技术领域Technical field
本发明属于纳米材料合成技术领域，具体涉及一种由聚乙烯亚胺为结构导向剂制备中空介孔二氧化硅的方法及中空介孔二氧化硅。The invention belongs to the technical field of nanomaterial synthesis, and specifically relates to a method for preparing hollow mesoporous silica using polyethyleneimine as a structural directing agent and hollow mesoporous silica.
背景技术Background technique
介孔材料具有特定的孔道结构、内部空间大、比表面积高、良好的热稳定性、易于官能化、更是丰富的合成原料等诸多优点而引起科研人员的广泛关注。中空介孔二氧化硅纳米微球做为一种骨架稳定、无毒性、强度出色的介孔材料。在光伏、电池、能源催化、生物医药、传感和纳米工程都有着重要的应用价值。Mesoporous materials have many advantages such as specific pore structure, large internal space, high specific surface area, good thermal stability, easy functionalization, and abundant synthetic raw materials, which have attracted widespread attention from scientific researchers. Hollow mesoporous silica nanospheres are mesoporous materials with stable skeleton, non-toxicity and excellent strength. It has important application value in photovoltaics, batteries, energy catalysis, biomedicine, sensing and nanoengineering.
目前二氧化硅空心微球的制备方法主要为牺牲模板法，包括硬模板法和软模板法。目前较为成熟的合成方法当属硬模板法，能够合成不同结构的介孔材料且普适性强，但在合成的过程中必须要先合成具有规整结构且符合要求的模板，这就导致步骤繁琐且产率低。软模板法又称为嵌段共聚物的自组装法，步骤简单，过程容易控制。另外，软模板法制备成本低，环境污染相对较小。At present, the preparation method of silica hollow microspheres is mainly the sacrificial template method, including hard template method and soft template method. At present, the more mature synthesis method is the hard template method, which can synthesize mesoporous materials with different structures and has strong universal applicability. However, in the synthesis process, a template with a regular structure and meeting the requirements must be synthesized first, which leads to cumbersome steps. And the yield is low. The soft template method is also called the self-assembly method of block copolymers. The steps are simple and the process is easy to control. In addition, the soft template method has low preparation cost and relatively little environmental pollution.
例如CN108912330A公开了一种聚吡咯中空介孔二氧化硅微球的制备方法及应用。首先需制备出不同粒径的单分散微球做为模板。后续合成中空介孔二氧化硅微球的制备过程繁琐，实验过程中需用到烘箱高温长时间的处理，反应周期较长。For example, CN108912330A discloses a preparation method and application of polypyrrole hollow mesoporous silica microspheres. First, monodisperse microspheres of different particle sizes need to be prepared as templates. The preparation process for subsequent synthesis of hollow mesoporous silica microspheres is cumbersome. During the experiment, high temperature and long-term treatment in an oven are required, resulting in a long reaction cycle.
此外，CN107970878B公开了一种磷酸基团官能化中空介孔二氧化硅微球复合材料的合成方法。采用葡萄糖水热法制备大粒径单分散的碳球为硬模板，同时在长时间高温水热制备前，还需通入一定时间的氮气气体用于保护。在对碳球模板表面预处理处理、调节反应溶液的PH值后，在表面活性剂的作用下合成核壳型前驱物。最后通过马弗炉的高温煅烧去除模板，得到中空介孔二氧化硅微球。实验过程较为复杂耗时，实验过程中还需要氮气保护，条件较为苛刻。In addition, CN107970878B discloses a synthesis method of phosphoric acid group functionalized hollow mesoporous silica microsphere composite materials. Large-sized monodispersed carbon spheres are prepared using glucose hydrothermal method as hard templates. At the same time, before long-term high-temperature hydrothermal preparation, nitrogen gas needs to be introduced for a certain period of time for protection. After pretreating the surface of the carbon sphere template and adjusting the pH value of the reaction solution, the core-shell precursor is synthesized under the action of surfactant. Finally, the template is removed through high-temperature calcination in a muffle furnace to obtain hollow mesoporous silica microspheres. The experimental process is complex and time-consuming. Nitrogen protection is also required during the experimental process, and the conditions are relatively harsh.
