CN114044667A - Mesoporous inorganic fiber composite material and preparation method and application thereof - Google Patents
Mesoporous inorganic fiber composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 238000011282 treatment Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000012452 mother liquor Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 230000032683 aging Effects 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 25
- 230000004048 modification Effects 0.000 claims description 22
- 238000012986 modification Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000010413 mother solution Substances 0.000 claims description 7
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001879 gelation Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004964 aerogel Substances 0.000 abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000013335 mesoporous material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000004965 Silica aerogel Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- -1 sensors Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
- C04B14/064—Silica aerogel
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/04—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
Abstract
The invention relates to a mesoporous inorganic fiber composite material and a preparation method and application thereof, belonging to the technical field of inorganic composite materials. The method adopts the high-temperature treatment technology to construct a nano structure on the surface of the halloysite fiber, adopts the hydrothermal treatment method to enrich the surface hydroxyl group, and then takes the fiber membrane as a base material to compound the fiber membrane with the silicon dioxide aerogel mother liquor so as to fill the silicon aerogel mother liquor into the gaps of the fiber membrane; and preparing the compact aerogel composite material by a normal pressure drying method. The preparation method can obtain the mesoporous inorganic fiber composite material by using a normal pressure drying method, has no volume shrinkage, is compact and has no cracks, can simplify the preparation process of the normal pressure drying method, greatly improves the preparation efficiency, saves the cost, and is expected to be widely applied to the fields of high-efficiency adsorption, nano catalyst loading, high-temperature gas catalysis and the like.
Description
Technical Field
The invention relates to the technical field of inorganic composite materials, in particular to a mesoporous inorganic fiber composite material and a preparation method and application thereof.
Background
Porous materials are generally classified into macroporous materials, mesoporous materials (pore diameter of 2-50nm) and micro-nanoporous materials according to the pore diameter distribution. The porous material rich in the nanometer pore channel structure is designed by a specific process, so that the specific surface area of the material can be greatly increased, the material can obtain more interfaces which interact with external substances, and the application field of the porous material can be further widened. In addition, the double mesoporous material has double mesoporous channels with different sizes, has the characteristics of efficiently dispersing active substances and simultaneously providing efficient diffusion channels, and has application potential particularly when being used as a catalyst carrier.
The silica aerogel is a mesoporous material, has high porosity (usually more than 80%) and a three-dimensional nano-pore network structure compared with a conventional porous material with the pore diameter of more than micron, and has various excellent performances required by super heat insulation, high-efficiency catalyst carriers, sensors, adsorbents, low dielectric materials and the like.
However, the high porosity causes a decrease in mechanical properties of the material itself, and the material has extremely low strength and is liable to cause sudden failure, and it is difficult to directly apply the aerogel in the form of a plate or a sheet. In practical application, the defect of insufficient strength or toughness can be obviously improved by compounding the aerogel and the fibers, so that the excellent performance of the aerogel and the fibers can be better exerted, and the requirement of engineering application on the comprehensive performance of the material is met.
Much research is currently focused on the preparation of fiber-reinforced flexible aerogels and the study of their insulating properties. However, in the various fiber reinforced materials used at present, the composite aerogel prepared by using the normal pressure drying technology has the problem of volume shrinkage and obvious cracks, and the existence of the cracks can reduce the mechanical property and obviously influence the service performance. It is very important to improve the interfacial adhesion between the fibers and the aerogel. In order to improve the bonding force of the two-phase interface, it is necessary to develop other interface interactions in addition to chemical bonding. In addition, in order to obtain the complete crack-free aerogel composite material, a supercritical drying technology is mostly adopted for preparation, and the technical conditions are harsh, the operation is complex, the equipment requirement is high, the energy consumption is also high, and the cost is high.
Disclosure of Invention
Therefore, it is necessary to provide a method for preparing a mesoporous inorganic fiber composite material, which can dry the prepared aerogel fiber composite material under normal pressure, and has the advantages of simple operation, low equipment requirement, low energy consumption and low cost.
