CN110372022B - One-step synthesis method of macroscopic 3D multi-stage porous nano material - Google Patents
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Abstract
The invention discloses a macroscopic 3D multi-stage porous nano material one-step synthesis method, which belongs to the technical field of nano materials and comprises the following steps: 1) adding a surfactant and an oil phase reaction precursor into an organic solvent to serve as an oil phase; adding a water phase reaction precursor into water to serve as a water phase; 2) contacting and mixing the oil phase and the water phase to form a bicontinuous emulsion of an oil-water bicontinuous phase interface; 3) standing to obtain the macroscopic 3D multi-stage porous nano material. The invention discloses a one-step synthesis method of a macroscopic 3D multi-stage porous nano material, which is characterized in that an integral macroscopic 3D nano material formed by entanglement of continuous nano layers is directly synthesized through liquid, the continuous nano layers form bicontinuous multi-stage pore channels, pores in the initial micron-scale pore channels and the nanometer-scale pores are all available, and the continuous nano layers are composite nano materials synthesized by nano materials. The continuous nanolayer provides structural strength that can easily overcome capillary pressure during liquid removal, and the volume shrinkage after dehydration is less than 15%.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a one-step synthesis method of a macroscopic 3D multi-stage porous nano material.
Background
Porous materials refer to a class of materials having a large number of pore structures of a certain size and a high specific surface area. Compared with continuous medium materials, porous materials generally have the characteristics of low relative density, high specific surface area, excellent adsorption performance, good sound insulation, heat insulation, permeability and the like, are widely used in the fields of aerospace, environmental protection, electronic communication, atomic energy, medicine, transportation, metallurgy, construction, machinery, electrochemistry, petrochemical industry and the like, relate to the application of a plurality of aspects such as adsorption, noise reduction, filtration, separation, circuit shielding, heat insulation, catalytic reaction, energy storage and conversion, bioengineering and the like, and play a great role in scientific technology and national economic construction.
Sol-gel process refers to a process in which one or more components in a solution form a sol, which is converted to a gel by a series of treatments to form a homogeneous, almost amorphous solid. As the reaction proceeds, the solid particles will crosslink and grow, and become a gelled substance with a network structure. Generally, the method is a method of obtaining an oxide or other compounds by subjecting a mixture of a metal organic compound, a metal inorganic compound or both of them as raw materials to a hydrolytic polycondensation process, gradual gelation, and corresponding aging and drying treatments.
The method for preparing the porous material based on the sol-gel method mainly comprises two steps: firstly, dissolving raw materials and auxiliary materials in a solvent to carry out a sol-gel process to finally form gel; and secondly, drying the gel to obtain the porous material. The state of the gel and the drying process techniques together affect the pore structure of the final product.
The macroscopic nanoporous material is typically represented by aerogel, and the aerogel material generally refers to a three-dimensional porous lightweight solid material which is formed by aggregating nano-scale particles with each other to form a nano-porous structure and filling gaseous dispersion media in nano-pores. The unique three-dimensional network pore structure of aerogels imparts a number of unique properties, including high surface area, low refractive index, low electrical conductivity, low heat transfer coefficient, low acoustic propagation velocity, low density, and the like. This makes aerogels very versatile in application. The aerogel is very easy to cause the crushing of aerogel materials and the damage of pore structures due to the existence of surface tension in the drying stage. The porosity of the aerogel necessarily results in a material that is itself brittle and fragile.
Aerogels in general have the following disadvantages: expensive manufacturing costs; the drying process is accompanied with huge volume shrinkage, so that cracking is easily caused, and particularly, the drying process is suitable for colloid with larger size; low strength, high brittleness and the like which are difficult to overcome by the material. These disadvantages become a bottleneck limiting the wide application of the method, and therefore become a key for the common efforts of scientists in various countries to break through in the future. The prior art is often applied to vibrating the powder of the nano material, such as consolidation forming of the powder, which actually reduces the specific surface area and simultaneously cannot form abundant hierarchical pores, and is very unfavorable for the application of the nano material.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a one-step synthesis method of a macroscopic 3D multi-stage porous nano material, which has rich nano structures and very large specific surface area; the shrinkage rate is very low in the preparation process, and the prepared material has very high strength compared with the traditional aerogel.
