CN110203937B - A kind of synthetic method of cubic phase ordered ultra-microporous silica - Google Patents
A kind of synthetic method of cubic phase ordered ultra-microporous silica Download PDFInfo
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- ammonium bromide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 70
- 238000010189 synthetic method Methods 0.000 title claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 98
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 48
- 238000002425 crystallisation Methods 0.000 claims description 30
- 230000008025 crystallization Effects 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000967 suction filtration Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 2
- 239000012686 silicon precursor Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 46
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 24
- 239000011148 porous material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 description 56
- 239000000463 material Substances 0.000 description 43
- 238000001308 synthesis method Methods 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- VVNBOKHXEBSBQJ-UHFFFAOYSA-M dodecyl(triethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](CC)(CC)CC VVNBOKHXEBSBQJ-UHFFFAOYSA-M 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000013333 ultra-microporous material Substances 0.000 description 1
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
本发明公开了一种立方相有序超微孔二氧化硅的合成方法，在一定温度下，将模板剂加入去离子水中并且加入一定量碱源，待模板剂完全溶解后在搅拌的条件下滴加入一定量的硅源，静置一段时间后移入水热反应釜中，于一定温度下静置晶化，在特定时间晶化后，抽滤、洗涤、干燥后得超微孔二氧化硅前驱体粉末，煅烧后得立方相有序超微孔二氧化硅分子筛。模板剂为天然松香衍生的N‑脱氢枞基‑N,N‑二甲基‑N‑羟乙基溴化铵，原料来源丰富，价格低廉；制备的有序超微孔二氧化硅具有立方相（Ia3d）结构，比表面积大、孔容高、孔径分布狭窄的特点，合成工艺简单，生产成本低，适合大规模工业化生产。
The invention discloses a method for synthesizing cubic phase ordered ultra-microporous silica. At a certain temperature, a template agent is added to deionized water and a certain amount of alkali source is added, and after the template agent is completely dissolved, under stirring conditions A certain amount of silicon source is added dropwise, and after standing for a period of time, it is moved into a hydrothermal reaction kettle, and crystallized at a certain temperature. The precursor powder is calcined to obtain a cubic phase ordered ultra-microporous silica molecular sieve. The template agent is N-dehydroabietyl-N,N-dimethyl-N-hydroxyethylammonium bromide derived from natural rosin, the raw material source is abundant, and the price is low; the prepared ordered ultra-microporous silica has cubic The phase (Ia3d) structure has the characteristics of large specific surface area, high pore volume and narrow pore size distribution, simple synthesis process and low production cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of inorganic porous materials, and particularly relates to a synthesis method of cubic phase ordered ultramicropore silicon dioxide.
Background
The ordered ultramicropore material is a series of special porous materials with the pore size of 1-2 nm. The material breaks through the limit of 1.2nm of the microporous molecular sieve and promotes the mass transfer of macromolecules. Meanwhile, they have smaller pore diameters than conventional ordered mesoporous materials to exhibit excellent shape-selective catalytic properties. In order to synthesize ordered ultramicropore materials, a short-chain surfactant is often required to be used as a template agent. However, the conventional short-chain templating agent has poor self-assembly ability and is difficult to obtain an ordered ultramicropore structure. The synthesis of ordered ultramicroporous materials remains a challenge in the field of molecular sieve synthesis due to the lack of suitable templating agents.
To solve this problem, a number of methods have been tried by researchers, such as orifice size cutting, high temperature treatment with stabilizers, composite templating agents, and special templating agents. Wherein, the last two soft template methods are more feasible, and a series of ordered ultramicropore materials are obtained according to the method. However, family members of ordered ultramicropore materials are relatively few compared to ordered mesoporous materials. For most templating agents, such as mixtures of short-chain cationic surfactants with butanol, short-chain cationic/anionic surfactants, gemini surfactants, semifluorinated surfactants, and rigid core surfactants, only hexagonally ordered ultramicropore materials with p6mm space group were synthesized. The ordered super microporous material of lamellar phase is synthesized by taking ionic liquid 1-alkyl-3-methylimidazole chloride as a template agent and adopting a nano casting method. In recent years, dodecyl triethyl ammonium bromide is used as a template agent, and bifunctional (weak acid medium and cosurfactant), succinic acid and malonic acid are used as auxiliary materials to prepare the ordered cubic Pm3n ultra-microporous aluminosilicate.
To our knowledge, no report has been made on the synthesis of cubic phase ordered ultramicropore materials with Ia3d space group by soft template method. In addition, although the above synthesis method can obtain ordered ultramicropore materials with various structures, the template agent has complex structure, high price or complex operation, and strict requirements on reaction conditions, and is not suitable for large-scale industrial production and application.
