CN116351388B - Mesoporous silica@molecular sieve core-shell structure material, preparation method thereof and application thereof in essence controlled release - Google Patents
Mesoporous silica@molecular sieve core-shell structure material, preparation method thereof and application thereof in essence controlled release Download PDFInfo
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- CN116351388B CN116351388B CN202310122472.3A CN202310122472A CN116351388B CN 116351388 B CN116351388 B CN 116351388B CN 202310122472 A CN202310122472 A CN 202310122472A CN 116351388 B CN116351388 B CN 116351388B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 245
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 114
- 239000000463 material Substances 0.000 title claims abstract description 68
- 239000011258 core-shell material Substances 0.000 title claims abstract description 52
- 238000013270 controlled release Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 42
- 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 41
- 239000004005 microsphere Substances 0.000 claims abstract description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000341 volatile oil Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910001868 water Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 239000000084 colloidal system Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 241000628997 Flos Species 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 241000717739 Boswellia sacra Species 0.000 claims description 3
- 235000009024 Ceanothus sanguineus Nutrition 0.000 claims description 3
- 239000004863 Frankincense Substances 0.000 claims description 3
- 240000003553 Leptospermum scoparium Species 0.000 claims description 3
- 235000015459 Lycium barbarum Nutrition 0.000 claims description 3
- 244000179970 Monarda didyma Species 0.000 claims description 3
- 235000010672 Monarda didyma Nutrition 0.000 claims description 3
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 3
- 235000008434 ginseng Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 244000131316 Panax pseudoginseng Species 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 20
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- 239000003205 fragrance Substances 0.000 abstract description 9
- 229910052710 silicon Inorganic materials 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 239000013335 mesoporous material Substances 0.000 abstract description 4
- 238000011426 transformation method Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000000686 essence Substances 0.000 description 62
- 238000001179 sorption measurement Methods 0.000 description 23
- 239000002304 perfume Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 6
- 239000011162 core material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- XYVDNBKDAAXMPG-UHFFFAOYSA-M decyl 2-(1-heptylazepan-1-ium-1-yl)acetate;hydroxide Chemical compound [OH-].CCCCCCCCCCOC(=O)C[N+]1(CCCCCCC)CCCCCC1 XYVDNBKDAAXMPG-UHFFFAOYSA-M 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a mesoporous silica@molecular sieve core-shell structure material, a preparation method thereof and application thereof in essence controlled release. According to the invention, firstly, the silicon dioxide microspheres are prepared, then the silicon dioxide microspheres are used as mesoporous silicon dioxide and a silicon source of a molecular sieve, sodium aluminate and phosphoric acid are used as an aluminum source and a phosphorus source of the molecular sieve, and a steam-assisted dry gel crystal transformation method is adopted, so that the silicon dioxide microspheres are subjected to pore-forming while the molecular sieve is prepared, and the mesoporous silicon dioxide@molecular sieve core-shell structure material is obtained. The material takes mesoporous silica as a core and molecular sieve as a shell, and combines the advantages and disadvantages of both mesoporous material and molecular sieve when being used as an adsorbent of essence. The core-shell structure material can adsorb and seal essence in the mesoporous material to realize high essence storage capacity, and can also utilize the diffusion resistance of molecular sieve micropores to achieve the purposes of slow release and controlled release, so as to greatly prolong the fragrance retention time of the essence.
Description
Technical Field
The invention belongs to the field of preparation of essence adsorbents, and particularly relates to a mesoporous silica@molecular sieve core-shell structure material, a preparation method thereof and application thereof in essence controlled release.