A preparation method of a mesoporous inorganic fiber composite material comprises the following steps:
preparing a base material: treating a halloysite fiber membrane at a high temperature to generate nano-scale protrusions on the surface of the halloysite fiber membrane, adding an acid solution, and treating by a hydrothermal method to increase the hydroxyl groups on the surface of the halloysite fiber membrane to obtain a substrate;
preparing mother liquor: preparing uniform silica sol mother liquor by acid-catalyzed ethyl orthosilicate hydrolysis and alkali-catalyzed gelation;
preparation of precursor composite: filling the mother solution into fiber gaps of the base material to obtain a precursor composite material;
aging treatment: gelling, aging and aging the precursor composite material;
modification treatment: carrying out surface modification on the precursor composite material subjected to aging treatment by using trimethylchlorosilane, and then cleaning by using normal hexane to regulate and control the aperture size of the precursor composite material;
and (3) drying: and drying the modified precursor composite material under normal pressure to obtain the modified precursor composite material.
According to the preparation method of the mesoporous inorganic fiber composite material, a nano structure is constructed on the surface of the halloysite fiber by adopting a high-temperature treatment technology, the surface hydroxyl groups are enriched by adopting a hydrothermal treatment method, and then the fiber membrane is taken as a base material and is compounded with the silicon dioxide aerogel mother liquor, so that the silicon aerogel mother liquor is filled in the gaps of the fiber membrane; the compact aerogel composite material is prepared by a normal pressure drying method, and can be subjected to secondary modification treatment as required to realize the regulation and control of the pore diameter.
Wherein, for the regulation and control of the aperture, the molar ratio of the ethyl orthosilicate to the ethanol in the mother solution can be controlled and controlled, if the aperture needs to be controlled and controlled to be increased, the proportion of the ethyl orthosilicate is increased, and if the aperture needs to be controlled and controlled to be reduced, the proportion of the ethanol is increased.
It can be understood that the halloysite fiber membrane is an inorganic fiber membrane of a multistage nano mechanism which is obtained by an electrostatic spinning process and calcination, has high porosity and high water flux, and has a large number of nano protrusions and abundant hydroxyl groups on the surface of the fiber. The nanofiber membrane prepared by the needle-free electrostatic spinning technology has controllable size and thickness, uniform and adjustable pore diameter, the integral porosity of the fiber membrane can reach 80%, the pore volume is extremely large, and a network pore channel formed by mutually overlapped ceramic fibers in the nanofiber membrane can be very firmly embedded and supported by silicon dioxide aerogel, so that the physical interface hinging effect is provided for the nanofiber membrane except for chemical bonding. And the surface of the nano-particles is subjected to high-temperature treatment to generate a large number of nano-protrusions, and the surface hydroxyl groups of the nano-particles can be increased by using an acid solution hydrothermal method for treatment.
In one embodiment, in the substrate preparation step, the high temperature condition is treatment at 800-1500 ℃ for 1-12 h;
the acid solution is a nitric acid aqueous solution with the concentration of 1-5 mol/L;
the hydrothermal temperature adopted in the hydrothermal method is 60-240 ℃, and the hydrothermal time is 2-24 h.
In one embodiment, the mother liquor preparation step comprises the following steps:
1) adding tetraethoxysilane and ethanol into a container, stirring and mixing uniformly, adding acid to adjust the pH value of the solution to 2-3, mixing uniformly to hydrolyze the tetraethoxysilane fully, and then adding a drying control agent;
2) adding ammonia water into the solution, and controlling the pH value to be 7-8 to form uniform silica sol liquid, namely obtaining the mother solution.
In one embodiment, the mother liquor preparation step comprises the following steps:
1) adding tetraethoxysilane and ethanol with the molar ratio of 1:4-20 into a container, stirring and mixing uniformly, adding a hydrochloric acid aqueous solution to adjust the pH value of the solution to 2-3, stirring for 1-10h to fully hydrolyze the tetraethoxysilane, and then adding nitrogen-nitrogen dimethylformamide; the molar ratio of water to hydrochloric acid in the hydrochloric acid aqueous solution is 1:2-6 × 10-4；
2) Adding ammonia water solution to control the pH value to be 7-8 to form uniform silica sol liquid; in the ammonia water solution, the molar ratio of water to strong ammonia water is 1:6-9 multiplied by 10-4。
In one embodiment, the mother liquor preparation step comprises the following steps:
1) adding tetraethoxysilane and ethanol with the molar ratio of 1:4-20 into a container, stirring for 5-30min and uniformly mixing by a magnetic stirrer at the speed of 100-500rpm, adding a hydrochloric acid aqueous solution to adjust the pH value of the solution to 2-3, magnetically stirring for 1-10h at room temperature to fully hydrolyze the tetraethoxysilane, and then adding nitrogen-nitrogen dimethylformamide; the molar ratio of water to hydrochloric acid in the hydrochloric acid aqueous solution is 1:2-6 × 10-4；
2) Adding ammonia water solution to control the pH value to be 7-8 to form uniform silica sol liquid; in the ammonia water solution, the molar ratio of water to strong ammonia water is 1:6-9 multiplied by 10-4。
In one embodiment, in the step of preparing the composite material, the mother liquid is filled into the substrate by using a dipping method, a pulling method or a dropping method.
