技术领域technical field
本发明是利用有机配体敏化荧光增强-溶胶种子法制备一种单分散二氧化硅荧光微球，即是以二氧化硅为核，以二氧化硅掺杂稀土配合物作为表面包覆物制备单分散二氧化硅荧光微球，属于荧光材料制备领域。The present invention uses organic ligand sensitized fluorescence enhancement-sol seed method to prepare monodisperse silica fluorescent microspheres, that is, silica is used as the core, and silica-doped rare earth complex is used as the surface coating The invention relates to the preparation of monodisperse silicon dioxide fluorescent microspheres, belonging to the field of fluorescent material preparation.
背景技术Background technique
单分散二氧化硅微球因其机械强度高、稳定性好以及在溶剂中容易分散等特点，而被广泛应用于色谱柱填料、涂料、添加剂等。同时，二氧化硅微球还具有无毒性、高生物活性、亲水性、表面硅羟基易功能化等优点，故在催化剂、生物、医学领域都有着非常大的应用价值。为了实现二氧化硅微球的更加广泛的应用，赋予其荧光功能，可制备二氧化硅荧光微球。荧光微球由于具有稳定的结构及高效的发光效率，可以作为标记物而在复合材料微观检测、生物检测成像、载药及 DNA 检测等领域发挥着重要的作用。相比于传统的有机荧光分子，稀土离子的发射光谱对称分布并且宽度窄，不易光漂白，荧光寿命长，发光性质不随基体材料而变化，所以正在得到越来越广泛的关注与研究。因此，以二氧化硅为基质的稀土掺杂荧光微球可以作为信号标记物或荧光分子而在复合材料微观检测、生命分析科学以及医药靶向研究等领域发挥重要作用。Monodisperse silica microspheres are widely used in chromatographic column fillers, coatings, additives, etc. due to their high mechanical strength, good stability, and easy dispersion in solvents. At the same time, silica microspheres also have the advantages of non-toxicity, high biological activity, hydrophilicity, and easy functionalization of surface silicon hydroxyl groups, so they have great application value in the fields of catalysts, biology, and medicine. In order to realize the wider application of silica microspheres and endow them with fluorescent functions, silica fluorescent microspheres can be prepared. Due to their stable structure and high luminous efficiency, fluorescent microspheres can be used as markers and play an important role in the fields of composite material microscopic detection, biological detection imaging, drug loading and DNA detection. Compared with traditional organic fluorescent molecules, the emission spectra of rare earth ions are symmetrically distributed and narrow in width, are not easy to photobleach, have long fluorescence lifetime, and the luminescent properties do not change with the matrix materials, so they are getting more and more attention and research. Therefore, rare earth-doped fluorescent microspheres based on silica can be used as signal markers or fluorescent molecules to play an important role in the fields of composite material microscopic detection, life analysis science, and medical targeting research.
大部分稀土离子本身不会发光，当在一定波长的紫外光或可见光照射时部分稀土离子会发出特征荧光，比如能够发射红色荧光的Eu3+、绿色荧光的Tb3+以及蓝色荧光的Ce3+和Eu2+等。关于二氧化硅荧光微球的研究目前大部分集中于将稀土离子直接掺杂在二氧化硅微球中，例如，Yen-Ming Liu 等通过溶胶-凝胶微乳液法制备出Eu3+掺杂的二氧化硅荧光微球并分析了不同的反应条件对产物形貌和单分散性的影响（Sol-Gel Sci Technol(2012) 63:36-44）。但是，单一的稀土离子存在发光强度低的缺陷，要增强复合材料的发光强度就必须增加稀土离子的掺杂量，这在一定程度上增加了复合材料的成本并影响二氧化硅本身的的结构和性能。大量研究表明，当稀土离子与有机配位体形成配合物后，其荧光强度会显著增强。因此，为了要得到荧光性能较好的单分散二氧化硅荧光微球，可将稀土配合物复合到二氧化硅微球中。目前，将稀土配合物与二氧化硅形成复合荧光微球的方法主要包括反相微乳液法、溶胶-凝胶法、表面修饰法等。秦品珠等利用反相微乳液法制备了Eu(TTA)3phen为核，TEOS碱催化条件水解得到的二氧化硅为壳的长寿命发光纳米颗粒（中国发明专利, CN101362944 A）。但是，反相微乳液法更适合应用于超细纳米颗粒的制备，制得的荧光微球易团聚，且其成本高，有机成分难以去除，易受实验条件等诸多因素的影响。陶栋梁等使用溶胶-凝胶法，制得了以一系列不同稀土配合物为核，以二氧化硅为壳层的纳米复合材料（中国发明专利, CN102153576 A）。Mingguang Yu等人采用聚乙烯吡咯烷酮作为稀土配合物Eu(DBM)3phen表面活性剂，利用正硅酸乙酯碱催化下水解制备了二氧化硅包覆稀土配合物的球形纳米复合材料，该复合材料在350nm激发光源照射下发射出强烈的红色荧光（Journal of Materials Science & Technology, 2013(9):801–805）。传统的溶胶-凝胶法虽然可以得到球形度较好的产物，但由于稀土配合物的团聚和其形貌的不规则性以及包覆层二氧化硅表面具有高活性的硅羟基，使得得到的荧光微球单分散性较差，在一定程度上较难实现粒径的均一性分布，并且通过包覆得到的复合材料需要的稀土配合物添加量较多。Daojun Zhang等通过表面修饰法在二氧化硅微球表面接枝稀土配合物，制备了具有较强发光强度的绿色和红色荧光微球（J. Phys. Chem. C 2010, 114, 12505–12510）。但是，表面修饰法会消耗掉荧光微球表面的硅羟基，从而降低荧光微球的表面活性以及生物相容性。