WO2017092644A1 - Method for inducing titanium dioxide nano particles to form pearl chain structure through self-assembly - Google Patents
Method for inducing titanium dioxide nano particles to form pearl chain structure through self-assembly Download PDFInfo
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- WO2017092644A1 WO2017092644A1 PCT/CN2016/107628 CN2016107628W WO2017092644A1 WO 2017092644 A1 WO2017092644 A1 WO 2017092644A1 CN 2016107628 W CN2016107628 W CN 2016107628W WO 2017092644 A1 WO2017092644 A1 WO 2017092644A1
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- C01G23/047—Titanium dioxide
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- the invention relates to the preparation of a self-assembled structure, in particular to a method for controlling self-assembly of colloidal particles and preparing a patterned structure by applying a direct external electric field, that is, self-assembly of titanium dioxide colloidal particles by applying a direct external electric field to prepare a pearl chain. structure.
- Nanoparticles have specific surface effects, quantum size effects, small size effects, and macroscopic quantum tunneling effects, and thus have extremely important applications in photovoltaic materials, microelectronic devices, biosensors, and catalysts. Utilizing the excellent physical and chemical properties of nanoparticles, one or more kinds of nanoparticles are used as structural units, and the agglomeration effect between nanoparticles is fully utilized by self-assembly technology to prepare large-sized, well-structured 2D arrays or 3D array supercrystals. , or structural units with specific functions, is the key to promoting the wide application of nanotechnology.
- titanium dioxide As an important semiconductor material, titanium dioxide has been widely used in coatings, photovoltaic cells, gas sensors, microelectronic devices, and biomedicine because of its outstanding chemical stability, photoelectric properties, biocompatibility, and corrosion resistance. Materials and photocatalysis. However, the application of titanium dioxide still needs to overcome some difficulties. As self-assembled materials and display materials, nano-titanium dioxide has a high density, poor dispersibility, easy agglomeration and sedimentation, and it is difficult to achieve the desired effect in practical use.
- Nanoparticles can be controlled by external environment or external field to achieve controlled assembly, resulting in an ordered structure.
- the external field capable of directing nanoparticles for self-assembly is mainly divided into electric field, magnetic field, fluid force field, thermal field, sound field, substrate surface energy and pressure.
- the direct self-assembly by the applied electric field has the advantage of being able to make the colloidal particles self-assemble quickly, and is easy to control and widely used, and is widely used.
- Nanoparticle self-assembly refers to the process of forming specific functional (optical, electrical, magnetic, and mechanical properties) structures by colloidal particles such as metal nanoparticles or semiconductor nanoparticles through dipole-dipole interaction, surface tension, and hydrophobic interaction.
- Guided self-assembly is a process of agglomeration of self-assembled systems in a direct form through a tangible template or field.
- the external fields commonly used include electric fields, magnetic fields, fluid force fields, thermal fields, sound fields, surface energy of substrates, and pressure.
- the principle of electric field guidance is that most of the nanoparticles can be polarized under an external electric field due to the mismatch between the dielectric properties and the surrounding medium.
- the moving charge is also susceptible to the external field, which is beneficial to the electric field of the nanoparticles.
- Polarization in the middle.
- the external electric field surrounding the nanoparticles causes the particles to polarize to create dipoles, resulting in very strong and anisotropic dipole-dipole interactions between the nanoparticles. If the interaction between the dipole-dipoles is strong enough to overcome the Brownian motion of the particles, a chain of dipoles will be produced. As time increases, the chains become longer and thicker and eventually crosslink together.
- the structure with the lowest energy such as body-centered square, hexagonal and face-centered cubics. The generation of a specific structure depends on factors such as the material, concentration, size, and electric field strength of the nanoparticles.
- the prior art mainly controls the self-assembly of the titanium dioxide particles by applying an alternating electric field, and generally needs to disperse the titanium dioxide in a polar solvent such as deionized water or acetone, the electric field strength. Need >10 6 V ⁇ cm -1 , frequency needs >10 kHz.
- the limitations of this method are mainly reflected in two aspects: First, the nanoparticles need to be dispersed in a solvent with a large polarity, which limits the range of use of the nanoparticles and the solvent; second, the electric field strength is large, and it is easy to break down and damage the device.
- a method for inducing self-assembly of titanium dioxide nanoparticles to form a pearl chain structure specifically: the titanium dioxide nanoparticles are modified to coat a surface of the polymer, and then the modified titanium dioxide nanoparticles are dispersed in a non-polar solvent, The titanium dioxide nanoparticles are self-assembled into a pearl chain structure by using an external DC electric field.
- titanium dioxide nanoparticles are 10 to 100 nm before the modification and 200 to 500 nm after the modification.
- the polymer is polymethyl methacrylate.
- titanium oxide nanoparticles are modified by dispersing the titanium dioxide nanoparticles in styrene and divinylbenzene, adding a surfactant, and then chemically synthesizing the surface of the titanium dioxide nanoparticles with a layer of polymethacrylic acid. Methyl ester.
