CN104909378A - Preparation method of monodisperse porous silicon dioxide microspheres - Google Patents
Preparation method of monodisperse porous silicon dioxide microspheres Download PDFInfo
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- CN104909378A CN104909378A CN201510333675.2A CN201510333675A CN104909378A CN 104909378 A CN104909378 A CN 104909378A CN 201510333675 A CN201510333675 A CN 201510333675A CN 104909378 A CN104909378 A CN 104909378A
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Abstract
The invention discloses a preparation method of monodisperse porous silicon dioxide microspheres, which comprises the following steps: hydrolyzing ethyl orthosilicate under alkaline conditions to generate nano solid silicon dioxide microspheres, and carrying out hydrothermal treatment to implement solid-to-porous transition, thereby obtaining the monodisperse porous silicon dioxide microsphere material with controllable microsphere diameter/pore size and favorable biocompatibility. The preparation method is simple, and has the advantages of mild reaction conditions and no harm to the environment. The prepared porous silicon dioxide microspheres have favorable monodispersity and biocompatibility, and can be widely used in the fields of biomedicine, catalytic carriers and the like.
Description
Technical field
The present invention relates to materials synthesis technology of preparing, particularly relate to a kind of preparation method of monodisperse porous silicon dioxide microsphere.
Background technology
Be since template successfully synthesizes M41S type series ordered mesoporous silicon-dioxide material from scientists such as the Kresge of Mobil company in 1992 with cats product, because of advantages such as its high-specific surface area, orderly pore distributions, have extremely wide application prospect in the field such as biological medicine and catalytic material, the porous material being representative with it becomes rapidly the study hotspot of domestic and international Material Field.
General porous silica silicon materials are using surfactant molecules aggregate body as template, using tetraethoxy as silicon source, by in aqueous, tensio-active agent self-assembled micelle and tetraethoxy interfacial assembly become cavernous structure, the Metaporous silicon dioxide materials such as such as already commercial MCM-41, be widely used in medicament slow release (Vallet-Regi M, Ramila A, Del Real R P, et al. [J] .Chemistry of Materials, 2001, 13 (2): 308-311.) and gene delivery (Vallet-Regi, F., Balas, M., Colilla, M., Manzano, M., Solid State Sci.2007, 9, 768-776.) etc. field, but its aperture is generally 3 ~ 5nm, its aperture is less, can only by the material of small-molecular-weight, thus its Application Areas is restricted.Therefore the material preparing the wide porous of pore size distribution becomes study hotspot.Such as, DechaoNiu etc. utilize segmented copolymer PS-b-PAA and cetyl trimethylammonium bromide (CTAB) double template to prepare macroporous silica, and for drug delivery field (Niu D, Liu Z, Li Y, et al. [J] .Advanced Materials, 2014), but the method has used traditional template CTAB, CTAB is quaternary ammonium salts cats product, bio-toxicity is large, limits with the application of the porous material of this synthesis of surfactant.
In Chinese patent literature, the anion surfactant (sarcosyl) that Chen Tiehong etc. (CN1923684A) utilize toxicity less is cooked Template preparation mesoporous silicon oxide, but the mesoporous silicon oxide particle diameter heterogeneity of preparation, and it is mesoporous to be aperture at ~ 3nm, and, owing to having used the structure directing agents such as (3-aminopropyl) Trimethoxy silane, reactant used is many, preparation process is complicated, significantly limit the Synthesis and applications of this material.Dai Zhao etc. (CN 102351200A) utilize the organic polymeric microspheres of small particle size for pore-forming material, finally utilize solvent or the inner organic template of calcining removing, have prepared macroporous silica microsphere; Use organic polymeric microspheres due to it and done template, made to utilize the means of solvent or calcining to remove this template, cause the method toxicity large not environmentally, and it has been high to consume energy, and is difficult to the utility value representing the method in actual applications.
Summary of the invention
The object of this invention is to provide a kind of monodisperse porous silicon dioxide microsphere preparation method, first prepare material based on the solid silicon dioxide microsphere of single dispersing, carry out hydrothermal treatment consists to it to realize by the solid transformation to porous, thus obtain desirable monodisperse porous silicon dioxide microsphere material.
Concrete synthesis step is as follows:
1) preparation of the solid silicon dioxide microsphere of single dispersing:
Tetraethoxy (TEOS) and a small amount of dehydrated alcohol mix in the ethanol solution joined containing proper ammonia, centrifuge washing after stirring reaction certain time length, dry the solid silicon dioxide microsphere of single dispersing.
