CN110227435B - Macroscopic 3D high-porosity low-permeability nano catalytic material and preparation method thereof - Google Patents
Macroscopic 3D high-porosity low-permeability nano catalytic material and preparation method thereof Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000011343 solid material Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical group NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 14
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical group [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 claims description 7
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- -1 aluminum ions Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052564 epsomite Inorganic materials 0.000 claims description 6
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 6
- 229940067606 lecithin Drugs 0.000 claims description 6
- 235000010445 lecithin Nutrition 0.000 claims description 6
- 239000000787 lecithin Substances 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004530 micro-emulsion Substances 0.000 claims description 5
- 229940094933 n-dodecane Drugs 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 3
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 claims description 3
- MZLKNWMNBXHXMA-UHFFFAOYSA-N 1-phenylheptylbenzene Chemical compound C=1C=CC=CC=1C(CCCCCC)C1=CC=CC=C1 MZLKNWMNBXHXMA-UHFFFAOYSA-N 0.000 claims description 3
- JZBKRUIGSVOOIC-UHFFFAOYSA-N 3-ethyl-4-methylheptane Chemical compound CCCC(C)C(CC)CC JZBKRUIGSVOOIC-UHFFFAOYSA-N 0.000 claims description 3
- KNMXZGDUJVOTOC-UHFFFAOYSA-N 4-methylundecane Chemical compound CCCCCCCC(C)CCC KNMXZGDUJVOTOC-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 claims description 3
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 230000003204 osmotic effect Effects 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 238000000593 microemulsion method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/14—Silica and magnesia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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Abstract
The invention discloses a macroscopic 3D high-porosity low-permeability nano catalytic material, which belongs to the technical field of nano materials, wherein the strength of the nano catalytic material is higher than 5kPa, the final solid shrinkage rate from liquid to solid is less than or equal to 15%, and the surface area is more than or equal to 100m2G, density is less than or equal to 0.1g/cm‑3The porosity of the whole solid material is more than or equal to 90 percent, and the osmotic pressure is less than or equal to 10 MPa/m. The invention also discloses a preparation method of the composition. According to the macroscopic 3D high-porosity low-permeability nano catalytic material, the macroscopic shape of the material can be easily controlled, the whole material has rich pores, the material has high porosity, the porosity is more than 90%, the osmotic pressure is less than or equal to 10MPa/m, the catalytic degradation performance on organic matters is good, and the degradation rate is more than 80%; the preparation method of the macroscopic 3D high-porosity low-permeability nano catalytic material has the advantages of simple process, easiness in operation and controllable process.
Description
Technical Field
The invention belongs to the technical field of nano material doping, and particularly relates to a macroscopic 3D high-porosity low-permeability nano catalytic material and a preparation method thereof.
Background
Nanomaterials generally refer to materials that have at least one dimension in three dimensions in the nanoscale range or that are composed of them as the basic unit. The nanometer catalytic material is used as a branch of the nanometer material, has the general properties of the nanometer material, and simultaneously meets the requirements of the catalytic material on the particle size, the surface area, the electronic property, the adsorption performance, the catalytic reaction performance and the like.
The synthesis method of the nano catalytic material is one of the most direct and key influencing factors on the catalytic performance. The synthesis methods commonly used at present are as follows: precipitation, sol-gel, hydrolysis, hydrothermal and microemulsion, etc., the microemulsions are usually composed of surfactants, cosurfactants, solvents and water. The microemulsion method is characterized in that two immiscible continuous media are utilized to form a hooked emulsion under the action of a surfactant, a solvent with a small dosage is wrapped in a solvent with a large dosage to form a plurality of micro-bubbles, the surfaces of the micro-bubbles are composed of the surfactant, and the processes of nucleation, growth, coagulation, agglomeration and the like of nano particles in the micro-bubbles are limited in a micro droplet micro-reactor, so that dispersed spherical particles are formed, and further agglomeration among the spherical particles is avoided. The microemulsion method has the advantages of narrow particle size distribution, controllable particle size, good stability, good monodispersity, easy modification and cutting, simple experimental device, easy operation and the like of the prepared nanoparticles, and has good development prospect.