Background
The essence is a mixture with various aroma components, has a certain aroma type, can directly perfume products, and has wide application in the fields of food processing, daily chemical products and the like, and is closely related to life of people. The chemical components of the essence mainly comprise aromatic compounds such as alcohols, aldehydes, ethers, ketones, phenols and the like (nonferrous materials and engineering 2021, 42 (2), 48-52). These components have a strong volatility, resulting in extremely fragile functions. In order to prolong the fragrance retention period and improve the stability of the perfume, the release of the fragrance needs to be controlled, and the fragrance components are protected. The current common controlled release methods of fragrances include microcapsule technology (CN 111481450 a) and adsorbent curing technology (CN 200710063079.2). The essence microcapsule technology generally uses vegetable gum, protein, cellulose or starch derivatives and the like as wall materials and uses essence as a core material, and the cost is relatively low, but the slow release performance of the product is not ideal, the fragrance retention time is short, and the application limitation is large. The adsorbent curing technique generally utilizes high specific surface area materials (e.g., mesoporous materials, zeolites, activated carbon, etc.) to adsorb the fragrances. Because of the physical adsorption effect between the essence and the surface of the material with high specific surface area, the release time of the essence can be prolonged to a certain extent, but the interaction is not specific, the storage amount of the essence is difficult to be improved and the persistent and stable release of the essence is realized by simply utilizing the high specific surface area of the material. The development of the novel essence adsorbent is started from a material structure, and the continuous and controllable release of the fragrance is kept while the storage capacity of the essence is improved through the design of the pore structure of the novel essence adsorbent, which is also the focus of the field research.
The basic principle of the invention is to solve the problems of essence storage and controlled release by constructing a hierarchical pore structure. From the aspect of pore structure design, the mesoporous or macroporous structure can contain more essence, which is favorable for improving the storage amount of the essence, but the pore canal is too large, the essence is quickly diffused, and the controllable release is unfavorable; while microporous materials such as zeolites can control the release of perfume (CN 1127011 a), their perfume storage capacity is limited. The invention combines the advantages and disadvantages of the two, takes mesoporous silicon dioxide as a core and takes molecular sieve as a shell. The core-shell structure material can adsorb and seal essence in the mesoporous material to realize high essence storage capacity, and can also utilize the diffusion resistance of molecular sieve micropores to achieve the purposes of slow release and controlled release, so as to greatly prolong the fragrance retention time of the essence.
Disclosure of Invention
The invention aims to overcome the defect of short use period of the existing essence and overcome the defect of the existing essence adsorbent, and provides a preparation method of mesoporous silica@molecular sieve core-shell structure material for controlled release of essence.
The invention discloses a preparation method of a mesoporous silica@molecular sieve core-shell structure for essence controlled release, which comprises the following steps:
Step (1), preparation of silicon dioxide (SiO 2) microspheres:
Mixing ammonia water, water and ethanol at room temperature, stirring for 30-60 minutes, adding tetraethyl orthosilicate, and continuously stirring for 2-6 hours to obtain white semitransparent colloidal solution; and centrifugally washing the colloidal solution, drying in a vacuum drying oven at 50-80 ℃, and finally roasting in a muffle furnace at 300-500 ℃ for 3-6 hours to obtain the silica nano-microsphere.
Preferably, the mol of the tetraethyl orthosilicate, the ammonia water, the ethanol and the water in the step (1) is 1 (2-4): 10-100): 5-50, more preferably 1 (3-4): 30-50): 20-40.
Preferably, the silica nanoparticle prepared in step (1) has an average particle size of 50 to 250nm, more preferably 100 to 200nm, as determined by transmission electron microscopy.
Step (2), mixing the silicon dioxide microspheres with a molecular sieve precursor:
placing the silica nano-microspheres obtained in the step (1), sodium aluminate, phosphoric acid and water into a polytetrafluoroethylene reaction vessel, mixing and stirring to obtain a viscous mixture colloid; wherein the silica nano microsphere is used as a precursor of core-mesoporous silica and is also used as a silicon source of shell-molecular sieve.
Preferably, the molar ratio of the silica nano-microspheres, sodium aluminate, phosphoric acid and water in the step (2) is (5-20): 1:1:100, more preferably 10:1:1:100.
