CN107298444A - It is a kind of using preparation of the abietyl Gemini surface active agent as the Metaporous silicon dioxide material of template and its performance - Google Patents
It is a kind of using preparation of the abietyl Gemini surface active agent as the Metaporous silicon dioxide material of template and its performance Download PDFInfo
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- CN107298444A CN107298444A CN201710492450.0A CN201710492450A CN107298444A CN 107298444 A CN107298444 A CN 107298444A CN 201710492450 A CN201710492450 A CN 201710492450A CN 107298444 A CN107298444 A CN 107298444A
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- silicon dioxide
- metaporous silicon
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention relates to a kind of using preparation of the abietyl Gemini surface active agent as the Metaporous silicon dioxide material of template and performance.The present invention gives the synthetic method of this kind of Metaporous silicon dioxide material, synthetic parameters and performance.The material has three-dimensional cubic phase structure, shows dumbbell shaped pattern.The specific surface area of the material is 1171m2·g‑1, pore volume is 1.47cm3·g‑1, pore-size distribution is concentrated mainly on 2.28nm.The Metaporous silicon dioxide material novel in shape, compound with regular structure and adsorbance is higher, due to its novel pattern and size selectivity, the material is with a wide range of applications in terms of catalysis, separation and drug delivery.
Description
Technical field
The present invention relates to a kind of preparation method of silicon-based mesoporous material, more particularly to one kind is with abietyl Gemini surface active
Agent is template, the method to prepare three-dimensional cubic phase mesoporous silicon oxide, belongs to surfactant application field.
Background technology
Mesoporous material is due to its novel pattern, the nanostructured of high-sequential, high specific surface area and duct volume etc.
Feature and be widely used in that novel macromolecule catalyst, inoranic membrane industrial separation, pharmaceutical carrier, enzyme be immobilized, photoelectron
In terms of the preparation of material and multi-functional microreactor.In the preparation process of mesoporous material, surfactant is used as structure
Directed agents, have important influence to the structure and pattern of mesoporous material.Therefore, the surfactant of synthesizing new structure is designed
It is used as the template in mesoporous material building-up process, is expected to obtain the mesoporous material with special appearance and performance.
Gemini surface active agent is greatly paid close attention to unique self-organizing behavior by people in recent years.Gemini surface active
Agent molecule is made up of two hydrophilic head bases, two hydrophobic tail chains and a coupling link, with abundant structural element.Therefore, with
Gemini surface active agent has also obtained more research as template in terms of synthesising mesoporous material.Rosin is a kind of natural production
Thing, is mainly made up of the resin acid containing diterpene structure.The present invention passes through using a kind of abietyl Gemini surface active agent as template
The addition of surfactant, silicon source, water, ether and alkaline medium is adjusted, novel in shape, compound with regular structure and suction is prepared for
The high mesoporous silicon oxide of attached amount.Due to its novel pattern and size selectivity, the material is in catalysis, separation and drug delivery
Aspect is with a wide range of applications.
The content of the invention
It is an object of the invention to provide one kind three-dimensional cubic phase is synthesized by template of abietyl Gemini surface active agent
The method of Metaporous silicon dioxide material, and the basic performance of the material is provided.
To achieve the above object, the present invention is adopted the following technical scheme that：
Using the main component dehydroabietic acid in disproportionated rosin as raw material, to synthesize a kind of abietyl Gemini surface active agent R-
6-R, is used as template, controls multiple synthetic parameters, obtains the novel Metaporous silicon dioxide material of structure.The template
Structural formula is as follows：
The specific synthesis step of the mesoporous material is as follows：
The first step：A certain amount of abietyl Gemini surface active agent R-6-R is dissolved by heating in deionized water, stirring is extremely
Solution is clarified, and is cooled to after room temperature, a certain amount of absolute ether is added under magnetic agitation.The volume ratio of deionized water and absolute ether
For 0.5~1.5.The pH value of alkaline medium ammoniacal liquor regulation system is added to 9.0~11.0, after magnetic agitation is well mixed, room temperature
Under the conditions of tetraethyl orthosilicate is slowly added dropwise.A mole composition for solution is tetraethyl orthosilicate：Abietyl Gemini surface active agent：
Water=1：0.075~0.25：100~450.After completion of dropping, mixture is continued to stirring 24h in water bath with thermostatic control, two are obtained
Siliconoxide precursor.Second step：To have in the turbid liquid immigration of gained in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, and
24~72h of crystallization under 353K~393K.3rd step：Product, for several times to neutral, is placed in baking oven in 363K through ethanol and water washing
Dry.Dried semi-finished product be placed in Muffle furnace with 2K/min heating rate be to slowly warm up to 823K roasting 5h remove removing template
Agent, obtains Metaporous silicon dioxide material.