The microstructure (such as composition, size, morphology, pore structure, and the like) of the nano catalytic material determines the electronic energy state density of the material, and finally determines the catalytic, optical, electrical, and other properties of the material. Generally, the microporous material can reduce the transmission speed of ions, further reduce the overall power performance of the material, and the mesopores can provide wider channels for ion transmission, so that the high-power characteristic of the material is ensured. However, the contribution of mesopores to the overall specific surface area of the material is low, more mesopores cause a sharp reduction in the specific surface area, and the difference in pore structure has an influence on the catalytic performance of the material. Therefore, designing and preparing nanocatalyst materials based on the different properties and requirements needed on the macro and micro scale is a challenge facing nanocatalyst materials.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a macroscopic 3D high-porosity low-permeability nano catalytic material, the strength of the nano catalytic material is higher than 5kPa, the solid shrinkage rate from liquid to final solid is less than or equal to 15%, and the surface area is more than or equal to 100m2G, density is less than or equal to 0.1g/cm-3The porosity of the whole solid material is more than or equal to 90 percent, and the osmotic pressure is less than or equal to 10 MPa/m; the invention also aims to provide a preparation method of the nano-material, which can realize the doping of the nano-material in the synthesis process.
The technical scheme is as follows: in order to achieve the purpose, the invention provides the following technical scheme:
the macroscopic 3D high-porosity low-permeability nano catalytic material has the strength higher than 5kPa, the solid shrinkage rate from liquid to final state is less than or equal to 15 percent, and the surface area is more than or equal to 100m2G, density is less than or equal to 0.1g/cm-3The porosity of the whole solid material is more than or equal to 90 percent, and the osmotic pressure is less than or equal to 10 MPa/m.
Furthermore, the nano catalytic material is a two-dimensional curved surface formed by nano materials, the curved surface comprises a plurality of layers of nano materials, and at least one layer of the nano catalytic material is a supporting layer; the curved surfaces are communicated through a nanometer pore structure.
Further, the preparation method of the macroscopic 3D high-porosity low-permeability nano catalytic material comprises the following steps:
1) adding a surfactant, tetraethoxysilane, an organic solvent and an alkaline organic matter into a reactor, and performing ultrasonic dissolution to obtain an oil phase;
2) dissolving aluminum salt and magnesium salt in water as water phase;
3) mixing the oil phase and the water phase to form bicontinuous microemulsion;
4) standing to promote the reaction precursor to generate designed reaction on the interface;
5) drying the product obtained in the step 4) at normal pressure and low temperature;
6) carrying out heat treatment on the product obtained in the step 5) to obtain the macroscopic 3D high-porosity low-permeability nano catalytic material.
Further, in the step 1), the surfactant is didodecyldimethylammonium bromide or lecithin.
Further, in step 1), the organic solvent is one or more of 1-bromotetradecane, n-dodecane, heptane, chlorocyclohexane, 1-bromohexadecane, 4-methyl-3-ethylheptane, 4-methylundecane, n-tridecane, n-eicosane, tert-butylbenzene, and 1, 1-diphenylheptane.
Further, in the step 1), the basic organic matter is benzylamine and/or propylamine.
Further, in the step 2), the aluminum salt is Al2(SO4)3·18H2O and/or Al (NO)3)3·9H2O, the magnesium salt is MgSO4·7H2O and/or Mg (NO)3)2·6H2O。
Further, in the step 1), the proportion of the addition volume of the surfactant in the total volume is 10 g/ml-0.01 g/ml, and the HLB of the surfactant is 2-7; the volume of the ethyl orthosilicate is 10-50% of the total volume of the oil phase; the organic solvent accounts for 10 to 80 percent of the volume ratio of the oil phase; the volume ratio of the alkaline organic matter to the oil phase is 0.05-0.2.
Further, in the step 2), the positive charge concentration of cations in the water phase is 0.00001-0.01 mol/mL, and the concentration ratio of aluminum ions to magnesium ions in the water phase is 1: 6-5: 1; in the step 3), the volume ratio of the water phase to the oil phase is 1: 3-3: 1, the density of the oil phase is 0.7-1.4 times of that of the water phase, and the viscosity of the oil phase is 0.8-1.2 times of that of the water phase.