Step (3), steam assisted dry gel crystal transformation:
Transferring the polytetrafluoroethylene reaction container filled with the mixture colloid in the step (2) into a polytetrafluoroethylene lining of a stainless steel water heating reaction kettle, and adding a certain amount of structure directing agent and water into the bottom of the lining of the reaction kettle; then sealing the hydrothermal reaction kettle, and placing the kettle in a baking oven at 140-200 ℃ for crystallization for 24-72 hours; and then cooling rapidly, washing the solid product obtained in the polytetrafluoroethylene reaction vessel for a plurality of times by adopting deionized water and ethanol, and drying in a vacuum drying oven at 60-80 ℃ for 12-24 hours to obtain white solid powder.
Preferably, the crystallization temperature in the step (3) is 180 ℃ and the crystallization time is 48 hours.
Preferably, the structure directing agent in step (3) is one or a mixture of tetraethylammonium hydroxide or tetrapropylammonium hydroxide in any ratio, more preferably tetraethylammonium hydroxide.
Preferably, the mass ratio of the structure directing agent to the mixture colloid in the step (3) is 2:1 to 10:1, more preferably 5:1 to 10:1.
Step (4), high-temperature roasting:
Roasting the white solid powder obtained in the step (3) for 3-6 hours at 350-600 ℃ to obtain the mesoporous silica@molecular sieve core-shell structure material.
Preferably, the firing temperature in step (4) is 550℃and the firing time is 5 hours.
The invention also aims to provide a mesoporous silica@molecular sieve core-shell structure material for essence controlled release, which takes mesoporous silica as a core and molecular sieves as shells and is prepared by adopting the steps (1) - (4).
The average pore diameter of the mesoporous silica is 2-20nm, and the pore diameter of the mesoporous silica is determined by an N 2 adsorption and desorption experiment.
Preferably, the average pore diameter of the mesoporous silica is 5-10nm.
The crystalline phase structure of the molecular sieve shell layer is any one or a combination of a plurality of SAPO-5, SAPO-18 and SAPO-34.
The invention also aims to provide an application of the mesoporous silica@molecular sieve core-shell structure material in essence controlled release, which is specifically as follows:
Adding a certain amount of mesoporous silica@molecular sieve core-shell structure material into ethanol solution of essence, stirring and soaking for a certain time, performing suction filtration until no liquid flows out, and naturally air-drying to obtain the aroma-carrying mesoporous silica@molecular sieve core-shell structure material.
The essence is at least one of fructus Gardeniae essential oil, flos Rosae Rugosae essential oil, tea tree essential oil, ginseng radix essential oil, herba Rosmarini officinalis essential oil, lignum Santali albi essential oil, olibanum essential oil, cortex Cinnamomi essential oil, bergamot essential oil, and flos Caryophylli essential oil.
Preferably, the mass volume ratio of the mesoporous silica@molecular sieve core-shell structure material to the ethanol solution of the essence is 10-100:1, more preferably 20-50:1, in g/L.
Preferably, the stirring impregnation time is 1 to 24 hours, more preferably 2 to 10 hours, and most preferably 5 hours.
The invention has the beneficial effects that:
according to the invention, firstly, the silicon dioxide microspheres are prepared, then the silicon dioxide microspheres are used as mesoporous silicon dioxide and a silicon source of a molecular sieve, sodium aluminate and phosphoric acid are used as an aluminum source and a phosphorus source of the molecular sieve, and a steam-assisted dry gel crystal transformation method is adopted, so that the silicon dioxide microspheres are subjected to pore-forming while the molecular sieve is prepared, and the mesoporous silicon dioxide@molecular sieve core-shell structure material is obtained. This method has significant advantages over directly using mesoporous silica as a starting material. First, silica microspheres are cheaper than mesoporous silica; secondly, mesoporous silica is directly adopted as a silicon source, when the molecular sieve grows on the surface of the mesoporous silica, an aluminum source and a phosphorus source possibly enter mesoporous silica pore channels, and the structure of the mesoporous silica can be damaged in the process of converting the mesoporous silica into the molecular sieve, so that the mesoporous silica@molecular sieve core-shell structure material cannot be obtained. The invention adopts non-porous silica microspheres as a silicon source, so that the problems can be avoided. In the process of steam-assisted dry gel crystal transformation, tetraethylammonium hydroxide or tetrapropylammonium hydroxide not only serves as a structure guiding agent formed by a molecular sieve, but also serves as a pore-forming agent for converting silicon dioxide into mesoporous silicon dioxide, and the method has vivid creativity.
