum oven at 70 ℃. Under the condition of negative pressure of 0.03MPa, the film casting solution is completely infiltrated into the first photon crystal template, and simultaneously DMF is evaporated and monodisperse SiO is induced 2 Colloidal microspheres (270 nm particle size) were assembled on the first photonic crystal template. After the solvent is completely evaporated, the SiO-containing material is obtained 2 Composite material of colloid microsphere double assembled layer.
(6) Immersing the composite material obtained in the step (5) in 2wt% hydrofluoric acid for 8 hours to sufficiently remove SiO 2 The microspheres are washed and dried to obtain the three-dimensional porous material with the double-uniform-pore layers.
The three-dimensional porous material obtained by observation has obvious double-uniform pore layers, the porosity is up to 87.3%, and the pure water flux is 1143L m -2 h -1 . The retention rate of carbon black particles in the paint wastewater can reach 100 percent, and after 3 times of paint wastewater separation, the method comprises the following steps ofThe retention rate of the three-dimensional porous material on carbon black particles can still reach 100%, the pure water flux recovery rate is as high as 97%, and the pollution resistance is higher.
Example 3
The three-dimensional porous material is prepared by the following steps:
(1) 0.6g of monodisperse SiO was weighed out 2 Colloidal microsphere powder (particle size 280 nm) was mixed with 59.4g of ethanol and uniformly dispersed by ultrasonic vibration to obtain a first colloidal particle dispersion having a mass fraction of 1%.
(2) And (3) placing the dispersion liquid obtained in the step (1) in an oven, and preparing a first photonic crystal template on the glass sheet by adopting a vertical deposition method.
(3) And (3) placing the first photonic crystal template obtained in the step (2) in a muffle furnace for calcination (700 ℃ for 2 h).
(4) Preparing a casting solution: separately, 0.8g of PES powder (polymerization degree: 40 w) and 1.2g of SiO were weighed out 2 Colloidal microspheres (particle size of about 320nm, monodisperse coefficient)<0.08 8g DMAc; firstly, making SiO implement ultrasonic vibration 2 The colloidal microspheres are uniformly dispersed in the DMAc solution (denoted as a first mixture); adding PES powder into the first mixture to obtain a second mixture; finally, the second mixture is placed into a water bath kettle with the temperature of 80 ℃ for heating and stirring for 24 hours, so that PES is completely dissolved in DMAc, and uniform casting solution is obtained.
(5) 1ml of the casting solution obtained in the step (4) is taken and dripped into the first photonic crystal template obtained in the step (3), and after standing for 2 hours, the casting solution is placed into a vacuum oven at 90 ℃. Under the condition of negative pressure of 0.06MPa, the casting solution is completely infiltrated into the first photonic crystal template, and simultaneously DMAc is evaporated and monodisperse SiO is induced 2 Colloidal microspheres (320 nm particle size) were assembled on the first photonic crystal template. After the solvent is completely evaporated, the SiO-containing material is obtained 2 Composite material of colloid microsphere double assembled layer.
(6) Immersing the composite material obtained in the step (5) in 3wt% hydrofluoric acid for 10 hours to sufficiently remove SiO 2 The microspheres are washed and dried to obtain the three-dimensional porous material with the double-uniform-pore layers.
The three-dimensional porous material obtained by observation has obvious double effectsPore-uniformizing layer with porosity up to 80.2% and pure water flux of 1124L m -2 h -1 . The retention rate of carbon black particles in the coating wastewater can reach 100%, the retention rate of the three-dimensional porous material on the carbon black particles can still reach 100% after 3 times of coating wastewater separation, the pure water flux recovery rate is as high as 93%, and the pollution resistance is higher.
Example 4
The three-dimensional porous material is prepared by the following steps:
(1) 0.6g of monodisperse SiO was weighed out 2 Colloidal microsphere powder (particle diameter: 230 nm), which was mixed with 59.4g of ethanol, and uniformly dispersed into a first colloidal particle dispersion having a mass fraction of 1% by ultrasonic vibration.
(2) And (3) placing the dispersion liquid obtained in the step (1) in an oven, and preparing a first photonic crystal template on the glass sheet by adopting a vertical deposition method.
(3) And (3) placing the first photonic crystal template obtained in the step (2) in a muffle furnace for calcination (800 ℃ for 1 h).