Further, in the step 4), the standing is carried out for 24 hours at normal temperature; in the step 5), the normal-pressure low-temperature drying conditions are as follows: drying for 12-24 h under the aerobic condition at the temperature of 60-90 ℃; in step 6), the heat treatment conditions are as follows: heating for 18-24 h at 400-600 ℃ under the condition of nitrogen.
Has the advantages that: compared with the prior art, the macroscopic 3D high-porosity low-osmotic-pressure nano catalytic material has the advantages that the macroscopic shape of the material can be easily controlled, the pore channels of the whole material are rich, the material has high porosity, the porosity is over 90 percent, the osmotic pressure is less than or equal to 10MPa/m, the catalytic degradation performance on organic matters is good, and the degradation rate is over 80 percent; the preparation method of the macroscopic 3D high-porosity low-permeability nano catalytic material has the advantages of simple process, easiness in operation and controllable process.
Drawings
FIG. 1 is a SEM image of a cross section of bulk nanomaterial-nanosurface material of example 1;
fig. 2 is a SEM image of the multi-stage porous structure of example 1.
Detailed Description
The invention will be further described with reference to the following drawings and specific embodiments.
The macroscopic 3D high-porosity low-permeability nano catalytic material has the strength higher than 5kPa, the solid shrinkage rate from liquid to final state less than or equal to 15 percent, the surface area more than or equal to 100m2/g, and the density less than or equal to 0.1g/cm-3The porosity of the whole solid material is more than or equal to 90 percent, and the osmotic pressure is less than or equal to 10 MPa/m.
The nano catalytic material is a two-dimensional curved surface consisting of nano materials, the curved surface comprises a plurality of layers of nano materials, and at least one layer of the nano catalytic material is a supporting layer; the curved surfaces are communicated through a nano-scale pore structure.
The preparation method of the macroscopic 3D high-porosity low-permeability nano catalytic material comprises the following steps:
1) adding a surfactant, tetraethoxysilane, an organic solvent and an alkaline organic matter into a reactor, and performing ultrasonic dissolution to obtain an oil phase;
2) dissolving aluminum salt and magnesium salt in water as water phase;
3) rapidly mixing the oil phase and the water phase to form bicontinuous microemulsion;
4) standing to promote the reaction precursor to generate designed reaction on the interface;
5) drying the product obtained in the step 4) at normal pressure and low temperature;
6) carrying out heat treatment on the product obtained in the step 5) to obtain the macroscopic 3D high-porosity low-permeability nano catalytic material.
In the step 1), the surfactant is didodecyldimethylammonium bromide or lecithin.
In the step 1), the organic solvent is one or more of 1-bromotetradecane, n-dodecane, heptane, chlorocyclohexane, 1-bromohexadecane, 4-methyl-3-ethylheptane, 4-methylundecane, n-tridecane, n-eicosane, tert-butyl benzene and 1, 1-diphenylheptane.
In the step 1), the alkaline organic matter is benzylamine and/or propylamine.
In step 2), the aluminum salt is Al2(SO4)3·18H2O and/or Al (NO)3)3·9H2O, magnesium salt is MgSO4·7H2O and/or Mg (NO)3)2·6H2O。
In the step 1), the proportion of the addition volume of the surfactant in the total volume is 10 g/ml-0.01 g/ml, and the HLB of the surfactant is 2-7; the volume of the ethyl orthosilicate is 10-50% of the total volume of the oil phase; the organic solvent accounts for 10 to 80 percent of the volume ratio of the oil phase; the volume ratio of the alkaline organic matter to the oil phase is 0.05-0.2.
In the step 2), the positive charge concentration of cations in the water phase is 0.00001-0.01 mol/mL, and the concentration ratio of aluminum ions to magnesium ions in the water phase is 0.3-3.0; the volume ratio of the water phase to the oil phase is 1: 3-3: 1, the density of the oil phase is 0.7-1.4 times of that of the water phase, and the viscosity of the oil phase is 0.8-1.2 times of that of the water phase.
In the step 4), standing is carried out for 24 hours at normal temperature; in the step 5), the normal-pressure low-temperature drying conditions are as follows: drying for 12-24 h under the aerobic condition at the temperature of 60-90 ℃; in step 6), the conditions of the further heat treatment are as follows: heating for 18-24 h at 400-600 ℃ under the condition of nitrogen.