In one embodiment, in the precursor composite preparation step, the fiber voids of the substrate are filled with the mother liquor by shaking, sonication or evacuation.
In one embodiment, in the precursor composite preparation step, the time for filling the mother liquor into the fiber voids of the substrate is 10 to 100 min.
In one embodiment, in the aging treatment step, the precursor composite material is transferred into a closed container for gelation, aging and aging, wherein the aging time is 0-24h, and the aging time is 6-72 h. It is understood that the gelling can also be carried out in an open system, but in a closed environment, the cracking of the composite fiber membrane caused by the too rapid evaporation of the liquid can be avoided.
It is understood that the aging and aging can be performed according to the conventional procedures in the art, such as aging, i.e. standing at room temperature, aging is soaking and standing after adding ethanol or ethanol/tetraethoxysilane mixed solution, and the aging time can be designed according to specific requirements, such as obtaining large aperture distribution without aging.
In one embodiment, in the modification treatment step, a mixed solution of trimethylchlorosilane and n-hexane with the volume of 1:10-20 is used for carrying out surface modification on the precursor composite material, the modification time is 0-24h, and the cleaning time is 12-36 h.
It can be understood that the minimum value of the modification time is 0h, that is, the pore diameter is not regulated through modification treatment, and the mesoporous inorganic fiber composite material can be obtained, but the performance is poor. If the pore diameter is regulated, the modification time can be controlled to be 0.5-24 h.
In one embodiment, in the drying step, the precursor composite material is dried in an air circulation oven at a first temperature of 45-80 ℃ for 6-12h, then dried at a second temperature of 80-150 ℃ for 2-8h, and naturally cooled to obtain the composite material.
In one embodiment, the rate of increasing the temperature from the first temperature to the second temperature in the drying step is 0.1-1 ℃/min. The composite fiber membrane material with complete structure can be obtained by selecting the speed to heat.
In one embodiment, the mesoporous inorganic fiber composite material is a double mesoporous inorganic fiber composite material, and the precursor composite material preparation, the aging treatment, the modification treatment and the drying step are sequentially repeated after the drying step. By repeating the modification treatment process, materials with different pore diameters can be obtained, and it can be understood that for the two modification treatments, the molar ratio of the tetraethoxysilane to the ethanol can be adjusted according to the pore diameter distribution to be obtained.
The invention also discloses the mesoporous inorganic fiber composite material prepared by the preparation method.
The invention also discloses application of the mesoporous inorganic fiber composite material as a catalyst carrier.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the mesoporous inorganic fiber composite material, a nano structure is constructed on the surface of the halloysite fiber by adopting a high-temperature treatment technology, the surface hydroxyl groups are enriched by adopting a hydrothermal treatment method, and the fiber membrane is taken as a base material and is compounded with the silica aerogel mother liquor to fill the silicon aerogel mother liquor into the gaps of the fiber membrane; the compact aerogel composite material is prepared by a normal pressure drying method, and the pore diameter of the aerogel composite material can be regulated and controlled by carrying out secondary modification treatment on the aerogel composite material according to the requirement. By the method, the constructed rigid nano multi-scale fiber membrane has strong bonding force with the silicon aerogel and stable structure, and can prevent the silicon aerogel from generating hole collapse in the drying process, so that the mesoporous composite membrane with narrow pore size distribution and the preparation of the double mesoporous aerogel composite material can be prepared under the condition of normal pressure drying.
Meanwhile, the preparation method can obtain the mesoporous inorganic fiber composite material by using a normal pressure drying method, has no volume shrinkage, is compact and has no crack, can simplify the preparation process of the normal pressure drying method, greatly improves the preparation efficiency and saves the cost.
In addition, the aperture of the mesoporous inorganic fiber composite material prepared by the method of the invention is adjustable within the range of 5nm to 50 nm. The silica aerogel/halloysite fiber membrane composite material is expected to be widely applied in the fields of high-efficiency adsorption, nano catalyst loading, high-temperature gas catalysis and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a composite aerogel prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the composite aerogel prepared in example 2 of the present invention;
fig. 3 is a pore size distribution diagram of the mesoporous material prepared in example 2 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
A mesoporous inorganic fiber composite material is prepared by the following method:
1. and (4) preparing a base material.