The meso-hole structure and crystal face parameter of Metaporous silicon dioxide material：A certain amount of meso-porous titanium dioxide Si powder is taken to dry
Afterwards, its meso-hole structure is determined using X-ray diffractometer.
The sample topography of Metaporous silicon dioxide material：Sample is scattered in absolute ethyl alcohol according to certain mass fraction, dripped
It is added in and is loaded with the copper mesh of carbon support film, dries naturally.The microscopic appearance of sample is observed using SEM.
The pore passage structure of Metaporous silicon dioxide material：Sample is scattered in absolute ethyl alcohol according to certain mass fraction,
It is added dropwise and is being loaded with the copper mesh of carbon support film, dries naturally.Use the pore passage structure of transmission electron microscope observation sample.
The adsorbance of Metaporous silicon dioxide material：Sample is under 523K after degassed 360min, using automatically comparing surface
The specific surface area of product and micropore physical adsorption appearance determination sample, pore volume and pore-size distribution.
Beneficial effect
Using rosin-based surfactant as template, by adjusting multiple synthetic parameters, novel Jie of structure can be obtained
Hole earth silicon material.The Metaporous silicon dioxide material has novel dumbbell shaped pattern, with three-dimensional cubic phase structure, space
Group belongs to Ia3d crystallographic systems.The Metaporous silicon dioxide material also has a higher specific surface area, larger pore volume and more collects
In pore-size distribution.Due to its novel pattern and size selectivity, the Metaporous silicon dioxide material is in catalysis, separation and medicine
It is with a wide range of applications in terms of conveying.
Brief description of the drawings
The small angle X-ray diffraction figure of Fig. 1 Metaporous silicon dioxide materials.
The scanning electron microscope (SEM) photograph of Fig. 2 Metaporous silicon dioxide materials.
The transmission electron microscope picture of Fig. 3 Metaporous silicon dioxide materials.
The N of Fig. 4 Metaporous silicon dioxide materials2Adsorption-desorption isothermal.
The BJH pore size distribution curves of Fig. 5 Metaporous silicon dioxide materials.
Embodiment
Embodiment 1：Take abietyl Gemini surface active agent (3.54g, 0.0035mol), add deionized water (157.5g,
8.75mol), dissolve by heating, stirring to solution clarification.Treat that solution is cooled to room temperature, absolute ether is added with vigorous stirring
(131.25mL).The pH value of alkaline medium ammoniacal liquor regulation system is added to 10.5.Positive silicic acid tetrem is slowly added dropwise under room temperature condition
Ester (7.40g, 0.035mol).A mole composition for solution is tetraethyl orthosilicate：Rosin-based surfactant：Deionized water=1：
0.1：250, the volume ratio of deionized water and ether is 1.2：1.24h is stirred in the water bath with thermostatic control that mixed liquor is placed in 303K, is obtained
To silica precursor.To have in the turbid liquid immigration of gained in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, in 373K
Lower crystallization 36h.Product is washed for several times to neutral through ethanol and deionized water, is placed in baking oven and is dried in 363K.Dried half
Finished product be placed in Muffle furnace with 2K/min heating rate be to slowly warm up to 823K roasting 5h remove template agent removing, obtain mesoporous dioxy
Silicon nitride material.
Embodiment 2：Take after a certain amount of Metaporous silicon dioxide material powder drying, determined using small angle X-ray diffraction instrument
Its meso-hole structure, test condition is tube voltage 40kV, tube current 40mA, 2 °/min of sweep speed, 0.01 ° of step-length.
Embodiment 3：By sample with 0.1% mass fraction ultrasonic disperse in absolute ethyl alcohol, be added dropwise be loaded with carbon support
On the copper mesh of film, dry naturally.The microscopic appearance of sample is observed using SEM.
Embodiment 4：By sample with 0.1% mass fraction ultrasonic disperse in absolute ethyl alcohol, be added dropwise be loaded with carbon support
On the copper mesh of film, dry naturally.Use the pore passage structure of transmission electron microscope observation sample.
Embodiment 5：Sample is deaerated under 523K after 360min, use full-automatic specific surface area and micropore physical adsorption appearance
The adsorbance of determination sample.