The technical scheme is as follows: in order to achieve the purpose, the invention provides the following technical scheme:
the macroscopic 3D multi-stage porous nano material one-step synthesis method comprises the following steps:
1) adding a surfactant and an oil phase reaction precursor into an organic solvent to serve as an oil phase; adding a water phase reaction precursor into water to serve as a water phase;
2) contacting and mixing the oil phase and the water phase to form a bicontinuous emulsion of an oil-water bicontinuous phase interface;
3) standing to obtain the macroscopic 3D multi-stage porous nano material.
The macroscopic 3D multi-stage porous nano material is composed of a two-dimensional curved surface composed of nano materials, wherein the curved surface is irregular and comprises a channel formed by the curved surface; the curved surface is composed of a plurality of layers of nano materials, wherein the curved surface at least comprises a supporting layer, a bonding layer and a functional layer, the supporting layer mainly can be a fixed bicontinuous interface and improves the structural strength, the bonding layer is the bonding layer of the functional layer and the supporting layer, and the functional layer endows the materials with other corresponding special functions; the porous membrane has a multi-stage pore channel structure, and comprises nano pores from micropores, mesopores to macropores, the maximum pore diameter can even reach the micron level, and the pore channels are communicated with one another.
Further, in the step 1), the oil phase reaction precursor is an alkaline organic matter, and the water phase reaction precursor is a metal salt; in the step 2), after the oil phase is contacted and mixed with water, hydroxide precipitation is generated on the oil-water interface of the alkaline organic matter and the metal salt, and the alkaline organic matter and the metal salt are further self-assembled under the action of a surfactant and surface tension to form a supporting layer with a nano structure.
In the step 2), the following reactions are included:
2.1) initiation reaction: basic organic matter and water generate OH on oil-water interface-；
2.2) support layer reaction: the cation of the metal salt in the water phase reacts with OH generated by the initiation reaction at the water side of the oil-water interface-Hydroxide precipitates are generated at an oil-water interface, and the nano-structure supporting layer is further self-assembled under the action of a surfactant and surface tension.
Further, the hydroxide precipitation chemistry molecule composition is
Wherein X is 0-1, M2+、M3+Is a metal ion, An-Is an interlayer anion.
Further, in step 1), the oil phase reaction precursor further comprises metal alkoxide for forming a functional layer and/or macromolecules in organic polymerization reaction.
Further, when the oil phase reaction precursor comprises macromolecules in organic polymerization reaction, the water phase reaction precursor also comprises small molecules in organic polymerization reaction, and the macromolecules in the organic polymerization reaction and the small molecules in the organic polymerization reaction are subjected to one or more of addition, condensation and polycondensation to generate the resin.
It can be seen that the functional layer reaction comprises the following steps:
2.3) when the oil phase reaction precursor further comprises a metal alkoxide, the metal alkoxide is on the oil phase side of the interface, at the OH group formed by the initiation reaction-Under the catalytic action of the catalyst, the catalyst and a water phase are subjected to hydrolytic polymerization reaction to form a nano-structure material;
2.4) when the oil phase reaction precursor also comprises macromolecules in organic polymerization reaction, the water phase reaction precursor also comprises micromolecules in organic polymerization reaction, and the macromolecules in the organic polymerization reaction and the micromolecules in the organic polymerization reaction are subjected to one or more of addition, condensation and polycondensation to generate resin;
2.5) when the oil phase reaction precursor also comprises metal alkoxide and macromolecules in organic polymerization reaction, the reactions of the steps 2.3) to 2.4) all occur.
The reactions of the steps 2.3) -2.5) are carried out on the interface, and a macroscopic 3D multi-stage porous nano material is formed along the growth of the bicontinuous phase interface; along with the reaction, the nano layer generated on the interface is more and more compact, so that the diffusion and contact of oil-water two phases and dissolved reaction precursors are limited, the reaction is choked, and the thickness of the nano layer is limited.
Further, in step 1), a surfactant is also added to the water as an aqueous phase.
Further, the addition amount of the surfactant in the oil phase accounts for more than 50% of the addition amount of the total surfactant, and the addition amount of the surfactant in the water phase accounts for less than 50% of the addition amount of the total surfactant; the total surfactant addition amount is 10 g/mL-0.01 g/mL in the volume sum of the oil phase and the water phase.