发明内容Contents of the invention
本发明的目的是为了解决现有的制备中空介孔二氧化硅微球的方法，实验过程较为复杂耗时，条件较为苛刻的技术问题，而提供一种由聚乙烯亚胺为结构导向剂制备中空介孔二氧化硅的方法及中空介孔二氧化硅。The purpose of the present invention is to solve the technical problems of the existing method for preparing hollow mesoporous silica microspheres, the experimental process is relatively complex and time-consuming, and the conditions are relatively harsh, and to provide a method prepared by using polyethyleneimine as a structural directing agent. Method for hollow mesoporous silica and hollow mesoporous silica.
为实现上述目的，本发明提供如下技术方案：In order to achieve the above objects, the present invention provides the following technical solutions:
一种由聚乙烯亚胺为结构导向剂制备中空介孔二氧化硅的方法，包括以下步骤：A method for preparing hollow mesoporous silica using polyethyleneimine as a structure directing agent, including the following steps:
步骤一：将聚乙烯亚胺、氨水和乙醇混合搅拌，得到混合液；Step 1: Mix and stir polyethyleneimine, ammonia and ethanol to obtain a mixed solution;
步骤二：在步骤一的混合液中加入CTAB水溶液和正硅酸乙酯反应，经回流、离心、洗涤、干燥得到反应产物；Step 2: Add CTAB aqueous solution and ethyl orthosilicate to the mixture in step 1 to react, and obtain the reaction product by refluxing, centrifuging, washing, and drying;
步骤三：将步骤二的反应产物进行煅烧，得到中空介孔二氧化硅。Step 3: Calculate the reaction product of Step 2 to obtain hollow mesoporous silica.
优选的，步骤一所述的聚乙烯亚胺的质量g：氨水的体积mL：乙醇的体积mL为(0.04～0.08):(0.7～2.8):(30～60)。Preferably, the mass g of polyethyleneimine described in step 1: the volume mL of ammonia water: the volume mL of ethanol is (0.04~0.08): (0.7~2.8): (30~60).
优选的，步骤一所述的搅拌温度为室温，搅拌时间为30-40min。Preferably, the stirring temperature in step one is room temperature, and the stirring time is 30-40 minutes.
优选的，步骤二所述的CTAB水溶液的制备方法包括：将CTAB、氨水、去离子水混合，超声分散后搅拌，得到CTAB水溶液。Preferably, the preparation method of the CTAB aqueous solution in step 2 includes: mixing CTAB, ammonia water, and deionized water, ultrasonic dispersion and then stirring to obtain a CTAB aqueous solution.
优选的，所述的CTAB的质量g：氨水的体积mL：去离子水的体积mL为(0.04～0.06)：(1～2)：(50～100)。Preferably, the mass g of CTAB: the volume mL of ammonia water: the volume mL of deionized water is (0.04~0.06): (1~2): (50~100).
优选的，所述正硅酸乙酯的体积mL:CTAB的质量g为:(0.6～1)(0.04～0.06)。Preferably, the volume mL of ethyl orthosilicate: the mass g of CTAB is: (0.6~1) (0.04~0.06).
优选的，所述的步骤二的反应温度为30～40℃，反应时间为12～24h。Preferably, the reaction temperature in step two is 30-40°C, and the reaction time is 12-24 hours.
优选的，所述的步骤二的回流为：在酸性的乙醇溶液中60℃下回流12h，离心洗涤后分散在水/醇体积比为0.4的混合溶液中70～90℃下再次回流6～12h。Preferably, the reflux in step two is: reflux in an acidic ethanol solution at 60°C for 12 hours, centrifuge and wash, disperse in a mixed solution with a water/alcohol volume ratio of 0.4, and reflux again at 70 to 90°C for 6 to 12 hours. .
优选的，所述的步骤三的煅烧温度为500-600℃，煅烧时间为3-8h。Preferably, the calcination temperature in step three is 500-600°C, and the calcination time is 3-8 hours.
本发明提供一种由上述方法制备的中空介孔二氧化硅。The invention provides hollow mesoporous silica prepared by the above method.