Disclosure of Invention
The invention provides a method for synthesizing cubic phase ordered ultramicropore silicon dioxide, which aims to solve the problems in the background technology. The technical scheme of the invention is realized as follows:
a synthesis method of cubic phase ordered ultramicropore silicon dioxide comprises the following steps: adding a template agent into deionized water at the temperature of 25-38 ℃, adding an alkali source, dropwise adding a silicon source under the stirring condition after the template agent is completely dissolved, standing, moving into a hydrothermal reaction kettle, crystallizing, performing suction filtration, washing, drying after crystallization is completed to obtain ultramicropore silicon dioxide precursor powder, calcining, and calcining to obtain a cubic-phase ordered ultramicropore silicon dioxide molecular sieve, wherein the template agent is N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, the silicon source is ethyl orthosilicate, and the alkali source is methylamine.
In the synthesis method of the cubic phase ordered ultramicropore silicon dioxide, the molar ratio of the silicon source to the template is 1: 0.05-0.20.
In the synthesis method of the cubic phase ordered ultramicropore silicon dioxide, the molar ratio of the silicon source to the alkali source is 1: 0.27-3.76.
In the synthesis method of the cubic phase ordered ultramicropore silicon dioxide, the crystallization temperature is 80-140 ℃, and the duration is 12-48 h.
In the synthesis method of the cubic phase ordered ultramicropore silicon dioxide, the calcination temperature is increased to 723-1123K at a heating rate of 1-5K/min, and the duration is 2-8 h.
The synthesis method of the cubic phase ordered ultramicropore silicon dioxide has the following advantages:
1. the invention adopts rich natural renewable resources rosin as raw material to synthesize the template agent, and has the characteristics of natural innocuity, renewable resources, safe operation and the like; compared with the traditional linear chain surfactant, the hydrophobic group of the surfactant is of a tricyclic phenanthrene skeleton structure, has the characteristics of strong self-assembly capability, small molecular size and the like, and is beneficial to the formation of ordered ultramicropore materials;
2. the product is prepared by adjusting the pH value with methylamine water solution, the process operation is simple, the reaction system is simple, and the method is suitable for large-scale industrial production;
3. the ordered ultramicropore silicon dioxide prepared by the technical method has a cubic phase (Ia3d) structure, the material has high specific surface area and narrow pore size distribution, the specific surface area is more than 1200m2/g, and the pore size is about 2 nm; can be used as a selective adsorbent or a shape-selective catalyst to be widely applied to the fields of adsorption and catalysis, and has wide application prospect in the fields of solubilization of insoluble drugs, controlled release of drugs and the like.
Drawings
FIG. 1 is a small-angle X-ray diffraction pattern of calcined ultra-microporous silica synthesized with different amounts of N-dehydroabietyl-N, N-dimethyl-N-hydroxyethylammonium bromide according to the present invention;
FIG. 2 is a small angle X-ray diffraction pattern of calcined ultra-microporous silica synthesized with different methylamine addition amounts;
FIG. 3 is a small angle X-ray diffraction pattern of calcined ultra-microporous silica synthesized at different crystallization temperatures according to the present invention;
FIG. 4 is a graph showing the adsorption-desorption curves of N2 for ultra-microporous silica after calcination in example 16 of the present invention;
FIG. 5 is a DFT pore size distribution curve for ultra-microporous calcined silica of example 16 of the present invention;
FIG. 6 is a graph showing the adsorption-desorption curves of N2 for ultra-microporous silica after calcination in example 17 of the present invention;
FIG. 7 is a DFT pore size distribution curve for ultra-microporous calcined silica of example 17 in accordance with the present invention;
FIG. 8 is a TEM photograph of calcined ultra-microporous silica in example 17 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.05: 2.68: 694.
example 2
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.08: 2.68: 694.
example 3
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.10: 2.68: 694.
example 4
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.13: 2.68: 694.
example 5
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.15: 2.68: 694.
example 6
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 2.68: 694.
example 7
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.18: 2.68: 694.
example 8
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.20: 2.68: 694.
as can be seen from fig. 1, with the gradual increase of the addition amount of N-dehydroabietyl-N, N-dimethyl-N-hydroxyethylammonium bromide, the samples of examples 1 and 2 had low or no order due to too low or too high concentration of the templating agent, and the peaks of the diffraction peaks of the other samples tended to increase first and then decrease in intensity, which was in the order of the ultramicropore structure. When the material ratio of ethyl orthosilicate to N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is 1: at 0.17, the sample has the highest degree of order, and exhibits diffraction peaks of cubic phase 211, 220, 420, and 322 crystal planes at 2 θ of 3.00 °, 3.46 °, 5.50 °, and 5.72 ° (d211 of 2.94nm, d220 of 2.55nm, d420 of 1.61nm, and d332 of 1.54), respectively (fig. 1, example 6), indicating that the sample has a highly ordered cubic ultramicropore structure.