2) preparation of monodisperse porous silicon dioxide microsphere:
Being joined by the solid silicon dioxide microsphere of gained is placed with in the hydrothermal reaction kettle of reaction solution, be heated to 100-140 DEG C and be incubated 8-20 hour, then be cooled to room temperature, by centrifuge washing, dry monodisperse porous silicon dioxide microsphere, wherein reaction solution at least includes deionized water; Obtained monodisperse porous silicon dioxide microsphere particle size range is 50-200nm, and pore diameter range is 5-30nm.
Preferably, step 1) in, the volume range of described tetraethoxy and ammoniacal liquor is 5:1 ~ 1:5; The cumulative volume of described dehydrated alcohol is the 80-95% of reaction soln.
Preferably, step 1) in, the mixing solutions of described tetraethoxy and dehydrated alcohol slowly joins in the mixing solutions of described ammoniacal liquor and dehydrated alcohol by the mode of dropping, mixing solutions heating in water bath to 30 ~ 40 DEG C of wherein said ammoniacal liquor and dehydrated alcohol.
Preferably, step 1) in, the time of described stirring reaction is 15-30 hour.
Preferably, step 2) in, the quality of described solid silicon dioxide microsphere is the 1-10% of deionized water quality.
Preferably, step 2) in, described reaction solution also comprises dehydrated alcohol, and the volume ratio of described dehydrated alcohol in reaction solution is less than 50%.
Preferably, step 2) in, described reaction solution also comprises water-soluble polymers, and the volume ratio of described water-soluble polymers in reaction solution is less than 10%.
Preferably, described water-soluble polymers is at least one of polyvinylpyrrolidone (PVP) or polyoxyethylene glycol (PEG).
Preferably, the particle diameter of described monodisperse porous silicon dioxide microsphere is 60-100nm, and pore diameter range is 8-20nm.。
Preparation method described in the present invention is simple, reaction conditions is gentle, can rate-determining steps 1 be passed through) in add TEOS and ammoniacal liquor amount and and the ratio of dehydrated alcohol control size, by rate-determining steps 2) in the amount of the water-soluble polymers such as PVP, PEG carry out the size of adjustment aperture, thus obtain particle diameter and the homogeneous adjustable monodisperse porous silicon dioxide microsphere of pore size, be applicable to various field; Especially the porous silica microballoon prepared does not comprise the template (as CTAB etc.) that traditional preparation methods adds, and not containing tensio-active agent and other hazardous and noxious substances, products pure, extends its application at biomedicine field greatly; In addition, compared to traditional method for removing template needs to carry out high temperature (~ 600 DEG C) calcining to silicon dioxide microsphere material, the present invention only needs lower temperature (~ 120 DEG C) to react, and more energy-conserving and environment-protective, are suitable for production application.
Below in conjunction with drawings and Examples, the present invention is described in further detail; But the preparation method of a kind of monodisperse porous silicon dioxide microsphere of the present invention is not limited to embodiment.
Accompanying drawing explanation
Fig. 1 is TEM (transmission electron microscope) photo of the solid silicon dioxide microsphere of single dispersing of the present invention;
Fig. 2 is the TEM photo of monodisperse porous silicon dioxide microsphere of the present invention (thermal treatment of pure water aqueous solvent);
Fig. 3 is the TEM photo of monodisperse porous silicon dioxide microsphere of the present invention (adding the thermal treatment of PVP polymer water);
Fig. 4 is the TEM photo of monodisperse porous silicon dioxide microsphere of the present invention (adding the thermal treatment of PEG polymer water).
Embodiment
Embodiment 1:
5mL ammoniacal liquor and 96mL dehydrated alcohol are added in single port flask, be uniformly mixed and be placed in 30 DEG C of water-baths, after temperature-stable, get after 4mL tetraethoxy (TEOS) mixes with 4mL dehydrated alcohol and dropwise add, stirred at ambient temperature 24h, by product centrifugation and with absolute ethanol washing repeatedly, final drying obtains the solid silicon dioxide microsphere of single dispersing, its transmission electron microscope photo as shown in Figure 1, visible obtained solid silicon dioxide microsphere structural integrity, size are even, and particle diameter is at about 70nm.