The mesoporous silica@molecular sieve core-shell structure material developed by the invention realizes efficient adsorption and slow release of essence, the storage amount of the essence reaches 6.95mg/mg at the highest, the retention rate of the essence after the essence is adsorbed for 30 days can reach more than 90%, and the material is suitable for various essences.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of mesoporous silica@molecular sieve core-shell structure material.
FIGS. 2 (a) - (b) are transmission electron microscope pictures of silica microspheres and mesoporous silica @ molecular sieve core-shell structured materials, respectively.
FIG. 3 is a scanning electron microscope-element distribution diagram of mesoporous silica @ molecular sieve core-shell structured material.
FIG. 4 is an X-ray diffraction pattern of a mesoporous silica @ molecular sieve core-shell structured material.
FIGS. 5 (a) - (b) are respectively the N 2 adsorption-desorption curve and the pore size distribution curve of the mesoporous silica@molecular sieve core-shell structure material.
Fig. 6 is a graph of flavor release curves for different adsorbent materials.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have long studied and practiced in a large number, and have proposed the technical solution of the present invention, which mainly depends on at least: according to the invention, firstly, the silicon dioxide microspheres are prepared, then the silicon dioxide microspheres are used as mesoporous silicon dioxide and a silicon source of a molecular sieve, sodium aluminate and phosphoric acid are used as an aluminum source and a phosphorus source of the molecular sieve, and a steam-assisted dry gel crystal transformation method is adopted, so that the silicon dioxide microspheres are subjected to pore-forming while the molecular sieve is prepared, and the mesoporous silicon dioxide@molecular sieve core-shell structure material is obtained. According to the invention, mesoporous silica is directly taken as a silicon source, when the molecular sieve grows on the surface of the mesoporous silica, an aluminum source and a phosphorus source possibly enter a mesoporous silica pore channel, and the structure of the mesoporous silica is damaged in the process of converting the mesoporous silica into the molecular sieve, so that the mesoporous silica@molecular sieve core-shell structure material cannot be obtained. In addition, in the steam-assisted dry gel crystal transformation process, tetraethylammonium hydroxide or tetrapropylammonium hydroxide serves as a structure guiding agent formed by a molecular sieve and also serves as a pore-forming agent for converting silicon dioxide into mesoporous silicon dioxide.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In a first aspect, a mesoporous silica@molecular sieve core-shell structure for controlled release of essence is provided, wherein the core-shell structure material takes mesoporous silica as a core and molecular sieve as a shell, and the average pore diameter of the mesoporous silica is 2-20nm, preferably 5-10nm. The crystalline phase structure of the molecular sieve shell layer is any one or a combination of a plurality of SAPO-5, SAPO-18 and SAPO-34.
The preparation method comprises the following steps:
Step (1), preparation of silicon dioxide (SiO 2) microspheres:
Mixing ammonia water, water and ethanol at room temperature, stirring for 30-60 minutes, adding tetraethyl orthosilicate, and continuously stirring for 2-6 hours to obtain white semitransparent colloidal solution; and centrifugally washing the colloidal solution, drying in a vacuum drying oven at 50-80 ℃, and finally roasting in a muffle furnace at 300-500 ℃ for 3-6 hours to obtain the silica nano-microsphere.
Preferably, the mol of the tetraethyl orthosilicate, the ammonia water, the ethanol and the water in the step (1) is 1 (2-4): 10-100): 5-50, more preferably 1 (3-4): 30-50): 20-40.
Preferably, the average particle diameter of the silica nanoparticle prepared in the step (1) is 50-250nm, more preferably 100-200nm.
Step (2), mixing the silicon dioxide microspheres with a molecular sieve precursor:
placing the silica nano-microspheres obtained in the step (1), sodium aluminate, phosphoric acid and water into a polytetrafluoroethylene reaction vessel, mixing and stirring to obtain a viscous mixture colloid; wherein the silica nano microsphere is used as a precursor of core-mesoporous silica and is also used as a silicon source of shell-molecular sieve.