Example 9
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 0.27: 694.
example 10
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 0.54: 694.
example 11
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 0.80: 694.
example 12
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 1.07: 694.
example 13
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 1.34: 694.
example 14
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 1.61: 694.
example 15
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 1.87: 694.
example 16
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 2.15: 694.
example 17
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 2.41: 694.
example 18
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 3.21: 694.
example 19
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 100 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 3.76: 694.
as can be seen from fig. 2, as the amount of methylamine added gradually increases, in examples 9, 18 and 19, the samples are disordered or layered due to too low or too high concentration of methylamine, and the sharpness of the diffraction peak shape and the peak intensity of other samples tend to increase first and then decrease, which means that the samples are in an ordered ultramicropore structure. When the material ratio of ethyl orthosilicate to methylamine is 1:2.41, the sample has the highest degree of order, and the sample has diffraction peaks of crystal planes 211, 220, 420 and 332 in cubic phases at 2 θ ═ 3.14 °, 3.62 °, 5.66 ° and 5.96 ° (d211 ═ 2.81nm, d220 ═ 2.44nm, d420 ═ 1.56nm and d332 ═ 1.48), respectively (fig. 2, example 17), which indicates that the sample has a highly ordered cubic ultramicropore structure. Example 16 shows the highly ordered cubic ultramicropore structure of this sample, as shown in fig. 2, example 16, in which cubic phase 211, 220, 420 and 322 crystal plane diffraction peaks respectively appear at 2 θ of 3.02 °, 3.46 °, 5.50 ° and 5.74 ° (d211 of 2.92 nm, d220 of 2.55nm, d420 of 1.61nm and d332 of 1.54). The pore size is about 1.5 nm. The N2 adsorption-desorption characteristics of example 16 are shown in FIGS. 4 and 5, the pore diameter of the material is intensively distributed at 1.5nm, the material is a typical ultramicropore material, the BET specific surface area of the material is 1911m2/g, and the pore volume is 0.71m 3/g. The N2 adsorption-desorption characteristics of example 17 are shown in FIGS. 6 and 7, the pore diameter of the material is intensively distributed at 1.5nm, the material is a typical ultramicropore material, the BET specific surface area of the material is 1399m2/g, and the pore volume is 0.54m 3/g. The transmission electron microscopy characterization of example 17 is shown in fig. 8, with the sample showing a well-ordered channel structure in the parallel channel direction.
Example 20
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at the temperature of 80 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 2.68: 694.
example 21
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at 120 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 2.68: 694.
example 22
Dissolving N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide in deionized water at 35 ℃, adding a methylamine solution, dropwise adding ethyl orthosilicate under the condition of stirring after the N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide is completely dissolved, standing, moving into a hydrothermal reaction kettle, standing and crystallizing at 140 ℃ for 2-48 h, after crystallization is completed, carrying out suction filtration, washing, drying to obtain ultra-microporous silicon dioxide precursor powder, and heating the ultra-microporous silicon dioxide precursor to 823K at the rate of 1K/min and calcining for 4 h. Wherein the material ratio of ethyl orthosilicate, N-dehydroabietyl-N, N-dimethyl-N-hydroxyethyl ammonium bromide, methylamine and water is 1.0: 0.17: 2.68: 694.
as can be seen from fig. 3, as the crystallization temperature increases, the samples of examples 20, 21 and 22 have disordered or lamellar phases due to too low or too high temperature, and the peaks of the diffraction peaks of other samples tend to increase in sharpness and decrease in peak intensity, and thus have an ordered ultramicropore structure. When the crystallization temperature is 100 ℃, the sample shows diffraction peaks of 211, 220, 420 and 322 crystal planes of cubic phase at 2 theta 3.00 degrees, 3.46 degrees, 5.50 degrees and 5.72 degrees (d211 is 2.94nm, d220 is 2.55nm, d420 is 1.61nm, and d332 is 1.54), respectively (fig. 3, example 6), which shows that the sample has a highly ordered cubic ultramicropore structure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
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| CN108975346A (en) * | 2018-08-13 | 2018-12-11 | 江西农业大学 | A kind of synthetic method of the orderly ultra-microporous material with semen viciae fabae shape pattern |
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| CN108975346A (en) * | 2018-08-13 | 2018-12-11 | 江西农业大学 | A kind of synthetic method of the orderly ultra-microporous material with semen viciae fabae shape pattern |
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