(4) Preparing a casting solution: 1g of PSF powder (molecular weight: 8 ten thousand) and 1.6g of SiO were weighed out respectively 2 Colloidal microspheres (particle size 280nm, monodisperse coefficient)<0.08 5g DMF; firstly, making SiO implement ultrasonic vibration 2 The colloidal microspheres are uniformly dispersed in DMF solution (denoted as first mixture); then adding PSF powder into the first mixture to obtain a second mixture; finally, the second mixture is placed into a water bath kettle with the temperature of 60 ℃ for heating and stirring for 10 hours, so that PSF is completely dissolved in DMF, and uniform casting solution is obtained.
(5) 1ml of the casting solution obtained in the step (4) is taken and dripped into the first photonic crystal template obtained in the step (3), and after standing for 2 hours, the casting solution is placed into a vacuum oven at 70 ℃. Under the condition of negative pressure of 0.04MPa, the film casting solution is completely infiltrated into the first photon crystal template, and simultaneously DMF is evaporated and monodisperse SiO is induced 2 Colloidal microspheres (particle size 280 nm) were assembled on the first photonic crystal template. After the solvent is completely evaporated, the SiO-containing material is obtained 2 Composite material of colloid microsphere double assembled layer.
(6) Immersing the composite material obtained in the step (5) in 3wt% hydrofluoric acid for 11h to sufficiently remove SiO 2 The microspheres are washed and dried to obtain the three-dimensional porous material with the double-uniform-pore layers.
The three-dimensional porous material obtained by observation has obvious double-uniform pore layer, the porosity is as high as 83.9%, and the pure water flux is 1125L m -2 h -1 . The retention rate of carbon black particles in the coating wastewater can reach 100%, the retention rate of the three-dimensional porous material on the carbon black particles can still reach 100% after 3 times of coating wastewater separation, the pure water flux recovery rate is as high as 94%, and the pollution resistance is higher.
Example 5
The three-dimensional porous material is prepared by the following steps:
(1) 0.6g of monodisperse SiO was weighed out 2 Colloidal microsphere powder (particle diameter 250 nm), which was mixed with 59.4g of ethanol, and uniformly dispersed into a first colloidal particle dispersion with a mass fraction of 1% by ultrasonic vibration.
(2) And (3) placing the dispersion liquid obtained in the step (1) in an oven, and preparing a first photonic crystal template on the glass sheet by adopting a vertical deposition method.
(3) And (3) placing the first photonic crystal template obtained in the step (2) in a muffle furnace for calcination (600 ℃ for 3 h).
(4) Preparing a casting solution: 1g of PVC powder (molecular weight is 6-7 w) and 2g of SiO are respectively weighed 2 Colloidal microspheres (particle size 290nm, single dispersion coefficient)<0.08 8g DMF/THF (mass ratio of DMF to THF 1:1); firstly, making SiO implement ultrasonic vibration 2 The colloidal microspheres were uniformly dispersed in DMF/THF solution (noted as first mixture); adding PES powder into the first mixture to obtain a second mixture; finally, the second mixture is placed into a water bath kettle with the temperature of 50 ℃ for heating and stirring for 12 hours, so that the PVC is completely dissolved in the DMF/THF, and a uniform casting solution is obtained.
(5) 1ml of the casting solution obtained in the step (4) is taken and dripped into the first photonic crystal template obtained in the step (3), and after standing for 2 hours, the casting solution is placed into a vacuum oven at 60 ℃. Under the condition of negative pressure of 0.02MPa, the casting solution is completely infiltrated into the first photonic crystal template, and simultaneously DMF/THF is evaporated and monodisperse SiO is induced 2 Colloidal microspheres (290 nm particle size) were assembled on the first photonic crystal template. Dissolving solutionAfter the agent is completely evaporated, the SiO-containing material is obtained 2 Composite material of colloid microsphere double assembled layer.
(6) Immersing the composite material obtained in the step (5) in 4wt% hydrofluoric acid for 12 hours to sufficiently remove SiO 2 The microspheres are washed and dried to obtain the three-dimensional porous material with the double-uniform-pore layers.
The three-dimensional porous material obtained by observation has obvious double-uniform pore layer, the porosity is up to 88.1 percent, and the pure water flux is 1130L m -2 h -1 . The retention rate of carbon black particles in the coating wastewater can reach 100%, the retention rate of the three-dimensional porous material on the carbon black particles can still reach 100% after 3 times of coating wastewater separation, the pure water flux recovery rate is as high as 96%, and the pollution resistance is higher.
