CN102616795A - Method for preparing pure silicon-based mesoporous silica nanoparticles - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 22
- 239000010703 silicon Substances 0.000 title claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 small molecule amine Chemical class 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000003093 cationic surfactant Substances 0.000 claims abstract 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical group OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 2
- 238000010306 acid treatment Methods 0.000 claims 2
- MZMRZONIDDFOGF-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical group CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCCCCCCCCC[N+](C)(C)C MZMRZONIDDFOGF-UHFFFAOYSA-M 0.000 claims 2
- GQZAJRZKIHOHHU-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;n,n-dimethylmethanamine Chemical compound CN(C)C.OCCN(CCO)CCO GQZAJRZKIHOHHU-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical compound CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 3
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 6
- PHOKZASIXRJZSU-UHFFFAOYSA-N azanium 2-hexadecyl-3,4,5,6-tetramethylbenzenesulfonate Chemical class [NH4+].C(CCCCCCCCCCCCCCC)C1=C(C(=C(C(=C1S(=O)(=O)[O-])C)C)C)C PHOKZASIXRJZSU-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 5
- 229960004418 trolamine Drugs 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
本发明公开了一种纯硅基介孔二氧化硅纳米颗粒的制备方法，该方法直接使用极低浓度的有机小分子胺为碱源、阳离子表面活性剂作为模板剂、四烷基硅酸酯为硅源、去离子水为水源作为原料；原料的摩尔组成为硅源:阳离子表面活性剂:有机小分子胺:水=1:0.03～0.1:0.001～0.24:40～200。本发明与现有技术相比最显著的优点在于直接使用极低浓度的有机小分子胺为碱源，不使用对环境有较大污染的氢氧化钠或氢氧化钾作为碱源，另外有机小分子胺对硅源的摩尔比可以控制在极低的浓度范围之内（0.001～0.24）。本发明合成方法简单、周期短、成本低、重复性好、易规模化，是一种环境友好的合成策略。
The invention discloses a preparation method of pure silicon-based mesoporous silica nanoparticles. The method directly uses an extremely low concentration of organic small molecule amine as an alkali source, a cationic surfactant as a template agent, and a tetraalkyl silicate Silicon source, deionized water as water source as raw material; the molar composition of raw material is silicon source: cationic surfactant: organic small molecule amine: water = 1:0.03～0.1:0.001～0.24:40～200. Compared with the prior art, the present invention has the most significant advantage of directly using extremely low concentration organic small molecule amines as the alkali source, without using sodium hydroxide or potassium hydroxide which pollutes the environment as the alkali source, and the organic small molecule The molar ratio of molecular amine to silicon source can be controlled within a very low concentration range (0.001-0.24). The synthesis method of the invention is simple, short in cycle, low in cost, good in repeatability and easy in scale, and is an environment-friendly synthesis strategy.
Description
Technical field
The present invention relates to a kind of preparation method of mesopore molecular sieve, relate in particular to a kind of preparation method of pure silicon base mesoporous silica nano-particle, belong to the synthetic field of inorganic chemistry.