Preferably, the molar ratio of the silica nano-microspheres, sodium aluminate, phosphoric acid and water in the step (2) is (5-20): 1:1:100, more preferably 10:1:1:100.
Step (3), steam assisted dry gel crystal transformation:
Transferring the polytetrafluoroethylene reaction container filled with the mixture colloid in the step (2) into a polytetrafluoroethylene lining of a stainless steel water heating reaction kettle, and adding a certain amount of structure directing agent and water into the bottom of the lining of the reaction kettle; then sealing the hydrothermal reaction kettle, and placing the kettle in a baking oven at 140-200 ℃ for crystallization for 24-72 hours; and then cooling rapidly, washing the solid product obtained in the polytetrafluoroethylene reaction vessel for a plurality of times by adopting deionized water and ethanol, and drying in a vacuum drying oven at 60-80 ℃ for 12-24 hours to obtain white solid powder.
Preferably, the crystallization temperature in the step (3) is 180 ℃ and the crystallization time is 48 hours.
Preferably, the structure directing agent in step (3) is one or a mixture of tetraethylammonium hydroxide or tetrapropylammonium hydroxide in any ratio, more preferably tetraethylammonium hydroxide.
Preferably, the mass ratio of the structure directing agent to the mixture colloid in the step (3) is 2:1 to 10:1, more preferably 5:1 to 10:1.
Step (4), high-temperature roasting:
Roasting the white solid powder obtained in the step (3) for 3-6 hours at 350-600 ℃ to obtain the mesoporous silica@molecular sieve core-shell structure material.
Preferably, the firing temperature in step (4) is 550℃and the firing time is 5 hours.
In a second aspect, the application of the mesoporous silica@molecular sieve core-shell structure material in essence controlled release is provided, specifically:
Adding a certain amount of mesoporous silica@molecular sieve core-shell structure material into ethanol solution of essence, stirring and soaking for a certain time, performing suction filtration until no liquid flows out, and naturally air-drying to obtain the aroma-carrying mesoporous silica@molecular sieve core-shell structure material.
The essence is at least one of fructus Gardeniae essential oil, flos Rosae Rugosae essential oil, tea tree essential oil, ginseng radix essential oil, herba Rosmarini officinalis essential oil, lignum Santali albi essential oil, olibanum essential oil, cortex Cinnamomi essential oil, bergamot essential oil, and flos Caryophylli essential oil.
Preferably, the mass volume ratio of the mesoporous silica@molecular sieve core-shell structure material to the ethanol solution of the essence is 10-100:1, more preferably 20-50:1, in g/L.
Preferably, the stirring impregnation time is 1 to 24 hours, more preferably 2 to 10 hours, and most preferably 5 hours.
The following description of the present invention is further provided with reference to several preferred embodiments, but the experimental conditions and setting parameters should not be construed as limiting the basic technical scheme of the present invention. And the scope of the present invention is not limited to the following examples.
The detection means used in the following examples are as follows:
1. the crystal structure of the material is measured on a diffractometer with model Rigaku Ultimate IV by adopting wide-angle X-ray diffraction (XRD), the excitation light source is CuK alpha (lambda=0.154 nm), the tube voltage is 40kV, the tube current is 30mA, the step length is 0.02 DEG, the scanning speed is 10 DEG min -1, and the scanning range is 5-40 deg.
2. The microscopic morphology of the material is observed by using a field emission scanning electron microscope of the type JECHI SU-8010 in Japan and a field emission transmission electron microscope of the type JEM-2100F in JEOL.
3. The N 2 adsorption-desorption curve and pore size distribution curve of the material were measured by a fully automatic physical adsorption analyzer of usa microphone ASAP 2460.
4. The material prepared by the invention is used for storing and releasing essence, and the adsorption quantity and the retention rate of the essence are two important parameters for evaluating the performance of the material. Definition of adsorption amount: the mass of essence capable of being adsorbed per milligram of adsorbent material at 25 ℃ is shown as mg/mg, and the formula is as follows:
Wherein Q is the adsorption quantity of essence, and the unit is mg/mg; m 0 represents the initial dry weight of the adsorbent in mg; m 1 represents the dry weight of the adsorbent after adsorption of the perfume in mg.