Example 1
A macroscopic 3D high-porosity low-permeability nano catalytic material and a preparation method thereof comprise the following steps:
1. weighing 1.05g of didodecyldimethylammonium bromide (DDAB), and placing into a reactor (25ml beaker);
2. pouring 3.5ml of Tetraethoxysilane (TEOS) into a reactor;
3. 3.5ml of the tetradecane monobromolate is poured into a reactor;
4. pouring 0.7ml of benzylamine into the reactor;
5. ultrasonic dissolving to obtain oil phase;
6、Al2(SO4)3·18H2o is dissolved in water at a concentration of 0.0000560243mol/mL, MgSO4·7H2O is dissolved in water, the concentration is 0.000168073mol/mL, and the O is used as a water phase;
7. taking 7ml of water phase and 7ml of oil phase, and quickly injecting the water phase and the 7ml of oil phase into the oil phase reactor through a double-continuous-phase preparation device;
8. standing for 24h at normal temperature;
9. drying for 24 hours at 80 ℃ under an aerobic condition;
10. heating for 24 hours at 500 ℃ under aerobic condition.
The material properties are shown in table 1 below.
TABLE 1 macroscopic 3D nanocatalysis Material Properties
| Porosity (%) | Shrinkage (%) | BET(m2/g) | Strength (kPa) | Osmotic pressure (MPa/m) | Phenol degradation Rate (%) |
| 96.16 | 8.9 | 121.45 | 6.52 | 8.82 | 83.5 |
As can be seen from FIGS. 1-2, the Mg and Al nano-catalytic material has a rough surface, stacked layers and a developed pore structure.
Example 2
A macroscopic 3D high-porosity low-permeability nano catalytic material and a preparation method thereof comprise the following steps:
1. 0.7g of DDAB was weighed and placed in a reactor (25ml beaker);
2. pouring 3.5ml of Tetraethoxysilane (TEOS) into a reactor;
3. 3.5ml of the tetradecane monobromolate is poured into a reactor;
4. 1ml of propylamine is poured into a reactor;
5. ultrasonic dissolving to obtain oil phase;
6、Al2(SO4)3·18H2o is dissolved in water at a concentration of 0.00008mol/mL, MgSO4·7H2Dissolving O in water at a concentration of 0.0001mol/mL to obtain a water phase;
7. taking 7ml of water phase and 7ml of oil phase, and quickly injecting the water phase and the 7ml of oil phase into the oil phase reactor through a double-continuous-phase preparation device;
8. standing for 24h at normal temperature;
9. drying for 24 hours at 80 ℃ under an aerobic condition;
10. heating for 24 hours at 500 ℃ under aerobic condition.
The material properties are shown in table 2 below.
TABLE 2 macroscopic 3D nanocatalysis material Properties
| Porosity (%) | Shrinkage (%) | BET(m2/g) | Strength (kPa) | Osmotic pressure (MPa/m) | Phenol degradation Rate (%) |
| 92.16 | 10.4 | 251.63 | 8.12 | 7.61 | 86.0 |
Example 3
A macroscopic 3D high-porosity low-permeability nano catalytic material and a preparation method thereof comprise the following steps:
1. 0.7g of DDAB was weighed and placed in a reactor (25mL beaker);
2. pouring 3.5mL of Tetraethoxysilane (TEOS) into the reactor;
3. 3.5mL of n-dodecane is poured into the reactor;
4. pouring 0.7mL of benzylamine into the reactor;
5. ultrasonic dissolving to obtain oil phase;
6、Al(NO3)3·9H2o is dissolved in water, the concentration is 0.0000560243mol/mL, MgNO3·6H2O is dissolved in water, the concentration is 0.000168073mol/mL, and the O is used as a water phase;
7. taking 7mL of water phase and quickly injecting the water phase into the 7mL of oil phase reactor;
8. standing for 24h at normal temperature;
9. drying for 24 hours at 80 ℃ under an aerobic condition;
10. heating for 24 hours at 500 ℃ under aerobic condition.
The material properties are shown in table 3 below.