The foregoing description is only of the preferred embodiments of the present application and is presented as a description of the principles of the technology being utilized. It will be appreciated by persons skilled in the art that the scope of the disclosure referred to in this application is not limited to the specific combinations of features described above, but it is intended to cover other embodiments in which any combination of features described above or equivalents thereof is possible without departing from the spirit of the disclosure. Such as the above-described features and technical features having similar functions (but not limited to) disclosed in the present application are replaced with each other.

Claims (16)

1. The preparation method of the three-dimensional porous material is characterized by comprising the following steps of:
forming a first photonic crystal template, wherein the first photonic crystal template is formed by self-assembly of first colloid particles;
mixing second colloid particles and a polymer in an organic solvent to form a casting solution, applying the casting solution to the first photonic crystal template, and filling the polymer into gaps of the first photonic crystal template;
self-assembling the second colloidal particles to form a second photonic crystal template layered on the first photonic crystal template;
removing the first colloid particles and the second colloid particles to obtain the three-dimensional porous material;
wherein the particle size of the first colloidal particles is smaller than the particle size of the second colloidal particles.
2. The method of claim 1, wherein the polymer is filled into the voids of the first photonic crystal template by vacuum negative pressure.
3. The method according to claim 2, wherein the vacuum negative pressure is 0.03 to 0.06MPa.
4. The method of claim 1, wherein the first and second colloidal particles are removed by acid or alkali etching.
5. The method of claim 4, wherein the first colloidal particles and the second colloidal particles are removed using a highly corrosive solution.
6. The method according to claim 5, wherein the highly corrosive solution is an HF solution having a mass concentration of 2 to 4%.
7. The method of preparing according to claim 1, further comprising, prior to applying the casting solution to the first photonic crystal template:
and calcining the first photonic crystal template, wherein the calcining temperature is 500-800 ℃ and the calcining time is 1-5 h.
8. The production method according to any one of claims 1 to 7, wherein the first colloidal particles and the second colloidal particles are each independently selected from at least one of silica microspheres, zirconium dioxide microspheres, calcium carbonate microspheres, zinc sulfide microspheres, and cadmium sulfide microspheres.
9. The method according to claim 8, wherein the first colloidal particles and the second colloidal particles are silica microspheres, the silica microspheres have a particle size of 220 to 320nm, and the monodispersity index is not more than 0.08.
10. The method according to claim 1, wherein the first colloidal particles have a mass concentration of 0.1 to 5% and are dispersed in a dispersant selected from at least one of water, ethanol, absolute ethanol, N-dimethylformamide and N, N-dimethylacetamide.
11. The method according to claim 10, wherein the mass concentration of the first colloidal particles is 0.5 to 3%.
12. The method of claim 11, wherein the first colloidal particles have a mass concentration of 1%.
13. The method according to claim 1, wherein the polymer is at least one selected from the group consisting of polyvinylidene fluoride, polystyrene, polyacrylonitrile, polyethersulfone, polysulfone, polyvinylidene chloride, polyvinylidene fluoride-hexafluoropropylene, polyurethane, polystyrene-polyisoprene-polystyrene block copolymer, styrene-butadiene-styrene block copolymer, and polystyrene methyl methacrylate.
14. The method according to claim 13, wherein the mass concentration of the polymer in the casting solution is 7 to 15%; the mass ratio of the polymer to the second colloid particles in the film casting liquid is 1 (1.5-2.5).
15. The preparation method of the three-dimensional porous material is characterized by comprising the following steps of:
1) Adopting a dispersion liquid of first colloid particles to form a first photonic crystal template through self-assembly and solidification;
2) Calcining the first photonic crystal template, wherein the calcining temperature is 500-800 ℃ and the calcining time is 1-5 h;
3) Mixing second colloid particles and a polymer in an organic solvent to form a casting solution, applying the casting solution to the first photonic crystal template, standing for 2-5 h, and filling the polymer into the gaps of the first photonic crystal template in a vacuum oven by adopting vacuum negative pressure of 0.03-0.06 MPa;
4) Evaporating to remove the organic solvent, so that the second colloid particles self-assemble to form a second photonic crystal template laminated on the first photonic crystal template;
5) Soaking the product obtained in the step 4) in an HF solution with the mass concentration of 2-4% for 8-12 h, removing the first colloid particles and the second colloid particles, and then cleaning and drying to obtain the three-dimensional porous material.
16. A three-dimensional porous material prepared by the preparation method of any one of claims 1 to 15.
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