Definition of perfume retention: after a period of time at 25 ℃, the residual essence amount on the adsorbent accounts for the total amount of the adsorbed essence, and the unit is shown as the formula:
Wherein S represents the release speed of essence, the unit is h -1;m0 represents the initial dry weight of the adsorbent, and the unit is mg; m 1 is the dry weight of the adsorbent after adsorbing essence, and the unit is mg; m 2 represents the dry weight of the adsorbent for adsorbing essence after a certain period of time, and the unit is mg.
Example 1 SiO 2 nanospheres with an average size of about 100-200nm
After mixing 4.5mL of ammonia (25%), 1.5mL of deionized water and 90mL of ethanol, stirring vigorously at 25℃for 30min. Subsequently, 3.45mL of ethyl orthosilicate was added to the solution, and stirring was continued for 6 hours, to obtain a white translucent colloidal solution. And (3) after the sample is centrifugally washed, drying the sample in a vacuum drying oven at 60 ℃, and finally roasting the sample in a muffle furnace at 350 ℃ for 5 hours to obtain the SiO 2 nano-microsphere with the average size of about 100-200nm. The transmission electron microscope picture is shown in figure 2a, and the prepared SiO 2 is nano solid microsphere with the size of 100-200nm.
Example 2. Synthetic route of mesoporous silica @ molecular sieve core-shell structured material, as shown in figure 1.
600Mg of the silica microspheres of example 1, 82mg of sodium aluminate, 98mg of phosphoric acid and 2mL of water were mixed and stirred in a polytetrafluoroethylene beaker to give a viscous colloid. Subsequently, the polytetrafluoroethylene beaker containing the mixture colloid was transferred to a polytetrafluoroethylene liner of a stainless steel hot-reaction vessel, and 4g of tetraethylammonium hydroxide was added to the bottom of the liner. And then the reaction kettle is put into a 180 ℃ oven for crystallization for 48 hours after being sealed. And then cooling rapidly, washing the solid product obtained in the polytetrafluoroethylene beaker with deionized water and ethanol for a plurality of times, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain white solid powder. And finally, roasting the white solid powder at 550 ℃ for 5 hours to obtain the mesoporous silica@molecular sieve core-shell structure material.
The transmission electron microscope picture of the prepared material is shown in fig. 2 b. It can be seen from the figure that although the silica still maintains a spherical structure, it has many mesopores inside, indicating that the silica changes from solid microspheres to mesoporous silica microspheres. In addition, a layer of substances can be seen to be wrapped outside the mesoporous silica microspheres, and the formation of a core-shell structure is confirmed. The X-ray diffraction pattern (fig. 4) can see a large packet of peaks at 15-30 deg., which are attributed to amorphous silica, while characteristic diffraction peaks observed at 9.29 deg., 12.8 deg. and 20.5 deg. can be attributed to SAPO-34 molecular sieves (PDF # 47-0429). The scanning electron microscope-energy spectrum analysis (figure 3) shows that the elements such as Si, al, P and the like in the core-shell structure material are uniformly distributed, which indicates that the molecular sieve is uniformly coated outside the mesoporous silica. The hysteresis is evident in the N 2 adsorption-desorption curve (FIG. 5 a) and the average pore diameter is 10nm in the pore size distribution curve (FIG. 5 b), further confirming that the core is mesoporous silica. The specific surface area of the material is 457m 2/g.
Example 3.
600Mg of the silica microspheres of example 1 were added to a polytetrafluoroethylene beaker and then transferred to a polytetrafluoroethylene liner of a stainless steel hot-water reactor, and 4g of tetraethylammonium hydroxide was added to the bottom of the liner. And then the reaction kettle is put into a 180 ℃ oven for crystallization for 48 hours after being sealed. And then cooling rapidly, washing the solid product obtained in the polytetrafluoroethylene beaker with deionized water and ethanol for a plurality of times, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain white solid powder. Finally, roasting the white solid powder at 550 ℃ for 5 hours to obtain the mesoporous silica material.