TABLE 3 macroscopic 3D nanocatalysis material Properties
| Porosity (%) | Shrinkage (%) | BET(m2/g) | Strength (kPa) | Osmotic pressure (MPa/m) | Phenol degradation Rate (%) |
| 95.36 | 12.1 | 301.45 | 8.33 | 9.24 | 87.3 |
Example 4
A macroscopic 3D high-porosity low-permeability nano catalytic material and a preparation method thereof comprise the following steps:
1. weighing 0.7g lecithin, and placing into a reactor (25ml beaker);
2. pouring 3.5ml of Tetraethoxysilane (TEOS) into a reactor;
3. 3.5ml of n-dodecane is poured into the reactor;
4. pouring 0.7ml of benzylamine into the reactor;
5. ultrasonic dissolving to obtain oil phase;
6、Al(NO3)3·9H2o is dissolved in water, the concentration is 0.000030278mol/mL, MgNO3·6H2O is dissolved in water, the concentration is 0.000019769mol/mL, and the O is used as a water phase;
7. taking 7ml of water phase and 7ml of oil phase, and quickly injecting the water phase and the 7ml of oil phase into the oil phase reactor through a double-continuous-phase preparation device;
8. standing for 24h at normal temperature;
9. drying for 24 hours at 80 ℃ under an aerobic condition;
10. heating for 24 hours at 500 ℃ under aerobic condition.
The material properties are shown in table 4 below.
TABLE 4 macroscopic 3D nanocatalysis material Properties
| Porosity (%) | Shrinkage (%) | BET(m2/g) | Strength (kPa) | Osmotic pressure (MPa/m) | Phenol degradation Rate (%) |
| 96.65 | 7.8 | 237.66 | 7.34 | 9.18 | 94.2 |
Example 5
A macroscopic 3D high-porosity low-permeability nano catalytic material and a preparation method thereof comprise the following steps:
1. weighing 0.7g lecithin, and placing into a reactor (25mL beaker);
2. pouring 3.5mL of Tetraethoxysilane (TEOS) into the reactor;
3. 3.5mL of the tetradecane monobromolate is poured into a reactor;
4. 0.7mL of propylamine is poured into the reactor;
5. ultrasonic dissolving to obtain oil phase;
6、Al2(SO4)3·18H2o is dissolved in water at a concentration of 0.0000560243mol/mL, MgSO4·7H2O is dissolved in water, the concentration is 0.000168073mol/mL, and the O is used as a water phase;
7. taking 7ml of water phase and 7ml of oil phase, and quickly injecting the water phase and the 7ml of oil phase into the oil phase reactor through a double-continuous-phase preparation device;
8. standing for 24h at normal temperature;
9. drying for 24 hours at 80 ℃ under an aerobic condition;
10. heating for 24 hours at 500 ℃ under aerobic condition.
The material properties are shown in table 5 below.
TABLE 5 macroscopic 3D nanocatalysis material Properties
| Porosity (%) | Shrinkage (%) | BET(m2/g) | Strength (kPa) | Osmotic pressure (MPa/m) | Phenol degradation Rate (%) |
| 92.47 | 13.9 | 260.23 | 5.78 | 8.95 | 90.1 |
Example 6
A macroscopic 3D high-porosity low-permeability nano catalytic material and a preparation method thereof comprise the following steps:
1. weighing 0.5g lecithin, and placing into a reactor (25mL beaker);
2. pouring 3.5mL of Tetraethoxysilane (TEOS) into the reactor; (ii) a
3.5mL of heptane is taken and put into a reactor;
4. pouring 0.5mL of benzylamine into the reactor;
5. ultrasonic dissolving to obtain oil phase;
6、Al2(SO4)3·18H2o is dissolved in water at a concentration of 0.0000560243mol/mL, MgSO4·7H2O is dissolved in water, the concentration is 0.000168073mol/mL, and the O is used as a water phase;
7. taking 7ml of water phase and 7ml of oil phase, and quickly injecting the water phase and the 7ml of oil phase into the oil phase reactor through a double-continuous-phase preparation device;
8. standing for 24h at normal temperature;
9. drying for 24 hours at 80 ℃ under an aerobic condition;
10. heating for 24 hours at 500 ℃ under aerobic condition.