Further, in the step 1), the organic solvent accounts for 10-80% of the oil phase by volume; in the step 1) and the step 2), the density of the oil phase is 0.6-1.3 times of the density of the water phase, and the viscosity of the oil phase is 0.7-1.6 times of the viscosity of the water phase; in the step 2), the mixing ratio of the water phase and the oil phase is 1: 3-3: 1, after the oil phase and the water phase are contacted and mixed, the concentration of positive cationic charges in a precursor of a water phase reaction is 0.00001-0.005 mol/mL, and the molar ratio of the number of positive cationic charges to the number of negative anionic charges theoretically generated by a basic organic matter is 0.5-0.8.
Further, the organic solvent is one or more of 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromoundecane, 1-bromotetradecane, chlorocyclohexane, 1-bromohexadecane, 4-methyl-3-ethylheptane, 4-methylundecane, n-tridecane, n-eicosane, tert-butylbenzene and 1, 1-diphenylheptane; the HLB of the surfactant is 2-7, and the surfactant is didodecyldimethylammonium bromide and/or lecithin.
Further, in the step 3), the standing is carried out for 12-48 hours at room temperature under normal pressure.
The reaction mechanism is as follows: respectively dissolving corresponding substances in a water phase and an oil phase (namely two incompatible phases), forming a liquid-liquid interface of the bicontinuous phase by liquid-liquid bicontinuous phase preparation equipment or method, quickly diffusing a dissolved surfactant on the interface to the interface, reducing the surface tension of the interface, maintaining the stability of the formed liquid-liquid interface, and simultaneously reacting a reaction initiator (for example, benzylamine) dissolved in the oil phase at the oil-water interface to generate OH-，OH-The method is characterized in that hydroxide precipitation reaction is rapidly carried out on the metal cations in water, the generated precipitate is rapidly self-assembled into supporting layers with different structures at an oil-water interface under the combined action of a surfactant and interfacial tension according to different properties of the precipitate, the surfactant and the nanoparticle precipitate interact to form surface active nanoparticles, the surface tension of the oil-water interface is greatly reduced, the difficulty of a reaction precursor penetrating the interface is increased along with the increase of the nanoparticles on the interface, so that the thickness of a nanolayer is limited, on the other hand, the bicontinuous phase is stable, even the oil-water interface is automatically expanded, so that a system is promoted to be developed to the bicontinuous microemulsion phase, when the consumption of the metal cations is more, and redundant OH is generated-In OH when-Under the catalysis, a reaction precursor (TEOS for example) dissolved in an oil phase is subjected to hydrolytic polycondensation reaction on an oil-water interface to form sol-gel, self-assembled to form a nano-silica sphere under the action of a surfactant, further self-assembled on the interface to form a nano-silica aggregate under the action of interfacial tension and capillary force, and after the reaction is finished, a stable bicontinuous phase emulsion gel is formed, and a layer of continuous and complete nano-material (comprising a supporting layer) is formed on the bicontinuous phase interfaceBonding layer, functional layer, etc.) the nanolayers, depending on the nanomaterial composition, nevertheless have different properties.
Has the advantages that: compared with the prior art, the macroscopic 3D multi-stage porous nano material one-step synthesis method has the advantages that the whole macroscopic 3D nano material formed by entanglement of continuous nano layers is directly synthesized through liquid, the continuous nano layers form bicontinuous multi-stage pore channels, pores in the initial micron-scale pore channels and the nanometer-scale pores are all arranged, and the continuous nano layers are composite nano materials synthesized by nano materials; a hydroxide supporting layer is formed on the water side of the oil-water interface, the thickness of the supporting layer is generally less than 2 microns, and the supporting layer has a complex nano structure, and particularly, the supporting layer is a continuous macro whole growing along a bicontinuous interface, and a macro 3D multi-stage porous structure is formed and maintained under the action of the supporting layer; the continuous nanolayer provides structural strength that can easily overcome capillary pressure during liquid removal, and the volume shrinkage after dehydration is less than 15%.
Drawings
FIG. 1 is an SEM image of macroscopic 3D multi-stage porous nanomaterial magnified 100 times by a one-step synthesis method without oscillation;
FIG. 2 is an SEM image of a macroscopic 3D multi-stage porous nanomaterial with 5000-fold magnification without oscillation by a one-step synthesis method;
FIG. 3 is a sectional structure of a macroscopic 3D multi-stage porous nano material;
FIG. 4 is an irregular continuous nanolayer formed by an irregular bicontinuous solution interface.
Detailed Description
The invention will be further described with reference to the following drawings and specific embodiments.