Most rare earth ions do not emit light by themselves. Some rare earth ions will emit characteristic fluorescence when irradiated by ultraviolet light or visible light of a certain wavelength, such as Eu3+ that can emit red fluorescence, Tb3+ that can emit green fluorescence, and Ce that can emit blue fluorescence.3+ and Eu2+ etc. Most of the research on silica fluorescent microspheres currently focuses on doping rare earth ions directly into silica microspheres. For example, Yen-Ming Liu et al prepared Eu3+ doped The silica fluorescent microspheres were used and the effects of different reaction conditions on the product morphology and monodispersity were analyzed (Sol-Gel Sci Technol(2012) 63:36-44). However, a single rare earth ion has the defect of low luminous intensity. To enhance the luminous intensity of the composite material, the doping amount of rare earth ions must be increased, which increases the cost of the composite material and affects the structure of the silica itself. and performance. A large number of studies have shown that when rare earth ions form complexes with organic ligands, their fluorescence intensity will be significantly enhanced. Therefore, in order to obtain monodisperse silica fluorescent microspheres with better fluorescent properties, rare earth complexes can be compounded into silica microspheres. At present, the methods for forming composite fluorescent microspheres from rare earth complexes and silica mainly include inverse microemulsion method, sol-gel method, surface modification method and so on. Qin Pinzhu et al. used the inverse microemulsion method to prepare Eu(TTA)3 phen as the core, and the silica obtained by TEOS alkali-catalyzed hydrolysis as the shell with long-lived luminescent nanoparticles (Chinese invention patent, CN101362944 A). However, the inverse microemulsion method is more suitable for the preparation of ultrafine nanoparticles. The prepared fluorescent microspheres are easy to agglomerate, and the cost is high, the organic components are difficult to remove, and are easily affected by many factors such as experimental conditions. Tao Dongliang and others used the sol-gel method to prepare nanocomposites with a series of different rare earth complexes as the core and silica as the shell (Chinese invention patent, CN102153576 A). Mingguang Yu et al. used polyvinylpyrrolidone as the rare earth complex Eu(DBM)3 phen surfactant, and prepared spherical nanocomposites of silica-coated rare earth complexes by hydrolysis of ethyl orthosilicate under alkali catalysis. The composite The material emits strong red fluorescence under the illumination of a 350nm excitation light source (Journal of Materials Science & Technology, 2013(9):801–805). Although the traditional sol-gel method can obtain products with better sphericity, due to the agglomeration of rare earth complexes and the irregularity of their morphology and the highly active silanol groups on the surface of the coating layer of silica, the obtained Fluorescent microspheres have poor monodispersity, and it is difficult to achieve uniform particle size distribution to a certain extent, and the composite material obtained by coating requires a large amount of rare earth complexes. Daojun Zhang et al grafted rare earth complexes on the surface of silica microspheres by surface modification, and prepared green and red fluorescent microspheres with strong luminous intensity (J. Phys. Chem. C 2010, 114, 12505–12510) . However, the surface modification method will consume the silanol on the surface of the fluorescent microspheres, thereby reducing the surface activity and biocompatibility of the fluorescent microspheres.