The material properties are shown in table 6 below.
TABLE 6 macroscopic 3D nanocatalysis material Properties
| Porosity (%) | Shrinkage (%) | BET(m2/g) | Strength (kPa) | Osmotic pressure (MPa/m) | Phenol degradation Rate (%) |
| 90.20 | 9.5 | 311.45 | 6.78 | 9.63 | 83.2 |
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 (7)
1. The preparation method of the macroscopic 3D high-porosity low-permeability nano catalytic material is characterized by comprising the following steps of: the strength of the nano catalytic material is higher than 5kPa, the solid shrinkage rate from liquid to final is less than or equal to 15%, the surface area is greater than or equal to 100 m/g, and the density is less than or equal to 0.1g/cm-3The porosity of the whole solid material is more than or equal to 90 percent; the nano catalytic material is a two-dimensional curved surface consisting of nano materials, the curved surface comprises a plurality of layers of nano materials, and at least one layer of the nano catalytic material is a supporting layer; the curved surfaces are communicated through a nano-scale pore structure; the preparation method comprises the following steps:
1) adding a surfactant, tetraethoxysilane, an organic solvent and an alkaline organic matter into a reactor, and ultrasonically dissolving to obtain an oil phase, wherein the surfactant is didodecyl dimethyl ammonium bromide or lecithin;
2) dissolving aluminum salt and magnesium salt in water as water phase;
3) mixing the oil phase and the water phase to form bicontinuous microemulsion;
4) standing to promote the reaction precursor to generate designed reaction on the interface;
5) drying the product obtained in the step 4) at normal pressure and low temperature;
6) carrying out heat treatment on the product obtained in the step 5) to obtain the macroscopic 3D high-porosity low-permeability nano catalytic material.
2. The method for preparing the macroscopic 3D high-porosity low-permeability nanocatalysis material according to claim 1, characterized in that: in the step 1), the organic solvent is one or more of 1-bromotetradecane, n-dodecane, heptane, chlorocyclohexane, 1-bromohexadecane, 4-methyl-3-ethylheptane, 4-methylundecane, n-tridecane, n-eicosane, tert-butyl benzene and 1, 1-diphenylheptane.
3. The method for preparing the macroscopic 3D high-porosity low-permeability nanocatalysis material according to claim 1, characterized in that: in the step 1), the basic organic matter is benzylamine and/or propylamine.
4. The method for preparing the macroscopic 3D high-porosity low-permeability nanocatalysis material according to claim 1, characterized in that: in the step 2), the aluminum salt is Al2(SO4)3·18H2O and/or Al (NO)3)3·9H2O, the magnesium salt is MgSO4·7H2O and/or Mg (NO)3)2·6H2O。
5. The method for preparing the macroscopic 3D high-porosity low-permeability nanocatalysis material according to claim 1, characterized in that: in the step 1), the proportion of the addition mass of the surfactant to the total volume is 10 g/ml-0.01 g/ml, and the HLB of the surfactant is 2-7; the volume of the ethyl orthosilicate is 10% -50% of the total volume of the oil phase; the organic solvent accounts for 10-80% of the volume ratio of the oil phase; the volume ratio of the alkaline organic matter to the oil phase is 0.05-0.2.
6. The method for preparing the macroscopic 3D high-porosity low-permeability nanocatalysis material according to claim 1, characterized in that: in the step 2), the positive charge concentration of the positive ions in the water phase is 0.00001-0.01 mol/mL, and the concentration ratio of the aluminum ions to the magnesium ions in the water phase is 1: 6-5: 1; in the step 3), the volume ratio of the water phase to the oil phase is 1: 3-3: 1, the density of the oil phase is 0.7-1.4 times of that of the water phase, and the viscosity of the oil phase is 0.8-1.2 times of that of the water phase.
7. The method for preparing the macroscopic 3D high-porosity low-permeability nanocatalysis material according to claim 1, characterized in that: in the step 4), the standing is carried out for 24 hours at normal temperature; in the step 5), the normal-pressure low-temperature drying conditions are as follows: drying for 12-24 h under the aerobic condition at the temperature of 60-90 ℃; in step 6), the heat treatment conditions are as follows: heating for 18-24 h at 400-600 ℃.
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