Claims (4)
1. a kind of Metaporous silicon dioxide material with three-dimensional cubic structure, is using a kind of abietyl Gemini surface active agent as mould
Plate, using tetraethyl orthosilicate as silicon source, using ammoniacal liquor as alkaline medium, after water-heat process, filtering, washing, dry and roasting
Obtain, the structural formula of abietyl Gemini surface active agent therein is as follows：
2. a kind of Metaporous silicon dioxide material with three-dimensional cubic structure according to claim 1, it is characterised in that should
Material is in preparation process, and the mol ratio of several raw materials is tetraethyl orthosilicate：Abietyl Gemini surface active agent：Water=1：
0.075~0.25：100~450, the pH value of system is 9~11.Crystallization temperature be 353K~393K, crystallization time be 24h~
72h, the water of addition and the volume ratio of ether are 0.5~1.5.
3. a kind of Metaporous silicon dioxide material with three-dimensional cubic structure according to claim 1, it is characterised in that should
The particle of material has the exterior appearance of dumbbell shaped.
4. a kind of Metaporous silicon dioxide material with three-dimensional cubic structure according to claim 1, it is characterised in that should
The specific surface area of material is 1171m2·g-1, pore volume is 1.47cm3·g-1, pore-size distribution is concentrated mainly on 2.28nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710492450.0A CN107298444A (en) | 2017-06-26 | 2017-06-26 | It is a kind of using preparation of the abietyl Gemini surface active agent as the Metaporous silicon dioxide material of template and its performance |
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| CN201710492450.0A CN107298444A (en) | 2017-06-26 | 2017-06-26 | It is a kind of using preparation of the abietyl Gemini surface active agent as the Metaporous silicon dioxide material of template and its performance |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108275687A (en) * | 2018-03-29 | 2018-07-13 | 东北林业大学 | A kind of preparation method of mesoporous hollow silica microsphere |
| CN109052416A (en) * | 2018-08-13 | 2018-12-21 | 江西农业大学 | A kind of orderly ultra-microporous material of stratiform and its synthetic method |
| CN110203937A (en) * | 2019-07-03 | 2019-09-06 | 江西农业大学 | A kind of synthetic method of the orderly super-microporous silicon dioxide of cubic phase |
| CN111939091A (en) * | 2020-07-17 | 2020-11-17 | 仲恺农业工程学院 | Antibacterial mesoporous silica composite and preparation method and application thereof |
Citations (1)
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|---|---|---|---|---|
| CN106268497A (en) * | 2016-07-16 | 2017-01-04 | 江南大学 | One class contains abietyl Gemini surface active agent and the performance thereof of polyoxyethylene ether coupling link |
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2017
- 2017-06-26 CN CN201710492450.0A patent/CN107298444A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106268497A (en) * | 2016-07-16 | 2017-01-04 | 江南大学 | One class contains abietyl Gemini surface active agent and the performance thereof of polyoxyethylene ether coupling link |
Non-Patent Citations (5)
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| 王海峰 等: "新型松香基阳离子Gemini表面活性剂的合成及分析", 《现代化工》 * |
| 王鹏 等: "松香基季铵盐为模板剂有序超微孔二氧化硅的合成", 《无机化学学报》 * |
| 韩世岩 等: "一种新颖的松香酰基甘氨酸型两性双子表面活性剂的合成及性能分析", 《现代化工》 * |
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| 马玉玲 等: "以松香改性物为模板制备多孔二氧化硅的表征", 《林产化学与工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108275687A (en) * | 2018-03-29 | 2018-07-13 | 东北林业大学 | A kind of preparation method of mesoporous hollow silica microsphere |
| CN109052416A (en) * | 2018-08-13 | 2018-12-21 | 江西农业大学 | A kind of orderly ultra-microporous material of stratiform and its synthetic method |
| CN109052416B (en) * | 2018-08-13 | 2021-05-11 | 江西农业大学 | Layered ordered ultramicropore material and synthesis method thereof |
| CN110203937A (en) * | 2019-07-03 | 2019-09-06 | 江西农业大学 | A kind of synthetic method of the orderly super-microporous silicon dioxide of cubic phase |
| CN110203937B (en) * | 2019-07-03 | 2021-02-26 | 江西农业大学 | Synthesis method of cubic phase ordered ultramicropore silicon dioxide |
| CN111939091A (en) * | 2020-07-17 | 2020-11-17 | 仲恺农业工程学院 | Antibacterial mesoporous silica composite and preparation method and application thereof |
| CN111939091B (en) * | 2020-07-17 | 2023-06-20 | 仲恺农业工程学院 | Antibacterial mesoporous silica compound and preparation method and application thereof |
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Application publication date: 20171027 |