因此，为了制备出球形度和单分散性良好、粒径均匀且发光性能优异的荧光微球，本专利拟结合有机配体敏化荧光增强技术，采用溶胶种子法制备二氧化硅荧光微球。溶胶种子法是利用单分散性胶粒作为种子，再通过物理或者化学的方法在种子表面继续生长二氧化硅，此方法的优点是可以通过产生种子数量控制微球粒径。目前，已有一些文献报道通过溶胶种子法来制备二氧化硅荧光微球。其中，Michiel J. A. de Dood等人通过种子法以及酸催化法制备了直径为194nmEr3+掺杂的SiO2荧光粉（Chemistry of materials, 2002,14(7): 2849-2853.）。Lina Gong等人使用Eu3+为发光中心，通过溶胶种子法在酸催化制备出SiO2@SiO2：Eu3+单分散红色荧光微球（Optical Materials, 2014, 37: 583-588）。因此，在溶胶种子法的基础上，通过引入稀土配合物敏化增强荧光性能，将大大提高稀土离子的发光量子转换效率，减少稀土添加量，从而制备出具有良好发光性能且球形度好、分散均匀的二氧化硅荧光微球。Therefore, in order to prepare fluorescent microspheres with good sphericity and monodispersity, uniform particle size and excellent luminescent performance, this patent intends to combine organic ligand-sensitized fluorescence enhancement technology to prepare silica fluorescent microspheres by sol seed method. The sol seed method uses monodisperse colloidal particles as seeds, and then continues to grow silica on the surface of the seeds by physical or chemical methods. The advantage of this method is that the particle size of the microspheres can be controlled by the number of seeds produced. At present, there have been some reports in the literature on the preparation of silica fluorescent microspheres by the sol-seed method. Among them, Michiel JA de Dood et al. prepared Er3+ doped SiO2 phosphors with a diameter of 194nm by seed method and acid catalysis method (Chemistry of materials, 2002,14(7): 2849-2853.). Lina Gong et al. used Eu3+ as the luminescent center to prepare SiO2 @SiO2 : Eu3+ monodisperse red fluorescent microspheres by sol seed method in acid catalysis (Optical Materials, 2014, 37: 583-588). Therefore, on the basis of the sol seed method, by introducing rare earth complexes to sensitize and enhance the fluorescence performance, the luminescence quantum conversion efficiency of rare earth ions will be greatly improved, and the amount of rare earth added will be reduced. Uniform silica fluorescent microspheres.
发明内容Contents of the invention
本发明利用一种有机配体敏化荧光增强-溶胶种子法制备二氧化硅荧光微球，这种荧光微球的化学通式为SiO2@SiO2:Ln(L)3，其中Ln表示稀土元素铕（Eu）、铽（Tb）、铈（Ce）中的一种，制备出的荧光微球所发出荧光颜色分别为红色、黄绿色、蓝色；L表示有机配体，主要包括一系列的β-二酮类的有机配位体如：2-噻吩甲酰三氟丙酮（TTFA）、三氟乙酰丙酮(TFA)、二苯甲酰甲烷（DBM）、乙酰丙酮（AcAc）、苯甲酰丙酮（BA）、苯甲酰三氟丙酮（BFA）、β-萘酰三氟丙酮（β-NTA）。The present invention utilizes an organic ligand sensitized fluorescence enhancement-sol seed method to prepare silica fluorescent microspheres. The general chemical formula of the fluorescent microspheres is SiO2 @SiO2 :Ln(L)3 , wherein Ln represents rare earth One of the elements europium (Eu), terbium (Tb), and cerium (Ce), the fluorescent colors of the prepared fluorescent microspheres are red, yellow-green, and blue; L represents an organic ligand, mainly including a series of The organic ligands of β-diketones such as: 2-thienoyltrifluoroacetone (TTFA), trifluoroacetylacetone (TFA), dibenzoylmethane (DBM), acetylacetone (AcAc), benzo Acylacetone (BA), Benzoyltrifluoroacetone (BFA), β-Naphthoyltrifluoroacetone (β-NTA).
本发明提供了二氧化硅荧光微球制备方法，具体包括如下步骤：The invention provides a method for preparing silica fluorescent microspheres, which specifically includes the following steps:
步骤(a)：制备稀土配合物Ln(L)3Step (a): Preparation of rare earth complex Ln(L)3
分别称取Eu(NO3)3、Tb(NO3)3、Ce(NO3)3晶体溶于95%无水乙醇中配制为a溶液，另取有机配体L、或三乙胺溶于95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间。反应结束后，过滤、洗涤、干燥得到稀土配合物Ln(L)3。Weigh Eu(NO3 )3 , Tb(NO3 )3 , Ce(NO3 )3 crystals and dissolve them in 95% absolute ethanol to prepare a solution, and take organic ligand L or triethylamine and dissolve them in Prepare solution b in 95% absolute ethanol. After it is completely dissolved, add solution a dropwise into solution b under constant stirring. During the entire reaction process, adjust the pH value of the entire reaction system with triethylamine Maintained between 6.5-7.0. After the reaction, filter, wash and dry to obtain the rare earth complex Ln(L)3 .