本发明的有益效果Beneficial effects of the invention
本发明提供一种由聚乙烯亚胺为结构导向剂制备中空介孔二氧化硅的方法及中空介孔二氧化硅，该方法是以正硅酸乙酯(TEOS)为硅源,聚乙烯亚胺(PEI)和十六烷基三甲基溴化铵(CTAB)分别作为氧化硅微球中空结构和介孔孔道的结构导向剂，一步法制备空心二氧化硅球，最后空气下煅烧彻底除去模板得到中空介孔二氧化硅球。和现有技术相对比，本发明的方法工艺简单、操作简便条件温和、合成周期短效率高。The invention provides a method for preparing hollow mesoporous silica using polyethyleneimine as a structure directing agent and hollow mesoporous silica. The method uses tetraethylorthosilicate (TEOS) as a silicon source and polyethyleneimine. Amine (PEI) and cetyltrimethylammonium bromide (CTAB) are used as structural guiding agents for the hollow structure and mesoporous channels of silica microspheres respectively. Hollow silica spheres are prepared in one step, and finally are completely removed by calcination under air. The template is used to obtain hollow mesoporous silica spheres. Compared with the existing technology, the method of the present invention has simple process, easy operation, mild conditions, short synthesis cycle and high efficiency.
附图说明Description of drawings
图1为本发明实施例1中制得的中空二氧化硅微球的扫描电镜照片；Figure 1 is a scanning electron microscope photograph of the hollow silica microspheres prepared in Example 1 of the present invention;
图2为本发明实施例1及对比例1-2中加入CTAB水溶液后不同搅拌时间下，对应的小角度XRD谱图；Figure 2 is the corresponding small-angle XRD spectrum under different stirring times after adding CTAB aqueous solution to Example 1 and Comparative Examples 1-2 of the present invention;
图3为本发明实施例1-3中不同煅烧时间制得的中空介孔二氧化硅微球的红外谱图；Figure 3 is an infrared spectrum of hollow mesoporous silica microspheres prepared at different calcination times in Examples 1-3 of the present invention;
图4为本发明实施例1中煅烧3h制得的中空介孔二氧化硅微球的孔径和比表面积图；Figure 4 is a diagram of the pore size and specific surface area of hollow mesoporous silica microspheres prepared by calcination for 3 hours in Example 1 of the present invention;
图5为本发明实施例1中回流后制得的中空二氧化硅微球的透射照片。Figure 5 is a transmission photograph of the hollow silica microspheres produced after reflow in Example 1 of the present invention.
具体实施方式Detailed ways
一种由聚乙烯亚胺为结构导向剂制备中空介孔二氧化硅的方法，包括以下步骤：A method for preparing hollow mesoporous silica using polyethyleneimine as a structure directing agent, including the following steps:
步骤一：将聚乙烯亚胺、氨水和乙醇混合搅拌，所述的搅拌温度优选为室温，搅拌时间优选为30-40min，得到混合液；所述的聚乙烯亚胺的质量g：氨水的体积mL：乙醇的体积mL优选为(0.04～0.08):(0.7～2.8):(30～60)；Step 1: Mix and stir polyethyleneimine, ammonia water and ethanol. The stirring temperature is preferably room temperature, and the stirring time is preferably 30-40 min to obtain a mixed solution; the mass g of the polyethyleneimine: the volume of ammonia water. mL: The volume mL of ethanol is preferably (0.04~0.08):(0.7~2.8):(30~60);
步骤二：在步骤一的混合液中加入CTAB水溶液和正硅酸乙酯反应，所述反应温度优选为30～40℃，反应时间优选为12～24h，经回流、离心、洗涤、干燥得到反应产物；所述正硅酸乙酯的体积mL:CTAB的质量g优选为:(0.6～1)(0.04～0.06)。Step 2: Add CTAB aqueous solution and ethyl orthosilicate to the mixture in step 1 to react. The reaction temperature is preferably 30 to 40°C, and the reaction time is preferably 12 to 24 hours. The reaction product is obtained by refluxing, centrifuging, washing, and drying. ; The volume mL of ethyl orthosilicate: the mass g of CTAB is preferably: (0.6~1) (0.04~0.06).
所述的CTAB水溶液的制备方法优选包括：将CTAB、氨水、去离子水混合，超声分散后搅拌，所述超声分散时间优选为5～10min，所述的搅拌温度优选为40～60℃，搅拌时间优选为5～10min，冷却，得到CTAB水溶液。所述的CTAB的质量g：氨水的体积mL：去离子水的体积mL优选为(0.04～0.06)：(1～2)：(50～100)。The preparation method of the CTAB aqueous solution preferably includes: mixing CTAB, ammonia and deionized water, ultrasonic dispersion and then stirring. The ultrasonic dispersion time is preferably 5 to 10 minutes. The stirring temperature is preferably 40 to 60°C. Stirring The time is preferably 5 to 10 minutes, and the mixture is cooled to obtain a CTAB aqueous solution. The mass g of CTAB: the volume mL of ammonia water: the volume mL of deionized water is preferably (0.04~0.06): (1~2): (50~100).