The macroscopic 3D multi-stage porous nano material one-step synthesis method comprises the following steps:
1) adding a surfactant and an oil phase reaction precursor into an organic solvent to serve as an oil phase; adding a water phase reaction precursor into water to serve as a water phase;
2) contacting and mixing the oil phase and the water phase to form a bicontinuous emulsion of an oil-water bicontinuous phase interface;
3) standing to obtain the macroscopic 3D multi-stage porous nano material.
The macroscopic 3D multi-stage porous nano material is composed of a two-dimensional curved surface composed of nano materials, wherein the curved surface is irregular and comprises a channel formed by the curved surface; the curved surface is composed of a plurality of layers of nano materials, wherein at least one layer is a supporting layer; the two sides of the curved surface have different structures and main components due to different reactions in preparation, and the thickness of the curved surface is limited by the preparation reaction; the nano particles composing the membrane are combined with the surfactant and the cosurfactant through interaction, meanwhile, the nano particles form a very rich regular nano-scale pore structure in the self-assembly process, and the surface of the pore structure is provided with a plurality of surfactant groups to form a basically selective mass transfer channel; the nano material is mainly generated by the reaction on a liquid/liquid interface, and can be designed and regulated according to the requirement; a relatively compact layer is arranged in the middle of the curved surface, so that the mass transfer of substances is difficult; the curved surface is provided with a plurality of folds and bulges; the integral material has rich pore passages from nano level to micron level; the shape of the finally prepared material is the same as the shape and the size of the precursor liquid; the macroscopic 3D multilevel porous nano material one-step synthesis method has a multilevel pore channel structure, including the nanometer pore diameters from micropores, mesopores to macropores, the maximum pore diameter can even reach the micron level, the pore channels are mutually communicated, the liquid flow and the material transmission are very facilitated, the large specific surface area is realized in one step, and meanwhile, the mass transfer capacity is higher.
In the step 1), the oil phase reaction precursor is an alkaline organic matter, and the water phase reaction precursor is a metal salt; in the step 2), after the oil phase is contacted and mixed with water, hydroxide precipitation is generated on the oil-water interface of the alkaline organic matter and the metal salt, and the alkaline organic matter and the metal salt are further self-assembled under the action of a surfactant and surface tension to form a supporting layer with a nano structure.
In the step 2), the following reactions are included:
2.1) initiation reaction: basic organic matter and water generate OH on oil-water interface-；
2.2) support layer reaction: the cation of the metal salt in the water phase reacts with OH generated by the initiation reaction at the water side of the oil-water interface-In the oil waterHydroxide precipitates are generated at the interface, and the hydroxide precipitates are further self-assembled into a nano-structure supporting layer under the action of a surfactant and surface tension.
The chemical molecular composition of hydroxide precipitation is
Wherein X is 0-1, M2 +、M3+Is a metal ion, An-Is an interlayer anion.
In step 1), the oil phase reaction precursor further comprises metal alkoxide for forming the functional layer and/or macromolecules in organic polymerization reaction.
When the oil phase reaction precursor comprises macromolecules in organic polymerization reaction, the water phase reaction precursor also comprises micromolecules in organic polymerization reaction, and the macromolecules in the organic polymerization reaction and the micromolecules in the organic polymerization reaction are subjected to one or more of addition, condensation and polycondensation reaction to generate the resin.
It can be seen that the functional layer reaction comprises the following steps:
2.3) when the oil phase reaction precursor further comprises a metal alkoxide, the metal alkoxide is on the oil phase side of the interface, at the OH group formed by the initiation reaction-Under the catalytic action of the catalyst, the catalyst and a water phase are subjected to hydrolytic polymerization reaction to form a nano-structure material;
2.4) when the oil phase reaction precursor also comprises macromolecules in organic polymerization reaction, the water phase reaction precursor also comprises micromolecules in organic polymerization reaction, and the macromolecules in the organic polymerization reaction and the micromolecules in the organic polymerization reaction are subjected to one or more of addition, condensation and polycondensation reaction to generate resin;
2.5) when the oil phase reaction precursor also comprises metal alkoxide and macromolecules in organic polymerization reaction, the reactions of the steps 2.3) to 2.4) all occur.
The reactions of the steps 2.3) -2.5) are carried out on the interface, and a macroscopic 3D multi-stage porous nano material is formed along the growth of the bicontinuous phase interface; along with the reaction, the nano layer generated on the interface is more and more compact, so that the diffusion and contact of oil-water two phases and dissolved reaction precursors are limited, the reaction is choked, and the thickness of the nano layer is limited.