步骤（b）：制备SiO2@SiO2: Ln(L)3荧光微球Step (b): Preparation of SiO2 @SiO2 : Ln(L)3 fluorescent microspheres
分别量取一定体积的蒸馏水、无水乙醇、氨水于烧杯中，超声振荡其使混合均匀，得到c溶液，在不断搅拌的条件下，准确量取一定体积的正硅酸乙酯（TEOS），缓慢加入c溶液中反应一定的时间得到d溶液；另量取一定体积的无水乙醇、蒸馏水、氨水于烧杯中，超声振荡其使混合均匀，得到e溶液，将e溶液一次性倒入d溶液中反应一段时间得到f溶液；称取一定质量的步骤(a)所得的稀土配合物Ln(L)3，并将其溶于丙酮中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，反应一段时间后再缓慢滴加一定体积的TEOS，反应后得到溶胶产物，再经过离心、洗涤、干燥，最后得到SiO2@SiO2: Ln(L)3荧光微球。Take a certain volume of distilled water, absolute ethanol, and ammonia water in a beaker, and ultrasonically oscillate it to mix evenly to obtain a c solution. Under the condition of constant stirring, accurately measure a certain volume of tetraethyl silicate (TEOS), Slowly add solution c to react for a certain period of time to obtain solution d; take a certain volume of absolute ethanol, distilled water, and ammonia water in a beaker, and ultrasonically oscillate it to mix evenly to obtain solution e, and pour solution e into solution d at one time react for a period of time to obtain f solution; weigh a certain mass of rare earth complex Ln(L)3 obtained in step (a), and dissolve it in acetone to obtain g solution, and use a micro-syringe to inject g solution under ultrasonic vibration conditions Slowly add to the f solution, react for a period of time, and then slowly add a certain volume of TEOS dropwise. After the reaction, the sol product is obtained, and then centrifuged, washed, and dried, and finally SiO2 @SiO2 : Ln(L)3 fluorescent microspheres are obtained .
本发明的优点：Advantages of the present invention:
(1)本发明利用溶胶种子法制备二氧化硅荧光微球，其制备工艺简单，在常温下就能够完成反应；(1) The present invention utilizes the sol seed method to prepare silica fluorescent microspheres, and its preparation process is simple, and the reaction can be completed at normal temperature;
(2) 本发明中在制备二氧化硅荧光微球中引入稀土配合物增强发光性能，降低稀土离子掺杂量，有利于节约成本；(2) In the present invention, in the preparation of silica fluorescent microspheres, rare earth complexes are introduced to enhance the luminescent performance, reduce the doping amount of rare earth ions, and help save costs;
(3) 本发明中制备所得二氧化硅荧光微球的球形度、单分散性、稳定性和发光性能均较好，这种荧光微球在光电材料、荧光标记、药物靶向等方面具有广泛的应用前景。(3) The sphericity, monodispersity, stability and luminescent properties of the silica fluorescent microspheres prepared in the present invention are all good, and this kind of fluorescent microspheres has a wide range of applications in photoelectric materials, fluorescent labels, drug targeting, etc. application prospects.
附图说明Description of drawings
图1 是本发明实施例1的单分散二氧化硅荧光微球A的TEM图。Fig. 1 is a TEM image of monodisperse silica fluorescent microspheres A of Example 1 of the present invention.
图2是本发明实施例1的单分散二氧化硅荧光微球A的激发和发射光谱图。Fig. 2 is the excitation and emission spectrograms of the monodisperse silica fluorescent microspheres A of Example 1 of the present invention.
具体实施方式detailed description
本发明可结合实施例进一步说明The present invention can be further illustrated in conjunction with embodiment
实施例1Example 1
称取1mmolEu(NO3)3晶体溶于20mL95%无水乙醇中配制为a溶液，另取3mmol DBM、3mmol三乙胺溶于20mL 95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间，搅拌1h后，抽滤、洗涤、干燥，得到浅黄色固体粉末。Weigh 1mmol of Eu(NO3 )3 crystals and dissolve in 20mL of 95% absolute ethanol to prepare a solution, and another 3mmol of DBM and 3mmol of triethylamine are dissolved in 20mL of 95% absolute ethanol to prepare as solution b. After completely dissolving, Under the condition of constant stirring, drop a solution into b solution drop by drop. During the whole reaction process, adjust the pH value of the whole reaction system by triethylamine to maintain between 6.5-7.0. After stirring for 1 hour, suction filter and wash , and dried to obtain light yellow solid powder.