Treating the halloysite fiber membrane at 1200 ℃ for 2h, then carrying out hydrothermal treatment on the halloysite fiber membrane in a nitric acid solution with the concentration of 2mol/L, wherein the hydrothermal temperature is 180 ℃ and the hydrothermal time is 12h, and then cleaning the halloysite fiber membrane to be neutral and drying the halloysite fiber membrane to obtain the base material.
2. And (5) preparing a mother solution.
The uniform silica sol mother liquor is prepared by acid-catalyzed ethyl orthosilicate hydrolysis and alkali-catalyzed gelation, and the specific preparation method comprises the following steps:
a. mixing Tetraethoxysilane (TEOS) and ethanol uniformly according to the molar ratio of 1:10, stirring the mixture for 5 to 30min under the condition of a magnetic stirrer of 100--4Stirring for 1h at room temperature to fully hydrolyze the mixture, and then adding a proper amount of DMF (dimethyl formamide) according to a molar ratio of TEOS to DMF (1: 0.6)
b. Then dripping 25 wt% of mixed solution of ammonia water and water into the liquid within 10min, adjusting the pH value to 7-8 to form uniform silica sol liquid, wherein the molar ratio of water to ammonia water is 1:9 × 10-4。
3. Preparing a precursor composite material.
And (3) soaking the base material treated in the step (1) in the sol mother liquor prepared in the step (2), and vibrating and filling for 10min in a shaking table at 40 ℃ and 200 r/min.
4. And (5) aging treatment.
(1) Transferring the precursor composite material obtained in the step into a closed container for gelling;
(2) after aging at room temperature for 5h, ethanol was added and aging continued for 24 h.
5. And (5) modification treatment.
(1) Adding a mixed solution of trimethylchlorosilane and normal hexane in a volume ratio of 1:15, and modifying for 12 hours.
(2) Then soaking the mixture in n-hexane for 12 h.
6. And (5) drying.
Drying at normal pressure, drying at 68 ℃ for 6h, drying at 100 ℃ for 2h, wherein the heating rate is 1 ℃/min, and naturally cooling to prepare the compact mesoporous inorganic fiber composite material.
7. And (5) characterizing.
According to BET pore size measurement, the average pore size of the mesoporous inorganic fiber composite material is 21.1nm, a scanning electron microscope image of the composite aerogel is shown in figure 1, and the obtained mesoporous inorganic fiber composite material has no volume shrinkage, is compact and has no cracks as can be seen from the image.
Example 2
A mesoporous inorganic fiber composite material is prepared by the following method:
1. and (4) preparing a base material.
Treating the halloysite fiber membrane at 1200 ℃ for 2h, then carrying out hydrothermal treatment on the halloysite fiber membrane in a nitric acid solution with the concentration of 2mol/L, wherein the hydrothermal temperature is 180 ℃ and the hydrothermal time is 12h, and then cleaning the halloysite fiber membrane to be neutral and drying the halloysite fiber membrane to obtain the base material.
2. And (5) preparing a mother solution.
The uniform silica sol mother liquor is prepared by acid-catalyzed ethyl orthosilicate hydrolysis and alkali-catalyzed gelation, and the specific preparation method comprises the following steps:
a. mixing Tetraethoxysilane (TEOS) and ethanol uniformly according to the molar ratio of 1:10, stirring the mixture for 5 to 30min under the condition of a magnetic stirrer of 100--4Stirring for 1h at room temperature to fully hydrolyze the mixture, and then adding a proper amount of DMF (dimethyl formamide) according to a molar ratio of TEOS to DMF (1: 0.6);
b. then dripping 25 wt% of mixed solution of ammonia water and water into the liquid within 10min, adjusting the pH value to 7-8 to form uniform silica sol liquid, wherein the molar ratio of water to ammonia water is 1:9 × 10-4。
3. Preparing a precursor composite material.
And (3) soaking the base material treated in the step (1) in the sol mother liquor prepared in the step (2), and vibrating and filling for 10min in a shaking table at 50 ℃ and 200 r/min.
4. And (5) aging treatment.
(1) Transferring the precursor composite material obtained in the step into a closed container for gelling;
(2) aging the mixture at room temperature for 5h, adding a mixed solution of ethanol and tetraethoxysilane in a volume ratio of 1:2, and continuing aging for 24 h.