In step 1), a surfactant is also added to the water as an aqueous phase.
In the step 1), the volume ratio of the organic solvent to the oil phase is 10-80%, the addition amount of the surfactant in the oil phase accounts for more than 50% of the addition amount of the total surfactant, and the addition amount of the surfactant in the water phase accounts for less than 50% of the addition amount of the total surfactant; the total surfactant addition amount is 1 g/mL-0.001 g/mL in the sum of the volumes of the oil phase and the water phase; in the step 1) and the step 2), the density of the oil phase is 0.6-1.3 times of the density of the water phase, and the viscosity of the oil phase is 0.7-1.6 times of the viscosity of the water phase; in the step 2), the mixing ratio of the water phase to the oil phase is 1: 3-3: 1; after the oil phase and the water phase are contacted and mixed, the concentration of positive cationic charges in the precursor of the water phase reaction is 0.00001-0.005 mol/mL, and the molar ratio of the number of the positive cationic charges to the number of negative anionic charges theoretically generated by the alkaline organic matter is 0.5-0.8.
The organic solvent is one or the combination of more of 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromoundecane, 1-bromotetradecane, chlorocyclohexane, 1-bromohexadecane, 4-methyl-3-ethylheptane, 4-methylundecane, n-tridecane, n-eicosane, tert-butyl benzene and 1, 1-diphenylheptane; the HLB of the surfactant is 2-7, and the surfactant is didodecyldimethylammonium bromide and/or lecithin.
In the step 3), the standing is carried out for 12-48 h at room temperature under normal pressure.
The supporting layer is a crystal which can form a lamellar, flaky or banded crystal form, and the supporting layer is formed by forming a banded, flaky or layered nano structure; the supporting layer is a part of the curved surface and plays a role in limiting the thickness of the curved surface, increasing the strength of the whole material, improving the porosity and reducing the shrinkage; the curved surface comprises a supporting layer and a functional layer, the same component can be the supporting layer and the functional layer, and the functional layer mainly endows the material with special performances such as catalysis, adsorptivity, selectivity, high specific surface area and the like; the special structure and components can be designed and prepared according to the needs, so that the nano material has catalytic property, adsorbability, selectivity and conductivity, and different layers can have one or more layers at the same time, so that the curved surface and the whole nano material have special performance and are applied to corresponding occasions.
The bicontinuous interface formed by the initial mixing has very obvious influence on the material performance; the reactions take place at the liquid-liquid interface and are different on the oil side and the water side; the reaction is generated by adsorbing the nano solid on the interface and combining the nano solid with the surfactant, so that the interfacial tension is further reduced, the interfacial area is further increased, the interface is increased to form a new oil-water interface, and structures such as folds, bulges and the like are formed; as the reaction proceeds, the oil phase (or the water phase) is continuously reduced, so that the newly formed interface is forced to be concave towards the oil phase, and regular structures such as folds, bulges and the like are formed; the bicontinuous interface is initially composed of a surfactant and then continuously composed with the generated nano-solid; the surfactant may be a single species or a combination of species, may include a co-surfactant, and the by-product of the reaction may also act as a surfactant or co-surfactant.
Example 1
The preparation method of the macroscopic 3D multi-stage porous nano material by one-step synthesis comprises the following steps:
1. 0.7g didodecyldimethylammonium bromide (DDAB) (concentration 0.05g/mL, 100% dissolved in the oil phase) was weighed into a reactor (25mL beaker);
2. pouring 3.5mL of Tetraethoxysilane (TEOS) into the reactor;
3. 3.5mL of n-dodecane was poured into the reactor (organic solvent about 50% of the oil phase);
4. 0.7mL of benzylamine was poured into the reactor (ca. 0.0063 mol);
5. ultrasonic dissolving to obtain oil phase;
6、Al2(SO4)3*18H2dissolving O in water at the concentration of 0.000112049mol/mL to serve as a water phase;
7. taking 7mL of water phase to rapidly inject into the oil phase reactor (the key is to ensure that the whole liquid is mixed milky, has no layering, has no bubbles and has no clear liquid stay after injection) (the molar ratio of the positive charge number of the cation to the negative charge number of the anion generated by the alkaline organic matter is about 0.7);
8. after the oil phase is injected with the water phase for 10 minutes, shaking up the mixture (the key point is to ensure that the whole liquid is mixed milky after injection, no layering, no bubbles and no clear liquid stay) and standing the mixture for 24 hours at normal temperature;
9. drying for 24 hours at 80 ℃ under an aerobic condition;
the whole is formed after drying for 24 hours at 80 ℃ under aerobic condition, and the shrinkage rate is 6.9%; the structure is shown in figure 1 and figure 2.