分别量取25mL蒸馏水、65mL无水乙醇、7mL氨水于烧杯中，超声振荡20min，使其混合均匀，作为c溶液，在不断搅拌的条件下，量取4mL正硅酸乙酯（TEOS）缓慢加入c溶液中，反应30min后得到d溶液；另分别量取18mL无水乙醇、8mL蒸馏水、2mL氨水于烧杯中，超声振荡5min，作为e溶液，将e溶液一次性倒入d溶液中反应20min得到f溶液，；称取0.09g稀土配合物溶于2mL丙酮溶液中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，继续超声振荡30min后，缓慢加入1mL TEOS，反应2h后得到溶胶产物，再经离心、洗涤、干燥，最后得到SiO2@SiO2: Eu(DBM)3荧光微球A，测试其微球平均直径为100-500nm，激发波长为285nm，发射波长为614nm，属于红色发光。Measure 25mL of distilled water, 65mL of absolute ethanol, and 7mL of ammonia water in a beaker, and ultrasonically oscillate for 20 minutes to mix them evenly. In solution c, react for 30 minutes to obtain solution d; separately measure 18 mL of absolute ethanol, 8 mL of distilled water, and 2 mL of ammonia water in a beaker, and ultrasonically oscillate for 5 minutes to obtain solution e. Pour solution e into solution d at one time and react for 20 minutes to obtain f solution; weigh 0.09g rare earth complex and dissolve it in 2mL acetone solution to obtain g solution, slowly add g solution into f solution with a micro-syringe under ultrasonic oscillation, continue ultrasonic oscillation for 30min, then slowly add 1mL TEOS, After reacting for 2 hours, the sol product was obtained, and then centrifuged, washed, and dried to obtain SiO2 @SiO2 : Eu(DBM)3 fluorescent microspheres A. The average diameter of the microspheres was tested to be 100-500nm, the excitation wavelength was 285nm, and the emission wavelength was 285nm. The wavelength is 614nm, which belongs to red light.
实施例2Example 2
称取1mmolEu(NO3)3晶体溶于20mL95%无水乙醇中配制为a溶液，另取3mmol TTFA、3mmol 三乙胺溶于20mL 95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间，搅拌1h后，抽滤、洗涤、干燥，得到白色固体粉末。Weigh 1mmol of Eu(NO3 )3 crystals and dissolve in 20mL of 95% dehydrated ethanol to prepare a solution, and another 3mmol of TTFA and 3mmol of triethylamine are dissolved in 20mL of 95% dehydrated ethanol to prepare a solution of b. After completely dissolving, Under the condition of constant stirring, drop a solution into b solution drop by drop. During the whole reaction process, adjust the pH value of the whole reaction system by triethylamine to maintain between 6.5-7.0. After stirring for 1 hour, suction filter and wash , and dried to obtain a white solid powder.
分别量取25mL蒸馏水、65mL无水乙醇、7mL氨水于烧杯中，超声振荡20min，使混合均匀，作为c溶液，在不断搅拌的条件下，量取4mL正硅酸乙酯（TEOS）缓慢加入c溶液中， 反应30min后得到d溶液；另分别量取18mL无水乙醇、8mL蒸馏水、2mL氨水于烧杯中，超声振荡5min，作为e溶液，将e溶液一次性倒入d溶液中反应20min得到f溶液，；称取0.09g稀土配合物溶于2mL丙酮溶液中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，继续超声振荡30min后，缓慢加入1mL TEOS，反应2h后得到溶胶产物，再经离心、洗涤、干燥，最后得到SiO2@SiO2: Eu(TTFA)3荧光微球B，测试其微球平均直径为100-500nm，激发波长为254nm，发射波长为612nm，属于红色发光。Measure 25mL of distilled water, 65mL of absolute ethanol, and 7mL of ammonia water in a beaker, and ultrasonically oscillate for 20 minutes to mix evenly. As a c solution, measure 4mL of tetraethyl orthosilicate (TEOS) and slowly add c solution, reacted for 30 minutes to obtain solution d; separately measure 18mL absolute ethanol, 8mL distilled water, and 2mL ammonia water in a beaker, ultrasonically oscillate for 5 minutes, as solution e, pour solution e into solution d at one time and react for 20 minutes to obtain f Solution,; Weigh 0.09g rare earth complex and dissolve it in 2mL acetone solution to obtain g solution, slowly add g solution to f solution with a micro-syringe under ultrasonic oscillation, continue ultrasonic oscillation for 30min, slowly add 1mL TEOS, and react After 2 hours, the sol product was obtained, and then centrifuged, washed, and dried to obtain SiO2 @SiO2 : Eu(TTFA)3 fluorescent microspheres B. The average diameter of the microspheres was tested to be 100-500nm, the excitation wavelength was 254nm, and the emission wavelength was 254nm. It is 612nm, which belongs to red light.
实施例3Example 3
称取1mmolEu(NO3)3晶体溶于20mL95%无水乙醇中配制为a溶液，另取3mmol TFA、3mmol三乙胺溶于20mL 95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间，搅拌1h后，抽滤、洗涤、干燥，得到稀土配合物。Weigh 1mmol of Eu(NO3 )3 crystals and dissolve in 20mL of 95% absolute ethanol to prepare solution a, and separately take 3mmol of TFA and 3mmol of triethylamine to dissolve in 20mL of 95% absolute ethanol to prepare solution b. After completely dissolving, Under the condition of constant stirring, drop a solution into b solution drop by drop. During the whole reaction process, adjust the pH value of the whole reaction system by triethylamine to maintain between 6.5-7.0. After stirring for 1 hour, suction filter and wash , drying to obtain rare earth complexes.