Get the above-mentioned solid silicon dioxide microsphere of 0.5g and 20mL deionized water has joined in teflon-lined hydrothermal reaction kettle, the thermostat container being placed in 130 DEG C leaves standstill 12h.Product is taken out centrifugation and with absolute ethanol washing repeatedly, drying both monodisperse porous silicon dioxide microsphere material, as shown in Figure 2, the micropore on visible obtained porous silica microballoon is evenly distributed its transmission electron microscope photo, and pore size is about 8nm.
In the present embodiment, tetraethoxy generates nano level solid silicon dioxide microparticle by the step of hydrolysis, nucleation and particle growth under the catalysis of ammoniacal liquor, under the condition of hydro-thermal reaction, the reaction environment of High Temperature High Pressure makes the nano particle forming solid silicon dioxide microsphere remove formation hole under pyrohydrolysis effect.
Embodiment 2:
In Example 1, the mixing solutions of the solid silicon dioxide microsphere of the 0.5g of step 1 gained and 20mL deionized water and dehydrated alcohol has joined in teflon-lined hydrothermal reaction kettle, and the thermostat container being placed in 120 DEG C leaves standstill 18h.Product is taken out centrifugation and with absolute ethanol washing repeatedly, drying both monodisperse porous silicon dioxide microsphere material.Wherein the volume ratio of deionized water and dehydrated alcohol is 2:1.Micropore on obtained porous silica microballoon is evenly distributed, and pore size is about 12nm.
In the present embodiment, dehydrated alcohol is added in hydrothermal reaction process, because ethanol has better solvency action to silicon-dioxide, the therefore dual function of second alcohol and water in the reaction environment of High Temperature High Pressure, causes the hole of the last porous silica formed to become large.
Embodiment 3:
In Example 1, the aqueous solution of the solid silicon dioxide microsphere of the 0.5g of step 1 gained and 20mL water-soluble polymers has joined in teflon-lined hydrothermal reaction kettle, and the thermostat container being placed in 100 DEG C leaves standstill 20h.Product is taken out centrifugation and with absolute ethanol washing repeatedly, drying both monodisperse porous silicon dioxide microsphere material.It is obtained that the aqueous solution of water-soluble polymers is that 0.05g polyvinylpyrrolidone (PVP) mixes with deionized water.
As shown in Figure 3, visible micropore is evenly distributed obtained porous silica microballoon transmission electron microscope photo, and pore size is about 20nm.In the present embodiment, because adding of PVP can penetrate into silica interior when hydrolytic action, more nano particle is removed, causes the hole of last porous silica microballoon to increase further.
Embodiment 4:
In Example 1, the aqueous solution of the solid silicon dioxide microsphere of the 0.5g of step 1 gained and 20mL water-soluble polymers has joined in teflon-lined hydrothermal reaction kettle, and the thermostat container being placed in 100 DEG C leaves standstill 20h.Product is taken out centrifugation and with absolute ethanol washing repeatedly, drying both monodisperse porous silicon dioxide microsphere material.It is obtained that the aqueous solution of water-soluble polymers is that 0.05g polyoxyethylene glycol (PEG) mixes with deionized water.
As shown in Figure 4, visible micropore is evenly distributed obtained porous silica microballoon transmission electron microscope photo, and pore size is about 20nm.In the present embodiment, due to adding of PEG, similar to Example 3, the effect acting on PVP of PEG is the same, can better remove nano SiO 2 particle and cause aperture to increase.
Above-described embodiment is only used for further illustrating the preparation method of a kind of monodisperse porous silicon dioxide microsphere of the present invention; but the present invention is not limited to embodiment; every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall in the protection domain of technical solution of the present invention.
Claims (9)
1. a preparation method for monodisperse porous silicon dioxide microsphere, is characterized in that comprising the following steps:
1) mixing solutions of tetraethoxy and dehydrated alcohol is joined in the mixing solutions of ammoniacal liquor and dehydrated alcohol, washs after stirring reaction, dry the solid silicon dioxide microsphere of single dispersing;
2) described solid silicon dioxide microsphere is joined be placed with in the hydrothermal reaction kettle of reaction solution, be heated to 100-140 DEG C and be incubated 8-20 hour, be cooled to washing after room temperature, dry monodisperse porous silicon dioxide microsphere, wherein said reaction solution at least comprises deionized water; The particle size range of obtained monodisperse porous silicon dioxide microsphere is 50-200nm, and pore diameter range is 5-30nm.
2. preparation method according to claim 1, is characterized in that: step 1) in, the volume range of described tetraethoxy and ammoniacal liquor is 5:1 ~ 1:5; The cumulative volume of described dehydrated alcohol is the 80-95% of reaction soln.