Example 4.
At 25 ℃,100 mg of mesoporous silica@molecular sieve core-shell structure material obtained in example 2 is added into 1mL of ethanol solution (2 wt%) of rose essential oil, stirred and immersed for 5 hours, suction filtration is carried out until no liquid flows out, natural air drying is carried out, the mesoporous silica@molecular sieve core-shell structure material carrying perfume is obtained, the importance of the mesoporous silica@molecular sieve core-shell structure material is weighed, and the adsorption quantity Q of essence is calculated to be 6.95mg/mg. At regular intervals, the mesoporous silica@molecular sieve core-shell structure material carrying the perfume is weighed, and a release curve of the perfume is obtained, as shown in figure 6.
Examples 5 to 8
The experimental parameters (adsorbents used) of the perfume adsorption process, which were carried out by referring to the method described in example 4, are different from those of example 4, and specific experimental parameters and perfume adsorption and release properties are shown in table 1.
Example 5 differs from example 4 in that the adsorbent used in example 5 is silica microspheres prepared as described in example 1.
Example 6 differs from example 4 in that the adsorbent used in example 6 is a mesoporous silica material prepared as described in example 3.
The essence release curves of examples 4-6 are shown in FIG. 6, and it is clear from the graph that the adsorption/controlled release capacity of the silica microspheres is very poor, the adsorption amount of the essence is very low (0.55 mg/mg), most of the adsorbed essence can be released in a short time, and only 9.6% of the adsorbed essence can be retained after 30 days; after the silicon dioxide microspheres are converted into mesoporous silicon dioxide, the adsorption quantity of essence is greatly improved (6.84 mg/mg), but the release speed of the essence is still high, and the retention rate of the essence is 50.6% after 30 days; after the mesoporous silica is coated with the molecular sieve shell, the mesoporous silica@molecular sieve core-shell structure material has high essence adsorption capacity and can realize slow controlled release of essence. After 30 days, the retention rate of the essence adsorbed by the material is up to 90%.
Example 7 differs from example 4 in that the adsorbent used in example 7 is a commercial SAPO-34 molecular sieve (Tianjin southbound catalyst limited). As can be seen from Table 1, the adsorption capacity of essence of the SAPO-34 molecular sieve is much worse than that of mesoporous silica and core-shell structure materials, but the controlled release capacity of the molecular sieve is good, and the retention rate of essence is as high as more than 90% in 30 days.
Example 8 differs from example 4 in that the adsorbent used in example 8 is a physical mixture of a commercial SAPO-34 molecular sieve (Tianjin southward catalyst limited) and a mesoporous silica material prepared as described in example 3, wherein the mesoporous silica: SAPO-34 molecular sieve=10:1.
As can be seen from table 1-1, the adsorption amounts of examples 8, 4 and 6 are almost the same, which indicates that mesoporous silica is a key factor for determining the adsorption amount of essence; while examples 8 and 6 have similar 30-day essence retention rates, which indicates that the physical mixed molecular sieve cannot improve the essence controlled release performance, and only when mesoporous silica and the molecular sieve form a uniform core-shell structure, the adsorption capacity of the mesoporous silica and the molecular sieve can be ensured and the controlled release capability of the mesoporous silica and the molecular sieve can be improved.
Examples 9 to 17
The experimental parameters of the perfume adsorption process (different perfumes were used) slightly different from those of example 4, and specific experimental parameters and perfume adsorption and release properties are shown in table 1-1, which were performed according to the method described in example 4. From the table, the mesoporous silica@molecular sieve core-shell structure material has good adsorption and controlled release capacities for various essences.