分别量取25mL蒸馏水、65mL无水乙醇、7mL氨水于烧杯中，超声振荡20min，使混合均匀，作为c溶液，在不断搅拌的条件下，量取4mL正硅酸乙酯（TEOS）缓慢加入c溶液中， 反应30min后得到d溶液；另分别量取18mL无水乙醇、8mL蒸馏水、2mL氨水于烧杯中，超声振荡5min，作为e溶液，将e溶液一次性倒入d溶液中反应20min得到f溶液，；称取0.09g稀土配合物溶于2mLDMF溶液中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，继续超声振荡30min后，缓慢加入1mL TEOS，反应2h后得到溶胶产物，再经离心、洗涤、干燥，最后得到SiO2@SiO2: Eu(TFA)3荧光微球C，测试其微球平均直径为100-500nm，激发波长为340nm，发射波长为617nm，属于红色发光。Measure 25mL of distilled water, 65mL of absolute ethanol, and 7mL of ammonia water in a beaker, and ultrasonically oscillate for 20 minutes to mix evenly. As a c solution, measure 4mL of tetraethyl orthosilicate (TEOS) and slowly add c solution, reacted for 30 minutes to obtain solution d; separately measure 18mL absolute ethanol, 8mL distilled water, and 2mL ammonia water in a beaker, ultrasonically oscillate for 5 minutes, as solution e, pour solution e into solution d at one time and react for 20 minutes to obtain f solution,; Weigh 0.09g rare earth complex and dissolve it in 2mL DMF solution to obtain g solution, slowly add g solution to f solution with a micro syringe under the condition of ultrasonic oscillation, continue ultrasonic oscillation for 30min, slowly add 1mL TEOS, and react for 2h Finally, the sol product was obtained, and then centrifuged, washed, and dried to finally obtain SiO2 @SiO2 : Eu(TFA)3 fluorescent microspheres C. The average diameter of the microspheres was tested to be 100-500nm, the excitation wavelength was 340nm, and the emission wavelength was 617nm, which belongs to red light.
实施例4Example 4
称取1mmolEu(NO3)3晶体溶于20mL95%无水乙醇中配制为a溶液，另取3mmol AcAc、3mmol 三乙胺溶于20mL 95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间，搅拌1h后，抽滤、洗涤、干燥，得到稀土配合物。Weigh 1mmol of Eu(NO3 )3 crystals and dissolve in 20mL of 95% absolute ethanol to prepare solution a, and separately take 3mmol of AcAc and 3mmol of triethylamine to dissolve in 20mL of 95% absolute ethanol to prepare solution b. After completely dissolving, Under the condition of constant stirring, drop a solution into b solution drop by drop. During the whole reaction process, adjust the pH value of the whole reaction system by triethylamine to maintain between 6.5-7.0. After stirring for 1 hour, suction filter and wash , drying to obtain rare earth complexes.
分别量取25mL蒸馏水、65mL无水乙醇、7mL氨水于烧杯中，超声振荡20min，使混合均匀，作为c溶液，在不断搅拌的条件下，量取4mL正硅酸乙酯（TEOS）缓慢加入c溶液中， 反应30min后得到d溶液；另分别量取18mL无水乙醇、8mL蒸馏水、2mL氨水于烧杯中，超声振荡5min，作为e溶液，将e溶液一次性倒入d溶液中反应20min得到f溶液，；称取0.09g稀土配合物溶于2mLDMF溶液中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，继续超声振荡30min后，缓慢加入1mL TEOS，反应2h后得到溶胶产物，再经离心、洗涤、干燥，最后得到SiO2@SiO2: Eu(AcAc)3荧光微球D，测试其微球平均直径为100-500nm，激发波长为320nm，发射波长为615nm，属于红色发光。Measure 25mL of distilled water, 65mL of absolute ethanol, and 7mL of ammonia water in a beaker, and ultrasonically oscillate for 20 minutes to mix evenly. As a c solution, measure 4mL of tetraethyl orthosilicate (TEOS) and slowly add c solution, reacted for 30 minutes to obtain solution d; separately measure 18mL absolute ethanol, 8mL distilled water, and 2mL ammonia water in a beaker, ultrasonically oscillate for 5 minutes, as solution e, pour solution e into solution d at one time and react for 20 minutes to obtain f solution,; Weigh 0.09g rare earth complex and dissolve it in 2mL DMF solution to obtain g solution, slowly add g solution to f solution with a micro syringe under the condition of ultrasonic oscillation, continue ultrasonic oscillation for 30min, slowly add 1mL TEOS, and react for 2h Finally, the sol product was obtained, and then centrifuged, washed, and dried to finally obtain SiO2 @SiO2 : Eu(AcAc)3 fluorescent microspheres D. The average diameter of the microspheres was tested to be 100-500nm, the excitation wavelength was 320nm, and the emission wavelength was 615nm, which belongs to red light.