Background technology
Mesopore silicon dioxide nano material is a kind of novel inorganic nano material with high-specific surface area, large pore volume, pattern and controllable size, and it has caused extensive concern in the applied research of Materials science, biological medicine, environmental protection, field of biosensors in recent years.The main synthesis strategy of current synthesizing mesoporous silicon dioxide nano particle (MSN) comprising: use single CTAB cats product (Angew. Chem. Int. Ed., 2002,2151; 2317.), early stage what react, through a large amount of water dilutions; With the cancellation particle growth; Thereby prepared the mesoporous silica nano-particle of size, but particle shape is irregular, and the yardstick very heterogeneity that distributes less than 100 nm; Through improved St ber method (J. Phys. Chem. B 2004,108,20122.), can prepare highly monodispersed mesoporous SiO as the cosurfactant of CTAB cats product with ethanol
2Nano particle, but size is often greater than 100 nm; Bein is through using trolamine (TEAH
3) the replacement mineral alkali can synthesize the mesoporous nano-grain (Adv. Funct. Mater. 2007,17,605.) of size less than 200 nm, but trolamine (TEAH
3) consumption very big, and need just can obtain final particle through ultracentrifugal method; Kuroda has reported that recently a new synthesis strategy comes the mesoporous SiO of preparation size less than 50nm
2Nano particle, but the molar ratio of CTAB/TMOS greater than 0.5, the high and tensio-active agent of synthetic cost will could be removed (Chem. Commu., 2009,5094.) through complicated dialysis process; Chinese patent CN1923684A utilizes sarcosyl to make template, is co-structured directed agents with (3-aminopropyl) Trimethoxy silane, synthesized big or small evenly, the SiO of controllable size
2Nano particle, higher but the synthetic cost compares; The synthesis strategy of mixed templates can be used for synthetic highly monodispersed mesoporous nano-grain equally, but the expensive price limit of tensio-active agent its use (SCI, 2011,32,560.) widely.In Chinese patent CN102275936A; Our reported first utilize two alkaline process to use cetyl trimethyl p-methyl benzenesulfonic acid ammonium salts (CTATos) as template; The mesoporous silica nano-particle that can synthesize highly single dispersion and controllable size; Although this compound method can greatly reduce the synthetic cost, two alkaline process building-up processes are loaded down with trivial details relatively.Visible from above-mentioned report, existing compound method existence condition harshness, cost is high, productive rate is low, pollution is big etc. is unfavorable for the shortcoming of scale operation.Therefore, the new synthetic technology of research and development is current mesoporous SiO
2The top priority of nano particle basis research.
Summary of the invention
The object of the present invention is to provide a kind of extensive, low-cost, pollute little mesoporous SiO
2The green technology of preparing of nano particle synthetic.
A kind of preparation method of mesoporous silica spheres shape nano particle, it is characterized in that organic molecule amine that this method directly uses extremely low concentration as alkali source, cats product as template, tetraalkyl silicon ester as silicon source, deionized water as the water source as raw material; The mole of raw material consists of the silicon source: cats product: organic molecule amine: water=1: 0.03～0.1: 0.001～0.24: 40～200; Concrete preparation may further comprise the steps:
Earlier be mixed in deionized water, alkali source, template in the reaction vessel successively; 80 ℃ of constant temperature are stirred to the solution clarification, then the silicon source are joined rapidly in the mixing solutions, and 80 ℃ of constant temperature continue to stir 2 hours; Directly product is filtered, washs and drying behind the cool to room temperature; Use roasting or acid-treated method with the removal of surfactant in the duct, obtain mesoporous silica spheres shape nano particle, particulate is of a size of 20～100nm; Wherein: said organic molecule amine is Trimethylamine 99, triethylamine, tripropyl amine, thanomin, methylamine, ethamine, propylamine, butylamine, tri methylol amino methane, diethylolamine or trolamine; Described cats product is that cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt is that CTATos, cetyl trimethylammonium bromide are that CTABr, palmityl trimethyl ammonium chloride are CTACl; Said tetraalkyl silicon ester is tetramethoxy silicon ester or tetraethoxy silicon ester; Said roasting is 550 ℃ of following roastings 5 hours; S.t. is that the HCl ethanolic soln with 1M at room temperature stirred 1 hour.
Cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt used in the present invention (CTATos) cats product comes from the Merck chemical reagents corporation of Germany; Other reagent is domestic commercially available.
The present invention compares with prior preparation method has following advantage:
⑴ the present invention does not use mineral alkali such as sodium hydroxide, Pottasium Hydroxide etc. that environment is had bigger pollution as alkali source; But directly use relatively inexpensive organic molecule amine as alkali source; And control organic molecule amine to the mol ratio in silicon source in the extremely low concentration scope; Promptly 0.001～0.24, greatly reduce material synthetic cost and to the pollution of environment.
⑵ the present invention can reduce tensio-active agent (CTATos)/Si mol ratio to 0.03, has reduced synthetic cost, has reduced environmental pollution.In addition, because the operation steps that sample reclaims has greatly been simplified in the foam generation that the tensio-active agent in the system by 100% utilization, has no in the middle of filtration, the washing process.
⑶ from the characterization result of product, and the product that the present invention obtains is that size is even, the ball shaped nano particle of aperture homogeneous, and surface-area reaches 534 m
2/ g, pore volume are 1.57 ml/g, and the aperture is 2.6 nm.
⑷ compound method of the present invention is simple, be easy to mass-producing, and the meso-porous nano material that lab scale obtains in the laboratory has reached the feather weight level.