5. And (5) modification treatment.
(1) Adding a mixed solution of trimethylchlorosilane and normal hexane in a volume ratio of 1:13, and modifying for 24 hours.
(2) Then soaking the mixture in n-hexane for 12 h.
6. And (5) drying.
Drying at normal pressure, drying at 68 ℃ for 6h, drying at 100 ℃ for 2h, wherein the heating rate is 1 ℃/min, and naturally cooling to prepare the compact mesoporous inorganic fiber composite material.
7. And (5) secondary modification.
Carrying out post-treatment on the composite material obtained in the previous step as follows:
a. soaking the composite material in sol mother liquor again, wherein the composition of the mother liquor is consistent with that of the mother liquor adopted in the first compounding in the step 3,
b. placing the materials at 50 ℃ for gelation, and adding ethanol to age the materials at 50 ℃ for 12 h;
c. and replacing the solvent with a mixed solution of trimethylchlorosilane and n-hexane in a volume ratio of 1:13, continuing to soak for 12 hours, and then replacing the solvent with n-hexane and soaking for 12 hours.
d. Drying by adopting a normal pressure drying method, specifically heating to 68 ℃ at a heating rate of 1 ℃/min for drying for 10h, heating to 100 ℃ at the same heating rate, drying for 2h, and finally, naturally cooling to obtain the double mesoporous composite membrane material.
8. And (5) characterizing.
The mesoporous inorganic fiber composite material is taken, BET pore size measurement shows that the average pore size is 9.07nm, and double mesoporous distribution is shown. The scanning electron microscope image of the composite aerogel is shown in fig. 2, and it can be seen from the image that the obtained mesoporous inorganic fiber composite material has no volume shrinkage, is dense and has no cracks, and the pore size distribution diagram of the double mesoporous material is shown in fig. 3.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the mesoporous inorganic fiber composite material is characterized by comprising the following steps:
preparing a base material: treating a halloysite fiber membrane at a high temperature to generate nano-scale protrusions on the surface of the halloysite fiber membrane, adding an acid solution, and treating by a hydrothermal method to increase the hydroxyl groups on the surface of the halloysite fiber membrane to obtain a substrate;
preparing mother liquor: preparing uniform silica sol mother liquor by acid-catalyzed ethyl orthosilicate hydrolysis and alkali-catalyzed gelation;
preparation of precursor composite: filling the mother solution into fiber gaps of the base material to obtain a precursor composite material;
aging treatment: gelling, aging and aging the precursor composite material;
modification treatment: carrying out surface modification on the precursor composite material subjected to aging treatment by using trimethylchlorosilane, and then cleaning by using normal hexane to regulate and control the aperture size of the precursor composite material;
and (3) drying: and drying the modified precursor composite material under normal pressure to obtain the modified precursor composite material.
2. The method for preparing the mesoporous inorganic fiber composite material according to claim 1, wherein in the step of preparing the base material, the high temperature condition is treatment at 800-1500 ℃ for 1-12 h;
the acid solution is a nitric acid aqueous solution with the concentration of 1-5 mol/l;
the hydrothermal temperature adopted in the hydrothermal method is 60-240 ℃, and the hydrothermal time is 2-24 h.
3. The method for preparing the mesoporous inorganic fiber composite material according to claim 1, wherein the mother liquor preparation step comprises the following steps:
1) adding tetraethoxysilane and ethanol into a container, stirring and mixing uniformly, adding acid to adjust the pH value of the solution to 2-3, mixing uniformly to hydrolyze the tetraethoxysilane fully, and then adding a drying control agent;
2) adding ammonia water into the solution, and controlling the pH value to be 7-8 to form uniform silica sol liquid, namely obtaining the mother solution.
4. The method for preparing the mesoporous inorganic fiber composite material according to claim 3, wherein the mother liquor preparation step comprises the following steps:
1) adding tetraethoxysilane and ethanol with the molar ratio of 1:4-20 into a container, stirring and mixing uniformly, adding a hydrochloric acid aqueous solution to adjust the pH value of the solution to 2-3, stirring for 1-10h to fully hydrolyze the tetraethoxysilane, and then adding nitrogen-nitrogen dimethylformamide; the molar ratio of water to hydrochloric acid in the hydrochloric acid aqueous solution is 1:2-6 × 10-4；
2) Adding ammonia water solution to control the pH value to be 7-8 to form uniform silica sol liquid; in the ammonia water solution, the molar ratio of water to strong ammonia water is 1:6-9 multiplied by 10-4。
5. The method for preparing the mesoporous inorganic fiber composite material according to claim 1, wherein in the aging treatment step, the aging time is 0-24 hours and the aging time is 6-72 hours.