3. preparation method according to claim 1 and 2, it is characterized in that: step 1) in, the mixing solutions of described tetraethoxy and dehydrated alcohol slowly joins in the mixing solutions of described ammoniacal liquor and dehydrated alcohol by the mode of dropping, mixing solutions heating in water bath to 30 ~ 40 DEG C of wherein said ammoniacal liquor and dehydrated alcohol.
4. preparation method according to claim 1, is characterized in that: step 1) in, the time of described stirring reaction is 15-30 hour.
5. preparation method according to claim 1, is characterized in that: step 2) in, the quality of described solid silicon dioxide microsphere is the 1-10% of deionized water quality.
6. preparation method according to claim 1, is characterized in that: step 2) in, described reaction solution also comprises dehydrated alcohol, and the volume ratio of described dehydrated alcohol in reaction solution is less than 50%.
7. preparation method according to claim 1, is characterized in that: step 2) in, described reaction solution also comprises water-soluble polymers, and the volume ratio of described water-soluble polymers in reaction solution is less than 10%.
8. preparation method according to claim 7, is characterized in that: described water-soluble polymers is at least one of polyvinylpyrrolidone or polyoxyethylene glycol.
9. preparation method according to claim 7, is characterized in that: the particle diameter of described monodisperse porous silicon dioxide microsphere is 60-100nm, and pore diameter range is 8-20nm.
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Cited By (7)
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| CN107399741A (en) * | 2017-08-18 | 2017-11-28 | 江西师范大学 | A kind of preparation method of the less monodisperse silica microspheres of size |
| CN108455620A (en) * | 2018-03-31 | 2018-08-28 | 蒋建华 | A kind of preparation method of nano silicon dioxide |
| CN110371992A (en) * | 2019-07-19 | 2019-10-25 | 国家纳米科学中心 | It is a kind of regulate and control microemulsion reaction methods monodisperse silica sphere particle method and products thereof and purposes |
| CN110683552A (en) * | 2019-10-17 | 2020-01-14 | 蚌埠市万科硅材料科技有限公司 | Preparation method of nano silicon dioxide microspheres with particle size of 10-20nm |
| CN110924193A (en) * | 2019-12-11 | 2020-03-27 | 苏州经贸职业技术学院 | Preparation method of reactive dye dyeing accelerating functional agent |
| CN112221474A (en) * | 2020-09-23 | 2021-01-15 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN112791739A (en) * | 2019-11-13 | 2021-05-14 | 中国科学院大连化学物理研究所 | Preparation and application of carbon dioxide electrochemical reduction catalyst |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107399741A (en) * | 2017-08-18 | 2017-11-28 | 江西师范大学 | A kind of preparation method of the less monodisperse silica microspheres of size |
| CN108455620A (en) * | 2018-03-31 | 2018-08-28 | 蒋建华 | A kind of preparation method of nano silicon dioxide |
| CN110371992A (en) * | 2019-07-19 | 2019-10-25 | 国家纳米科学中心 | It is a kind of regulate and control microemulsion reaction methods monodisperse silica sphere particle method and products thereof and purposes |
| CN110683552A (en) * | 2019-10-17 | 2020-01-14 | 蚌埠市万科硅材料科技有限公司 | Preparation method of nano silicon dioxide microspheres with particle size of 10-20nm |
| CN110683552B (en) * | 2019-10-17 | 2022-05-03 | 蚌埠市万科硅材料科技有限公司 | Preparation method of nano silicon dioxide microspheres with particle size of 10-20nm |
| CN112791739A (en) * | 2019-11-13 | 2021-05-14 | 中国科学院大连化学物理研究所 | Preparation and application of carbon dioxide electrochemical reduction catalyst |
| CN110924193A (en) * | 2019-12-11 | 2020-03-27 | 苏州经贸职业技术学院 | Preparation method of reactive dye dyeing accelerating functional agent |
| CN112221474A (en) * | 2020-09-23 | 2021-01-15 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN112221474B (en) * | 2020-09-23 | 2023-04-07 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
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Effective date of registration: 20230922 Address after: 361000 1st floor, 128 Guankou Middle Road, Guankou Town, Jimei District, Xiamen City, Fujian Province Patentee after: Wanxin (Xiamen) new materials Co.,Ltd. Address before: 361000 Siming South Road, Xiamen, Fujian Province, No. 422 Patentee before: XIAMEN University |