实施例5Example 5
称取1mmolEu(NO3)3晶体溶于20mL95%无水乙醇中配制为a溶液，另取3mmol BFA、3mmol三乙胺溶于20mL 95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间，搅拌1h后，抽滤、洗涤、干燥，得到稀土配合物。Weigh 1mmol of Eu(NO3 )3 crystals and dissolve in 20mL of 95% absolute ethanol to prepare a solution, and another 3mmol of BFA and 3mmol of triethylamine are dissolved in 20mL of 95% absolute ethanol to prepare a solution of b. After completely dissolving, Under the condition of constant stirring, drop a solution into b solution drop by drop. During the whole reaction process, adjust the pH value of the whole reaction system by triethylamine to maintain between 6.5-7.0. After stirring for 1 hour, suction filter and wash , drying to obtain rare earth complexes.
分别量取25mL蒸馏水、65mL无水乙醇、7mL氨水于烧杯中，超声振荡20min，使混合均匀，作为c溶液，在不断搅拌的条件下，量取4mL正硅酸乙酯（TEOS）缓慢加入c溶液中， 反应30min后得到d溶液；另分别量取18mL无水乙醇、8mL蒸馏水、2mL氨水于烧杯中，超声振荡5min，作为e溶液，将e溶液一次性倒入d溶液中反应20min得到f溶液，；称取0.09g稀土配合物溶于2mLDMF溶液中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，继续超声振荡30min后，缓慢加入1mL TEOS，反应2h后，得到溶胶产物，再经离心、洗涤、干燥，最后得到SiO2@SiO2: Eu(BFA)3荧光微球E，测试其微球平均直径为100-500nm，激发波长为340nm，发射波长为620nm，属于红色发光。Measure 25mL of distilled water, 65mL of absolute ethanol, and 7mL of ammonia water in a beaker, and ultrasonically oscillate for 20 minutes to mix evenly. As a c solution, measure 4mL of tetraethyl orthosilicate (TEOS) and slowly add c solution, reacted for 30 minutes to obtain solution d; separately measure 18mL absolute ethanol, 8mL distilled water, and 2mL ammonia water in a beaker, ultrasonically oscillate for 5 minutes, as solution e, pour solution e into solution d at one time and react for 20 minutes to obtain f solution,; Weigh 0.09g rare earth complex and dissolve it in 2mL DMF solution to obtain g solution, slowly add g solution to f solution with a micro syringe under the condition of ultrasonic oscillation, continue ultrasonic oscillation for 30min, slowly add 1mL TEOS, and react for 2h Finally, the sol product was obtained, and then centrifuged, washed, and dried to finally obtain SiO2 @SiO2 : Eu(BFA)3 fluorescent microspheres E. The average diameter of the microspheres was tested to be 100-500nm, the excitation wavelength was 340nm, and the emission wavelength was 340nm. It is 620nm, which belongs to red light.
实施例6Example 6
称取1mmolTb(NO3)3晶体溶于20mL95%无水乙醇中配制为a溶液，另取3mmol AcAc、3mmol 三乙胺溶于20mL 95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间，搅拌1h后，抽滤、洗涤、干燥，得到稀土配合物。Weigh 1mmol of Tb(NO3 )3 crystals and dissolve in 20mL of 95% absolute ethanol to prepare solution a, and separately take 3mmol of AcAc and 3mmol of triethylamine and dissolve them in 20mL of 95% absolute ethanol to prepare solution b. After completely dissolving, Under the condition of constant stirring, drop a solution into b solution drop by drop. During the whole reaction process, adjust the pH value of the whole reaction system by triethylamine to maintain between 6.5-7.0. After stirring for 1 hour, suction filter and wash , drying to obtain rare earth complexes.