Table 1 perfume adsorption and Release Properties of the examples
Claims (10)
1. The preparation method of the mesoporous silica@molecular sieve core-shell structure is characterized by comprising the following steps of:
Step (1), preparation of silicon dioxide (SiO 2) microspheres:
Mixing ammonia water, water and ethanol at room temperature, stirring for 30-60 minutes, adding tetraethyl orthosilicate, and continuously stirring for 2-6 hours to obtain white semitransparent colloidal solution; centrifugally washing the colloid solution, drying in a vacuum drying oven at 50-80 ℃, and finally roasting in a muffle furnace at 300-500 ℃ for 3-6 hours to obtain the silica nano-microspheres;
step (2), mixing the silicon dioxide microspheres with a molecular sieve precursor:
placing the silica nano-microspheres obtained in the step (1), sodium aluminate, phosphoric acid and water into a polytetrafluoroethylene reaction vessel, mixing and stirring to obtain a viscous mixture colloid;
Step (3), steam assisted dry gel crystal transformation:
Transferring the polytetrafluoroethylene reaction container filled with the mixture colloid in the step (2) into a polytetrafluoroethylene lining of a stainless steel water heating reaction kettle, and adding a certain amount of structure directing agent and water into the bottom of the lining of the reaction kettle; then sealing the hydrothermal reaction kettle, and placing the kettle in a baking oven at 140-200 ℃ for crystallization for 24-72 hours; then cooling rapidly, washing the solid product obtained in the polytetrafluoroethylene reaction vessel for a plurality of times by adopting deionized water and ethanol, and drying in a vacuum drying oven at 60-80 ℃ for 12-24 hours to obtain white solid powder; wherein the structure directing agent is one or a mixture of tetraethylammonium hydroxide or tetrapropylammonium hydroxide in any proportion;
Step (4), high-temperature roasting:
Roasting the white solid powder obtained in the step (3) for 3-6 hours at 350-600 ℃ to obtain the mesoporous silica@molecular sieve core-shell structure material.
2. The method according to claim 1, wherein the molar ratio of tetraethyl orthosilicate, ammonia water, ethanol and water in the step (1) is 1 (2-4): 10-100): 5-50; the average particle size of the silica nano microsphere is 50-250nm.
3. The method according to claim 1, wherein in the step (2), the molar ratio of the silica nano-microspheres, sodium aluminate, phosphoric acid and water is (5-20): 1:1:100.
4. The method according to claim 1, wherein the crystallization temperature in step (3) is 180 ℃ and the crystallization time is 48 hours.
5. The method of claim 1, wherein the structure directing agent in step (3) is tetraethylammonium hydroxide.
6. The method according to claim 1 or 5, wherein the mass ratio of the structure directing agent to the mixture colloid in step (3) is 2:1 to 10:1.
7. The method according to claim 1, wherein the firing temperature in the step (4) is 550 ℃ and the firing time is 5 hours.
8. A mesoporous silica @ molecular sieve core-shell structure material, wherein the core-shell structure material is prepared by taking mesoporous silica as a core and taking a molecular sieve as a shell by adopting the method of any one of claims 1-6; the method is characterized in that:
the average pore diameter of the mesoporous silica is 2-20nm;
the crystalline phase structure of the molecular sieve shell layer is any one or a combination of a plurality of SAPO-5, SAPO-18 and SAPO-34.
9. The application of the mesoporous silica@molecular sieve core-shell structure material in essence controlled release as claimed in claim 8, which specifically comprises the following steps:
Adding a certain amount of mesoporous silica@molecular sieve core-shell structure material into ethanol solution of essence, stirring and soaking for a certain time, performing suction filtration until no liquid flows out, and naturally air-drying to obtain the aroma-carrying mesoporous silica@molecular sieve core-shell structure material;
The essence is at least one of fructus Gardeniae essential oil, flos Rosae Rugosae essential oil, tea tree essential oil, ginseng radix essential oil, herba Rosmarini officinalis essential oil, lignum Santali albi essential oil, olibanum essential oil, cortex Cinnamomi essential oil, bergamot essential oil, and flos Caryophylli essential oil.
10. The use according to claim 9, characterized in that the mass-to-volume ratio of the mesoporous silica @ molecular sieve core-shell structured material to the ethanol solution of the essence is 10-100:1, a step of; the stirring and soaking time is 1-24 hours.
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