所述加入CTAB水溶液和正硅酸乙酯为：优选先全部加入CTAB水溶液后搅拌反应，所述的反应时间优选为30min，然后再滴加入正硅酸乙酯溶液。The method of adding CTAB aqueous solution and ethyl orthosilicate is: preferably add all the CTAB aqueous solution first and then stir the reaction. The reaction time is preferably 30 minutes, and then add the ethyl orthosilicate solution dropwise.
所述的回流条件优选为：在酸性的乙醇溶液中60℃下回流12h，离心洗涤后分散在水/醇体积比为0.4的混合溶液中70～90℃下再次回流6～12h。The reflux conditions are preferably: reflux in an acidic ethanol solution at 60°C for 12 hours, centrifuge and wash, disperse in a mixed solution with a water/alcohol volume ratio of 0.4, and reflux again at 70 to 90°C for 6 to 12 hours.
所述洗涤为优选采用水/乙醇洗涤多次。The washing is preferably carried out multiple times with water/ethanol.
步骤三：将步骤二的反应产物进行煅烧，得到中空介孔二氧化硅。所述的煅烧温度优选为500-600℃，更优选为500℃，煅烧时间优选为3-8h，更优选为3h。Step 3: Calculate the reaction product of Step 2 to obtain hollow mesoporous silica. The calcination temperature is preferably 500-600°C, more preferably 500°C, and the calcination time is preferably 3-8h, more preferably 3h.
本发明提供一种由上述方法制备的中空介孔二氧化硅纳米微球材料。The invention provides a hollow mesoporous silica nanometer microsphere material prepared by the above method.
下面结合附图和具体实施例对本发明做进一步详细的说明，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例,应理解这些实施例仅用于说明本发明，本发明能实施的范围不限于这些条件，也不限于这些实施例。The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. The described embodiments are only some of the embodiments of the present invention, rather than all of the embodiments. It should be understood that these embodiments are only used to illustrate the present invention. The scope of implementation is not limited to these conditions, nor is it limited to these examples.
对比例1Comparative example 1
在烧杯称量0.06g聚乙烯亚胺(Mw＝1800)，依次加入1.4mL氨水、45mL乙醇在25℃、500rpm的条件下搅拌30min。将1.65mL氨水与0.055g十六烷基三甲基溴化铵(CTAB)溶解在65mL的去离子水中，超声5min后在50℃下搅10min，冷却至室温，将得到的CTAB水溶液全部加入上述烧杯继续反应0min后快速添加0.9mL正硅酸乙酯(TEOS)，并将温度升高至35℃继续搅拌12h。离心收集(9000rpm，10min)并洗涤后使用100ml乙醇将离心得到的产物分散在双颈烧瓶中，最后加入200ul盐酸【37％】回流12h，将产物离心洗涤后分散在水/醇体积比为0.4的100mL的混合溶液中，70℃下搅拌6h。离心收集洗涤后置于50℃烘箱中干燥10h，最后将产物置于500℃马弗炉中焙烧3h，得到中空介孔二氧化硅微球。Weigh 0.06g polyethyleneimine (Mw=1800) in a beaker, add 1.4mL ammonia water and 45mL ethanol in sequence, and stir for 30 minutes at 25°C and 500rpm. Dissolve 1.65mL ammonia water and 0.055g cetyltrimethylammonium bromide (CTAB) in 65mL deionized water, sonicate for 5 minutes, stir at 50°C for 10 minutes, cool to room temperature, and add all the CTAB aqueous solution obtained above. The beaker continued to react for 0 min, then quickly added 0.9 mL of tetraethyl orthosilicate (TEOS), and raised the temperature to 35°C and continued stirring for 12 h. Collect by centrifugation (9000rpm, 10min) and wash. Use 100ml of ethanol to disperse the centrifuged product in a double-neck flask. Finally, add 200ul of hydrochloric acid [37%] and reflux for 12h. Centrifuge and wash the product and disperse it in a water/alcohol volume ratio of 0.4. into 100 mL of mixed solution and stirred at 70°C for 6 hours. After centrifugal collection and washing, it was dried in an oven at 50°C for 10 hours. Finally, the product was roasted in a muffle furnace at 500°C for 3 hours to obtain hollow mesoporous silica microspheres.