Example 2
The preparation method of the macroscopic 3D multi-stage porous nano material by one-step synthesis comprises the following steps:
1. weighing 0.7g didodecyldimethylammonium bromide (DDAB concentration is 0.05g/mL, 100% is dissolved in oil phase), and placing into a reactor (25mL beaker);
2. pouring 3.5mL of Tetraethoxysilane (TEOS) into the reactor;
3. 3.5mL of monobromo tetradecane is poured into a reactor (the organic solvent accounts for about 50 percent of the oil phase);
4. 0.7mL of benzylamine was poured into the reactor (ca. 0.0063 mol);
5. ultrasonic dissolving to obtain oil phase;
6、Zn(NO3)2*6H2dissolving O in water at the concentration of 0.000336146mol/mL to serve as a water phase;
7. taking 7mL of water phase to rapidly inject into the oil phase reactor (the key is to ensure that the whole liquid is mixed milky, has no layering, has no bubbles and has no clear liquid stay after injection) (the molar ratio of the positive charge number of the cation to the negative charge number of the anion generated by the alkaline organic matter is about 0.7);
8. standing for 24h at normal temperature;
9. drying for 24 hours at 70 ℃ under an aerobic condition;
FIG. 3 shows that the shrinkage of the whole is 2.9% after drying for 24 hours at 70 ℃ in the presence of oxygen.
Example 3
A macroscopic 3D multi-stage porous nano material one-step synthesis method comprises the following steps:
1. weighing 0.5g lecithin (with concentration of 0.035g/mL, 100% dissolved in oil phase), and placing into a reactor (25mL beaker);
2. pouring 2.5mL of Tetraethoxysilane (TEOS) into the reactor;
3. 0.2g of diisopropyl peroxydicarbonate;
4. 5mL of heptane was taken and placed in the reactor (organic solvent accounted for about 60% of the oil phase);
5. 0.5mL of benzylamine was poured into the reactor (ca. 0.0004 mol);
6. ultrasonic dissolving in water bath at 40-42 deg.C to obtain oil phase;
7. taking 2g of chloroethylene;
8. 0.5g of polyvinyl alcohol is taken;
9. adding 10mL of deionized water;
10、Al2(SO4)3*18H2o is dissolved in the water phase, the concentration is 0.000112049mol/mL, and the water phase is used;
11. heating the aqueous phase to 95 ℃;
12. taking 7mL of water phase and quickly injecting the water phase into the 7mL of oil phase reactor (the key point is to ensure that the whole liquid is mixed milky, does not separate layers, does not have bubbles and does not retain clear liquid after being injected) (the molar ratio of the positive charge number of the cation to the negative charge number of the anion theoretically generated by the alkaline organic matter is about 0.8);
13. keeping the temperature at 95 ℃ for 12 h;
14. cooling to 60 ℃ and drying for 10h under aerobic condition;
15. thermal polymerization is carried out for 2h at the temperature of 100 ℃.
The whole was dried at 100 ℃ for 2 hours in the presence of oxygen, and the shrinkage was 14.3%.
Example 4
A macroscopic 3D multi-stage porous nano material one-step synthesis method comprises the following steps:
1. 1.5g of cetyltrimethylammonium bromide (CTAB) (concentration 0.105g/mL, 100% dissolved in the oil phase) was weighed into a reactor (25mL beaker);
2. weighing 0.5g of phenol and putting into a reactor;
3. pouring 1.0mL of methyl titanate Tetraethoxysilane (TEOS) into a reactor;
4. 5mL of monobromo tetradecane is poured into a reactor (the organic solvent accounts for about 70 percent of the oil phase);
5. 0.5mL of benzylamine was poured into the reactor (ca. 0.0004 mol);
6. ultrasonic dissolving in water bath at 40-42 deg.C to obtain oil phase;
7. dissolving formaldehyde in water at a concentration of 0.05g/mL to obtain a water phase;
8、Al2(SO4)3*18H2o is dissolved in the water phase, the concentration is 0.000112049mol/mL, and the water phase is used;
9. taking 7mL of water phase and quickly injecting the water phase into the 7mL of oil phase reactor (the key point is to ensure that the whole liquid is mixed milky, does not separate layers, does not have bubbles and does not retain clear liquid after being injected) (the molar ratio of the positive charge number of the cation to the negative charge number of the anion theoretically generated by the alkaline organic matter is about 0.8);
10. standing for 24h at normal temperature;
11. drying for 10 hours at 60 ℃ under an aerobic condition;
12. thermally polymerizing for 24 hours at the temperature of 100 ℃;
the whole was dried at 100 ℃ for 24 hours in the presence of oxygen, and the shrinkage was 14%.