分别量取25mL蒸馏水、65mL无水乙醇、7mL氨水于烧杯中，超声振荡20min，使混合均匀，作为c溶液，在不断搅拌的条件下，量取4mL正硅酸乙酯（TEOS）缓慢加入c溶液中， 反应30min后得到d溶液；另分别量取18mL无水乙醇、8mL蒸馏水、2mL氨水于烧杯中，超声振荡5min，作为e溶液，将e溶液一次性倒入d溶液中反应20min得到f溶液，；称取0.09g稀土配合物溶于2mLDMF溶液中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，继续超声振荡30min后，缓慢加入1mL TEOS，反应2h后得到溶胶产物，再经离心、洗涤、干燥，最后得到SiO2@SiO2: Tb(AcAc)3荧光微球F，测试其微球平均直径为100-500nm，激发波长为400nm，发射波长为550nm，属于绿色发光。Measure 25mL of distilled water, 65mL of absolute ethanol, and 7mL of ammonia water in a beaker, and ultrasonically oscillate for 20 minutes to mix evenly. As a c solution, measure 4mL of tetraethyl orthosilicate (TEOS) and slowly add c solution, reacted for 30 minutes to obtain solution d; separately measure 18mL absolute ethanol, 8mL distilled water, and 2mL ammonia water in a beaker, ultrasonically oscillate for 5 minutes, as solution e, pour solution e into solution d at one time and react for 20 minutes to obtain f solution,; Weigh 0.09g rare earth complex and dissolve it in 2mL DMF solution to obtain g solution, slowly add g solution to f solution with a micro syringe under the condition of ultrasonic oscillation, continue ultrasonic oscillation for 30min, slowly add 1mL TEOS, and react for 2h Finally, the sol product was obtained, and then centrifuged, washed, and dried to finally obtain SiO2 @SiO2 : Tb(AcAc)3 fluorescent microspheres F. The average diameter of the microspheres was tested to be 100-500nm, the excitation wavelength was 400nm, and the emission wavelength was 550nm, which belongs to green light.
实施例7Example 7
称取1mmol Ce(NO3)3晶体溶于20mL95%无水乙醇中配制为a溶液，另取3mmol AcAc、3mmol 三乙胺溶于20mL 95%无水乙醇中配制为b溶液，待完全溶解后，在不断搅拌的条件下将a溶液逐滴滴入b溶液中，在整个反应过程中，通过三乙胺调节整个反应体系的pH值维持在6.5-7.0之间，搅拌1h后，抽滤、洗涤、干燥，得到稀土配合物Weigh 1mmol Ce(NO3 )3 crystal and dissolve it in 20mL 95% absolute ethanol to prepare a solution, and take another 3mmol AcAc and 3mmol triethylamine and dissolve it in 20mL 95% absolute ethanol to prepare b solution. , under the condition of constant stirring, drop a solution into b solution drop by drop, in the whole reaction process, adjust the pH value of the whole reaction system by triethylamine to maintain between 6.5-7.0, after stirring for 1h, suction filtration, Washing and drying to obtain rare earth complexes
分别量取25mL蒸馏水、65mL无水乙醇、7mL氨水于烧杯中，超声振荡20min，使混合均匀，作为c溶液，在不断搅拌的条件下，量取4mL正硅酸乙酯（TEOS）缓慢加入c溶液中， 反应30min后得到d溶液；另分别量取18mL无水乙醇、8mL蒸馏水、2mL氨水于烧杯中，超声振荡5min，作为e溶液，将e溶液一次性倒入d溶液中反应20min得到f溶液，；称取0.09g稀土配合物溶于2mLDMF溶液中得到g溶液，在超声振荡条件下用微量注射器将g溶液缓慢加入到f溶液中，继续超声振荡30min后，缓慢加入1mL TEOS，反应2h后得到溶胶产物，再经离心、洗涤、干燥，最后得到SiO2@SiO2: Ce(AcAc)3荧光微球G，测试其微球平均直径为100-500nm，激发波长为335nm，发射波长为452nm，属于蓝色发光。Measure 25mL of distilled water, 65mL of absolute ethanol, and 7mL of ammonia water in a beaker, and ultrasonically oscillate for 20 minutes to mix evenly. As a c solution, measure 4mL of tetraethyl orthosilicate (TEOS) and slowly add c solution, reacted for 30 minutes to obtain solution d; separately measure 18mL absolute ethanol, 8mL distilled water, and 2mL ammonia water in a beaker, ultrasonically oscillate for 5 minutes, as solution e, pour solution e into solution d at one time and react for 20 minutes to obtain f solution,; Weigh 0.09g rare earth complex and dissolve it in 2mL DMF solution to obtain g solution, slowly add g solution to f solution with a micro syringe under the condition of ultrasonic oscillation, continue ultrasonic oscillation for 30min, slowly add 1mL TEOS, and react for 2h Finally, the sol product was obtained, and then centrifuged, washed, and dried to finally obtain SiO2 @SiO2 : Ce(AcAc)3 fluorescent microspheres G. The average diameter of the microspheres was tested to be 100-500nm, the excitation wavelength was 335nm, and the emission wavelength was 452nm, which belongs to blue light.
| Application Number | Priority Date | Filing Date | Title |
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| CN201610528622.0ACN106221692A (en) | 2016-07-07 | 2016-07-07 | A kind of preparation method of monodisperse silica fluorescent microsphere |
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| CN201610528622.0ACN106221692A (en) | 2016-07-07 | 2016-07-07 | A kind of preparation method of monodisperse silica fluorescent microsphere |
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| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20161214 | |
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