对比例2Comparative example 2
在烧杯称量0.06g聚乙烯亚胺(Mw＝1800)，依次加入1.4mL氨水、45mL乙醇在25℃、500rpm的条件下搅拌30min。将1.65mL氨水与0.055g十六烷基三甲基溴化铵(CTAB)溶解在65mL的去离子水中，超声5min后在50℃下搅10min，冷却至室温，将得到的CTAB水溶液全部加入上述烧杯继续反应60min后快速添加0.9mL正硅酸乙酯(TEOS)，并将温度升高至35℃继续搅拌12h。离心收集(9000rpm，10min)并洗涤后使用100ml乙醇将离心得到的产物分散在双颈烧瓶中，最后加入200ul盐酸【37％】回流12h，将产物离心洗涤后分散在水/醇体积比为0.4的100mL的混合溶液中，70℃下搅拌6h。离心收集洗涤后置于50℃烘箱中干燥10h，最后将产物置于500℃马弗炉中焙烧3h，得到中空介孔二氧化硅微球。Weigh 0.06g polyethyleneimine (Mw=1800) in a beaker, add 1.4mL ammonia water and 45mL ethanol in sequence, and stir for 30 minutes at 25°C and 500rpm. Dissolve 1.65mL ammonia water and 0.055g cetyltrimethylammonium bromide (CTAB) in 65mL deionized water, sonicate for 5 minutes, stir at 50°C for 10 minutes, cool to room temperature, and add all the CTAB aqueous solution obtained above. The beaker continued to react for 60 minutes, then quickly added 0.9 mL of ethyl orthosilicate (TEOS), and raised the temperature to 35°C and continued stirring for 12 hours. Collect by centrifugation (9000rpm, 10min) and wash. Use 100ml of ethanol to disperse the centrifuged product in a double-neck flask. Finally, add 200ul of hydrochloric acid [37%] and reflux for 12h. Centrifuge and wash the product and disperse it in a water/alcohol volume ratio of 0.4. into 100 mL of mixed solution and stirred at 70°C for 6 hours. After centrifugal collection and washing, it was dried in an oven at 50°C for 10 hours. Finally, the product was roasted in a muffle furnace at 500°C for 3 hours to obtain hollow mesoporous silica microspheres.
实施例1Example 1
在烧杯称量0.06mg聚乙烯亚胺(Mw＝1800)，依次加入1.4mL氨水、45mL乙醇在25℃、500rpm的条件下搅拌30min。将1.65mL氨水与0.055g十六烷基三甲基溴化铵(CTAB)溶解在65mL的去离子水中，超声5min后在50℃下搅10min，冷却至室温，将得到的CTAB水溶液全部加入上述烧杯继续反应30min后快速添加0.9mL正硅酸乙酯(TEOS)，并将温度升高至35℃继续搅拌12h。离心收集(9000rpm，10min)并洗涤后使用100ml乙醇将离心得到的产物分散在双颈烧瓶中，最后加入200ul盐酸【37％】回流12h，将产物离心洗涤后分散在水/醇体积比为0.4的100mL的混合溶液中，70℃下搅拌6h。离心收集洗涤后置于50℃烘箱中干燥10h，最后将产物置于500℃马弗炉中焙烧3h，得到中空介孔二氧化硅微球。Weigh 0.06 mg of polyethyleneimine (Mw=1800) in a beaker, add 1.4 mL of ammonia water and 45 mL of ethanol in sequence, and stir for 30 min at 25°C and 500 rpm. Dissolve 1.65mL ammonia water and 0.055g cetyltrimethylammonium bromide (CTAB) in 65mL deionized water, sonicate for 5 minutes, stir at 50°C for 10 minutes, cool to room temperature, and add all the CTAB aqueous solution obtained above. The beaker continued to react for 30 minutes, then quickly added 0.9 mL of ethyl orthosilicate (TEOS), and raised the temperature to 35°C and continued stirring for 12 hours. Collect by centrifugation (9000rpm, 10min) and wash. Use 100ml of ethanol to disperse the centrifuged product in a double-neck flask. Finally, add 200ul of hydrochloric acid [37%] and reflux for 12h. Centrifuge and wash the product and disperse it in a water/alcohol volume ratio of 0.4. into 100 mL of mixed solution and stirred at 70°C for 6 hours. After centrifugal collection and washing, it was dried in an oven at 50°C for 10 hours. Finally, the product was roasted in a muffle furnace at 500°C for 3 hours to obtain hollow mesoporous silica microspheres.