⑸ the tensio-active agent in the mesopore orbit was removed through one step of way of direct pickling or high-temperature roasting.
⑹ sample can obtain through the way of direct suction filtration, has saved loaded down with trivial details steps such as high speed centrifugation sedimentation.
⑺ the method for sample through simple supersound process can be distributed in the middle of water, the ethanol isopolarity protonated solvent, obtains high stability colloidal solution.
Description of drawings
Fig. 1 is the mesoporous SiO of synthetic pure silicon base of the present invention
2The ESEM of nano particle (SEM) figure;
Fig. 2 is the mesoporous SiO of synthetic pure silicon base of the present invention
2The high-resolution-ration transmission electric-lens of nano particle (TEM) figure.
Embodiment
Through embodiment the present invention is described further below, its purpose only is to understand better research contents of the present invention and unrestricted protection scope of the present invention.
Embodiment 1
At first 2.74g cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) is joined the trolamine (TEAH that contains 144ml deionized water and 0.37g
3) beaker in, 80 ℃ of constant temperature stir 1 hour to the solution becomes clarification, then 20.83g tetraethoxy silicon ester (TEOS) are joined rapidly in this beaker, 80 ℃ of constant temperature continue to stir 2 hours, obtain white precipitate, the mole of this mixture consists of SiO
2: CTATos: TEAH
3: H
2O=1: 0.06: 0.025: 80; To obtain the direct suction filtration of mixture, washing, oven dry, obtain mesoporous SiO
2Nano particle, productive rate 90%, median size 65 nm.Utilize high-temperature roasting or acid-treated method can a step with the removal of surfactant in the duct, concrete grammar is following: the directly roasting 6 hours in 550 ℃ of retort furnaces of the former powder of (1) 1.0g; (2) the former powder of 1.0g is in the ethanol solution hydrochloride of 40ml 1M, and stirring at room 1 hour is filtered, washs, dried.Finally obtain particulate specific surface area 534 m
2/ g, pore volume 1.57 ml/g, aperture 2.6 nm.
Embodiment 2
At first 2.74g cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) is joined in the beaker that contains 144ml deionized water, 0.61g tri methylol amino methane (TMAM) mixing solutions 80
oC constant temperature stirs 1 hour to the solution becomes clarification, then 20.83g tetraethoxy silicon ester (TEOS) is joined in this beaker 80 rapidly
oC constant temperature continues to stir 2 hours, obtains white precipitate, and the mole of this mixture consists of SiO
2: CTATos: TMAM: H
2O=1: 0.06: 0.05: 80; With the direct suction filtration of gained mixture, washing, oven dry, obtain containing the mesoporous SiO of V-shape hole
2Nano particle, productive rate 88%, median size 70 nm, specific surface area 600 m
2/ g, pore volume 1.6 ml/g, aperture 2.5 nm.
Embodiment 3
Remove with triethylamine (TEA) and replace the trolamine (TEAH among the embodiment 1
3) outside, other preparation condition is all identical with embodiment 1, and obtaining median size is the mesoporous SiO of 60 nm
2Nano particle.
Embodiment 4
Except that the cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) that replaces with cetyl trimethylammonium bromide (CTABr) among the embodiment 1, other preparation condition is all identical with embodiment 1, and obtaining median size is the mesoporous SiO of 50 nm
2Nano particle.
Embodiment 5
Except that the tetraethoxy silicon ester (TEOS) that replaces with tetramethoxy silicon ester (TMOS) among the embodiment 1, other preparation condition is all identical with embodiment 1, and obtaining median size is the mesoporous SiO of 40 nm
2Nano particle.
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| CN102847514A (en) * | 2012-09-26 | 2013-01-02 | 复旦大学 | Nanometer mesoporous material capable of serving as capillary electrochromatography pseudostationary phase and preparation method thereof |
| CN103241723A (en) * | 2013-04-22 | 2013-08-14 | 华东师范大学 | Preparation method of mesoporous carbon/silica composite nanoparticles |
| CN103539135A (en) * | 2013-10-24 | 2014-01-29 | 华东师范大学 | Preparation method of mesoporous silica suspension with stable colloidal state |
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| KUN ZHANG ET AL.: "Novel synthesis and molecularly scaled surface hydrophobicity control of colloidal mesoporous silica", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 143, 22 March 2011 (2011-03-22), pages 401 - 405 * |
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