6. The method for preparing the mesoporous inorganic fiber composite material according to claim 1, wherein in the modification treatment step, the precursor composite material is subjected to surface modification by using a mixed solution of trimethylchlorosilane and n-hexane with a volume of 1:10-20, the modification time is 0-24h, and the cleaning time is 12-36 h.
7. The method for preparing the mesoporous inorganic fiber composite material according to claim 1, wherein in the drying step, the precursor composite material is dried in an air circulation oven at a first temperature of 45-80 ℃ for 6-12h, then dried at a second temperature of 80-150 ℃ for 2-8h, and naturally cooled to obtain the mesoporous inorganic fiber composite material.
8. The method of preparing the mesoporous inorganic fiber composite material according to claim 1, wherein the mesoporous inorganic fiber composite material is a bi-mesoporous inorganic fiber composite material, and the steps of preparing the precursor composite material, aging, modifying, and drying are sequentially repeated after the drying step.
9. The mesoporous inorganic fiber composite material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the mesoporous inorganic fiber composite of claim 9 as a catalyst support.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005022881A (en) * | 2003-06-30 | 2005-01-27 | Japan Science & Technology Agency | Mesoporous silica having bimodal type pore structure, and method of preparing the same |
| CN102557577A (en) * | 2011-11-01 | 2012-07-11 | 厦门纳美特新材料科技有限公司 | Preparation and method of silicon dioxide aerogel composite material |
| CN102965848A (en) * | 2012-11-15 | 2013-03-13 | 广州市香港科大***研究院 | Nanometre porous ceramic film and preparation method thereof |
| CN103102135A (en) * | 2013-02-21 | 2013-05-15 | 吴会军 | Electrospun micro-nanofiber reinforced aerogel flexible thermal insulation material and its preparation method |
| CN108467276A (en) * | 2018-03-20 | 2018-08-31 | 中国科学院城市环境研究所 | A kind of preparation method of electrostatic spinning nano fiber enhancing aerosil |
| CN108569912A (en) * | 2018-04-29 | 2018-09-25 | 浙江工业大学 | A kind of preparation method of hydrophobic type aerosil composite fibre felt material |
| CN112661482A (en) * | 2021-01-11 | 2021-04-16 | 中广核研究院有限公司 | Fiber composite aerogel material and preparation method and application thereof |
-
2021
- 2021-11-23 CN CN202111394302.8A patent/CN114044667A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005022881A (en) * | 2003-06-30 | 2005-01-27 | Japan Science & Technology Agency | Mesoporous silica having bimodal type pore structure, and method of preparing the same |
| CN102557577A (en) * | 2011-11-01 | 2012-07-11 | 厦门纳美特新材料科技有限公司 | Preparation and method of silicon dioxide aerogel composite material |
| CN102965848A (en) * | 2012-11-15 | 2013-03-13 | 广州市香港科大***研究院 | Nanometre porous ceramic film and preparation method thereof |
| US20140131271A1 (en) * | 2012-11-15 | 2014-05-15 | The Hkust Fok Ying Tung Research Institute | Nanoporous ceramic membrane and preparation method thereof |
| CN103102135A (en) * | 2013-02-21 | 2013-05-15 | 吴会军 | Electrospun micro-nanofiber reinforced aerogel flexible thermal insulation material and its preparation method |
| CN108467276A (en) * | 2018-03-20 | 2018-08-31 | 中国科学院城市环境研究所 | A kind of preparation method of electrostatic spinning nano fiber enhancing aerosil |
| CN108569912A (en) * | 2018-04-29 | 2018-09-25 | 浙江工业大学 | A kind of preparation method of hydrophobic type aerosil composite fibre felt material |
| CN112661482A (en) * | 2021-01-11 | 2021-04-16 | 中广核研究院有限公司 | Fiber composite aerogel material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 许亚军: "羟基化玻璃纤维增强硅气凝胶常温常压制备与性能分析" * |
| 许亚军: "羟基化玻璃纤维增强硅气凝胶常温常压制备与性能分析", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
| 郭翠梨等: "双介孔材料的合成与应用研究进展" * |
| 郭翠梨等: "双介孔材料的合成与应用研究进展", 《化工进展》 * |
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