Example 5
A macroscopic 3D multi-stage porous nano material one-step synthesis method comprises the following steps:
1. weighing 0.7g lecithin (with concentration of 0.05g/mL, 100% dissolved in oil phase), and placing into a reactor (25mL beaker);
2. pouring 2.5mL of Tetraethoxysilane (TEOS) into the reactor;
3. 3.5mL of monobromo tetradecane is poured into a reactor (the organic solvent accounts for about 50 percent of the oil phase);
4. pouring 1.0mL of phenol into the reactor;
5. 0.7mL of propylamine was poured into the reactor (ca. 0.0085 mol);
6. ultrasonic dissolving to obtain oil phase;
7、Zn(NO3)2*6H2o is dissolved in water at a concentration of 0.0001mol/mL, Al2(SO4)3*18H2Dissolving O in water at the concentration of 0.00008mol/mL, and dissolving formaldehyde in water at the concentration of 0.0014mol/mL to serve as a water phase;
8. taking 7mL of water phase and 7mL of oil phase, and quickly injecting the water phase and the oil phase into the oil phase reactor through a double-continuous-phase preparation device (the key point is to ensure that the whole liquid is mixed milky, has no layering, no bubbles and no clear liquid to retain after injection) (the molar ratio of the number of positive charges of cations to the number of negative charges of anions theoretically generated by alkaline organic matters is about 0.55);
9. standing for 24h at normal temperature;
10. drying for 24 hours at 60 ℃ under an aerobic condition;
11. thermally polymerizing for 24 hours at the temperature of 100 ℃;
the whole is obtained after 24 hours of drying at 100 ℃ in the presence of oxygen, and the shrinkage rate is 10%.
Example 6
1. A macroscopic 3D multi-stage porous nano material one-step synthesis method comprises the following steps:
2. 0.7g didodecyldimethylammonium bromide (DDAB) (concentration 0.05g/mL, 100% dissolved in the oil phase) was weighed into a reactor (25mL beaker);
3. pouring 3.5mL of Tetraethoxysilane (TEOS) into the reactor;
4. 3.5mL dodecane was poured into the reactor (organic solvent about 50% of the oil phase);
5. 0.7mL of benzylamine was poured into the reactor (ca. 0.0063 mol);
6. ultrasonic dissolving to obtain oil phase;
7、Zn(NO3)2*6H2dissolving O in water at the concentration of 0.000336146mol/mL to serve as a water phase;
8. taking 7mL of water phase to rapidly inject into the oil phase reactor (the key is to ensure that the whole liquid is mixed milky, has no layering, has no bubbles and has no clear liquid stay after injection) (the molar ratio of the positive charge number of the cation to the negative charge number of the anion generated by the alkaline organic matter is about 0.7);
9. standing for 24h at normal temperature;
10. drying for 24 hours at 70 ℃ under an aerobic condition;
the whole is obtained after 24 hours of drying at 70 ℃ under aerobic condition, and the shrinkage rate is 5.6%.