实施例2Example 2
在烧杯称量0.06mg聚乙烯亚胺(Mw＝1800)，依次加入1.4mL氨水、45mL乙醇在25℃、500rpm的条件下搅拌30min。将1.65mL氨水与0.055g十六烷基三甲基溴化铵(CTAB)溶解在65mL的去离子水中，超声5min后在50℃下搅10min，冷却至室温，将得到的CTAB水溶液全部加入上述烧杯继续反应30min后快速添加0.9mL正硅酸乙酯(TEOS)，并将温度升高至35℃继续搅拌12h。离心收集(9000rpm，10min)并洗涤后使用100ml乙醇将离心得到的产物分散在双颈烧瓶中，最后加入200ul盐酸【37％】回流12h，将产物离心洗涤后分散在水/醇体积比为0.4的100mL的混合溶液中，70℃下搅拌6h。离心收集洗涤后置于50℃烘箱中干燥10h，最后将产物置于500℃马弗炉中焙烧5h，得到中空介孔二氧化硅微球。Weigh 0.06 mg of polyethyleneimine (Mw=1800) in a beaker, add 1.4 mL of ammonia water and 45 mL of ethanol in sequence, and stir for 30 min at 25°C and 500 rpm. Dissolve 1.65mL ammonia water and 0.055g cetyltrimethylammonium bromide (CTAB) in 65mL deionized water, sonicate for 5 minutes, stir at 50°C for 10 minutes, cool to room temperature, and add all the CTAB aqueous solution obtained above. The beaker continued to react for 30 minutes, then quickly added 0.9 mL of ethyl orthosilicate (TEOS), and raised the temperature to 35°C and continued stirring for 12 hours. Collect by centrifugation (9000rpm, 10min) and wash. Use 100ml of ethanol to disperse the centrifuged product in a double-neck flask. Finally, add 200ul of hydrochloric acid [37%] and reflux for 12h. Centrifuge and wash the product and disperse it in a water/alcohol volume ratio of 0.4. into 100 mL of mixed solution and stirred at 70°C for 6 hours. After centrifugal collection and washing, it was dried in an oven at 50°C for 10 hours. Finally, the product was roasted in a muffle furnace at 500°C for 5 hours to obtain hollow mesoporous silica microspheres.
实施例3Example 3
在烧杯称量0.06mg聚乙烯亚胺(Mw＝1800)，依次加入1.4mL氨水、45mL乙醇在25℃、500rpm的条件下搅拌30min。将1.65mL氨水与0.055g十六烷基三甲基溴化铵(CTAB)溶解在65mL的去离子水中，超声5min后在50℃下搅10min，冷却至室温，将得到的CTAB水溶液全部加入上述烧杯继续反应30min后快速添加0.9mL正硅酸乙酯(TEOS)，并将温度升高至35℃继续搅拌12h。离心收集(9000rpm，10min)并洗涤后使用100ml乙醇将离心得到的产物分散在双颈烧瓶中，最后加入200ul盐酸【37％】回流12h，将产物离心洗涤后分散在水/醇体积比为0.4的100mL的混合溶液中，70℃下搅拌6h。离心收集洗涤后置于50℃烘箱中干燥10h，最后将产物置于500℃马弗炉中焙烧8h，得到中空介孔二氧化硅微球。Weigh 0.06 mg of polyethyleneimine (Mw=1800) in a beaker, add 1.4 mL of ammonia water and 45 mL of ethanol in sequence, and stir for 30 min at 25°C and 500 rpm. Dissolve 1.65mL ammonia water and 0.055g cetyltrimethylammonium bromide (CTAB) in 65mL deionized water, sonicate for 5 minutes, stir at 50°C for 10 minutes, cool to room temperature, and add all the CTAB aqueous solution obtained above. The beaker continued to react for 30 minutes, then quickly added 0.9 mL of ethyl orthosilicate (TEOS), and raised the temperature to 35°C and continued stirring for 12 hours. Collect by centrifugation (9000rpm, 10min) and wash. Use 100ml of ethanol to disperse the centrifuged product in a double-neck flask. Finally, add 200ul of hydrochloric acid [37%] and reflux for 12h. Centrifuge and wash the product and disperse it in a water/alcohol volume ratio of 0.4. into 100 mL of mixed solution and stirred at 70°C for 6 hours. After centrifugal collection and washing, it was dried in an oven at 50°C for 10 hours. Finally, the product was roasted in a muffle furnace at 500°C for 8 hours to obtain hollow mesoporous silica microspheres.
图1为本发明实施例1中制得的中空二氧化硅微球的扫描电镜照片；图1的扫描图可以看出样品的形貌为球形，表面光滑且分散良好，粒径大小寸约为500nm。Figure 1 is a scanning electron microscope photograph of the hollow silica microspheres prepared in Example 1 of the present invention; from the scanning picture in Figure 1, it can be seen that the morphology of the sample is spherical, the surface is smooth and well dispersed, and the particle size is approximately 500nm.
图2为本发明实施例1及对比例1-2中加入CTAB水溶液后不同搅拌时间下，对应的小角度XRD谱图；图2的小角度XRD谱图可以看出当CTAB水溶液加入后搅拌30min的这组样品具有的介孔孔道有序性程度最高。Figure 2 is the corresponding small-angle XRD spectrum under different stirring times after adding CTAB aqueous solution in Example 1 and Comparative Examples 1-2 of the present invention; the small-angle XRD spectrum in Figure 2 can be seen that when the CTAB aqueous solution is added and stirred for 30 minutes This group of samples has the highest degree of mesoporous channel ordering.
图3为本发明实施例1-3中不同煅烧时间制得的中空介孔二氧化硅微球的红外谱图；图3的红外谱图可以明显的看出中空介孔二氧化硅微球中的聚乙烯亚胺在500℃下煅烧3h后即可去除干净。Figure 3 is an infrared spectrum of hollow mesoporous silica microspheres prepared at different calcination times in Examples 1-3 of the present invention; the infrared spectrum of Figure 3 can clearly see that there are The polyethyleneimine can be removed after calcining at 500°C for 3 hours.
图4为本发明实施例1中煅烧3h制得的中空介孔二氧化硅微球的孔径和比表面积图；从图中可以看出样品的氮气等温曲线都符合IV型吸附等温线，表明孔道结构为介孔结构。制得的中空介孔二氧化硅微球的比表面积的数值为879.8665m2/g，孔径数值为2.0446nm。Figure 4 is a diagram of the pore diameter and specific surface area of hollow mesoporous silica microspheres prepared by calcination for 3 hours in Example 1 of the present invention; it can be seen from the figure that the nitrogen isotherm curves of the samples are consistent with the IV type adsorption isotherm, indicating that the pore channels The structure is mesoporous. The specific surface area value of the prepared hollow mesoporous silica microspheres is 879.8665m2 /g, and the pore diameter value is 2.0446nm.
图5为本发明实施例1中回流后制得的中空二氧化硅微球的透射照片。可以明显看出二氧化硅微球的中空结构。Figure 5 is a transmission photograph of the hollow silica microspheres produced after reflow in Example 1 of the present invention. The hollow structure of the silica microspheres can be clearly seen.
以上所述实施例仅表达了本发明的几种实施方式，该描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-described embodiments only express several implementation modes of the present invention. The descriptions are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims.
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| CN101559951A (en)* | 2009-05-15 | 2009-10-21 | 江苏大学 | Method for preparing nanoscale silica hollow microspheres |
| CN101683983A (en)* | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
| CN104974518A (en)* | 2015-07-24 | 2015-10-14 | 陕西师范大学 | Polyethyleneimine/silicon dioxide core-shell structure composite nano material and preparation method |
| CN105923636A (en)* | 2016-04-13 | 2016-09-07 | 哈尔滨工业大学 | Preparation method of monodisperse hollow mesoporous silica nanoparticle |
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| CN101168440A (en)* | 2007-09-27 | 2008-04-30 | 上海交通大学 | A kind of silica mesoporous material and preparation method thereof |
| CN101683983A (en)* | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
| CN101559951A (en)* | 2009-05-15 | 2009-10-21 | 江苏大学 | Method for preparing nanoscale silica hollow microspheres |
| CN104974518A (en)* | 2015-07-24 | 2015-10-14 | 陕西师范大学 | Polyethyleneimine/silicon dioxide core-shell structure composite nano material and preparation method |
| CN105923636A (en)* | 2016-04-13 | 2016-09-07 | 哈尔滨工业大学 | Preparation method of monodisperse hollow mesoporous silica nanoparticle |
| KR20180105796A (en)* | 2017-03-16 | 2018-10-01 | 한국과학기술연구원 | Preparation methode of porous silica and tne porous silica thereby |
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