Example 7
A macroscopic 3D multi-stage porous nano material one-step synthesis method comprises the following steps:
1. 0.7g didodecyldimethylammonium bromide (DDAB) (concentration 0.05g/mL, 100% dissolved in the oil phase) was weighed into a reactor (25mL beaker);
2. pouring 3.5mL of Tetraethoxysilane (TEOS) into the reactor;
3. 3.5mL of monobromo tetradecane is poured into a reactor (the organic solvent accounts for about 50 percent of the oil phase);
4. 0.7mL of benzylamine was poured into the reactor (ca. 0.0063 mol);
5. ultrasonic dissolving to obtain oil phase;
6、MgSO4·7H2o of 0.000168073mol/mL and Al2(SO4)3*18H2O of 5.60243E-05mol/mL as the aqueous phase;
7. taking 7mL of water phase and quickly injecting the water phase into the oil phase reactor; (the molar ratio of the number of positive cationic charges to the number of negative anionic charges theoretically generated by the basic organic substance is about 0.7)
8. Standing for 24h at normal temperature;
9. drying for 24 hours at 70 ℃ under an aerobic condition;
FIG. 4 shows that the shrinkage of the whole is 6.6% after 24 hours of drying at 70 ℃ in the presence of oxygen.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The macroscopic 3D multi-stage porous nano material one-step synthesis method is characterized by comprising the following steps of: the method comprises the following steps:
1) adding a surfactant and an oil phase reaction precursor into an organic solvent to serve as an oil phase; adding a water phase reaction precursor into water to serve as a water phase;
2) contacting and mixing the oil phase and the water phase to form a bicontinuous emulsion of an oil-water bicontinuous phase interface;
3) standing to obtain a macroscopic 3D multi-stage porous nano material; in the step 1), the oil phase reaction precursor is an alkaline organic matter, and the water phase reaction precursor is a metal salt; in the step 2), after the oil phase is contacted and mixed with water, hydroxide precipitation is generated on an oil-water interface between the basic organic matter and the metal salt, and the hydroxide precipitation is further self-assembled under the action of a surfactant and surface tension to form a supporting layer with a nano structure;
in the step 1), the volume ratio of the organic solvent to the oil phase is 10-80%; in the step 1) and the step 2), the density of the oil phase is 0.6-1.3 times of the density of the water phase, and the viscosity of the oil phase is 0.7-1.6 times of the viscosity of the water phase; in the step 2), the mixing ratio of the water phase and the oil phase is 1: 3-3: 1, after the oil phase and the water phase are contacted and mixed, the concentration of positive cationic charges in a precursor of a water phase reaction is 0.00001-0.005 mol/mL, and the molar ratio of the number of positive cationic charges to the number of negative anionic charges theoretically generated by a basic organic matter is 0.5-0.8.
2. The macroscopic 3D multi-stage porous nano-material one-step synthesis method according to claim 1, characterized in that: the chemical molecular composition of hydroxide precipitation is
Wherein X is 0-1, M2+、M3+Is a metal ion, An-Is an interlayer anion.
3. The macroscopic 3D multi-stage porous nano-material one-step synthesis method according to claim 1, characterized in that: in the step 1), the oil phase reaction precursor further comprises metal alkoxide for forming a functional layer and/or macromolecules in organic polymerization reaction.
4. The macroscopic 3D multi-stage porous nano-material one-step synthesis method according to claim 3, characterized in that: when the oil phase reaction precursor comprises macromolecules in organic polymerization reaction, the water phase reaction precursor also comprises micromolecules in organic polymerization reaction, and the macromolecules in the organic polymerization reaction and the micromolecules in the organic polymerization reaction are subjected to one or more of addition, condensation and polycondensation reaction to generate resin.
5. The macroscopic 3D multi-stage porous nano-material one-step synthesis method according to claim 1, characterized in that: in step 1), a surfactant is also added to the water as an aqueous phase.
6. The macroscopic 3D multi-stage porous nano-material one-step synthesis method according to claim 5, wherein: the addition amount of the surfactant in the oil phase accounts for more than 50% of the addition amount of the total surfactant, and the addition amount of the surfactant in the water phase accounts for less than 50% of the addition amount of the total surfactant; the total surfactant is added in a ratio of the total volume of the oil phase and the water phase, and the concentration of the total surfactant is 1 g/mL-0.001 g/mL.
7. The one-step synthesis method of macroscopic 3D multi-stage porous nano-materials according to any one of claims 1 to 6, characterized in that: the organic solvent is one or a combination of more of 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromoundecane, 1-bromotetradecane, chlorocyclohexane, 1-bromohexadecane, 4-methyl-3-ethylheptane, 4-methylundecane, n-tridecane, n-eicosane, tert-butyl benzene and 1, 1-diphenylheptane; the HLB of the surfactant is 2-7, and the surfactant is didodecyldimethylammonium bromide and/or lecithin.
8. The one-step synthesis method of macroscopic 3D multi-stage porous nano-materials according to any one of claims 1 to 6, characterized in that: in the step 3), the standing is carried out for 12-48 h at room temperature under normal pressure.
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