- the titanium oxide nanoparticles are modified by: dispersing the titanium dioxide nanoparticles in styrene and divinylbenzene, and then ultrasonically pouring into a solution of polyvinylpyrrolidone in methanol, dispersing and pouring into a flask. Under the protection of nitrogen, azobisisobutyronitrile is added thereto, stirred and heated to carry out a reaction, and then methyl methacrylate is added to the flask to continue the reaction. After the reaction is finished, the product is washed and dried to obtain a modified titanium oxide. Nanoparticles.
- non-polar solvent is an alkane, benzene, toluene, dimethyl ether, ethyl acetate, tetrahydrofuran, chloroform, dichloromethane or carbon tetrachloride.
- alkane is n-hexane, cyclohexane, isooctane, n-undecane or n-dodecane.
- the intensity of the direct current electric field is 1 to 6000 V/cm.
- the method comprises: dispersing the titanium dioxide nanoparticles in styrene and divinylbenzene, and then ultrasonically pouring into a solution of polyvinylpyrrolidone in methanol, dispersing, pouring into a flask, and under the protection of nitrogen, Nitrogen diisobutyronitrile is added thereto, stirred and heated to carry out a reaction, and then methyl methacrylate is added to the flask to continue the reaction.
- the product is washed and dried to obtain modified titanium dioxide nanoparticles;
- the titanium dioxide nanoparticles are dispersed in a non-polar solvent, and a dispersant is added, and the titanium dioxide nanoparticles are used as an assembly unit, and the titanium dioxide nanoparticles are self-assembled into a pearl chain on the flat conductive glass by applying a direct current electric field between the two electrodes. structure.
- the invention controls the surface of the titanium dioxide nanoparticles by using a direct current external electric field of less than 6000V/cm.
- the colloidal particles self-assemble into a pearl chain structure, which can significantly reduce the electric field strength, ensure a safe voltage, protect the electrode, improve the self-assembly speed, shorten the self-assembly time, ensure high preparation efficiency, and form a pearl chain structure. It is used in optoelectronic devices and sensors; it can also be self-assembled in non-polar solvents, broadening the use of nanoparticles and solvents.
- FIG. 1 is a schematic view of a self-assembly apparatus of Embodiment 1;
- Example 2 is a schematic diagram of the self-assembly of titanium dioxide nano-assembly into a pearl chain structure of Example 1;
- Figure 3 is a micrograph of the first embodiment when no voltage is applied
- FIG. 4 is a micrograph of a first embodiment after a voltage is applied.
- the unmodified titanium dioxide particles adsorb the cation, the colloidal particles are positively charged, and the zeta potential and mobility of the dispersion are positive, and the modified titanium dioxide particles are coated with a layer of polymer on the surface, which can adsorb anions and disperse them.
- the zeta potential and mobility of the liquid are negative, indicating the success of the polymer modified titanium dioxide.
- FIG. 1 is a schematic view showing the structure of a device of the method of the present invention, i.e., a schematic diagram of a device for applying a direct external electric field, 1 being a dioxane Titanium dispersion, 2 is a cover glass, 3 is glass, 4 is ITO electrode, Fig. 2 is a schematic diagram of titanium dioxide nano self-assembly into a pearl chain structure, using an external DC electric field, using titanium dioxide nanoparticles as an assembly unit, An electric field is applied between the two electrodes to achieve assembly and patterning of randomly dispersed titanium dioxide nanoparticles.
- 1 being a dioxane Titanium dispersion
- 2 is a cover glass
- 3 is glass
- 4 is ITO electrode
- Fig. 2 is a schematic diagram of titanium dioxide nano self-assembly into a pearl chain structure, using an external DC electric field, using titanium dioxide nanoparticles as an assembly unit, An electric field is applied between the two electrodes to achieve assembly and patterning of randomly
- 0.005 g of the modified titanium dioxide nanoparticles were dispersed in 5 mL of n-undecane, 10 w/v% of Span 80 as a dispersing agent, and then a DC electric field of 1 to 6000 V/cm was applied for 10 s, and the negatively charged titanium dioxide nanoparticles were electrically conductive on the plate.
- 3 is a random dispersion of titanium dioxide nanoparticles in n-undecane when no voltage is applied;
- FIG. 4 is a self-assembly of titanium dioxide nanoparticles into a pearl chain structure after voltage application.
- titanium dioxide nanoparticles were dispersed in 0.5 g of styrene and 0.04 g of divinylbenzene for 30 min, then poured into a methanol solution of 3 w/v% polyvinylpyrrolidone for 30 min, dispersed, and poured into a three-necked flask. Under nitrogen protection, 0.02 g of azobisisobutyronitrile was added thereto, the stirring speed was 500 r/min, and the temperature was raised to 60 ° C, and the reaction was stirred for 8 hours under nitrogen;
- modified titanium dioxide nanoparticles were dispersed in 15 mL of n-dodecane, 20 w/v% of Span 80 as a dispersing agent, and then a DC electric field of 6000 V/cm was applied for 5 s, and negatively charged titanium dioxide nanoparticles were used in flat conductive glass. Directly self-assembled into a pearl chain structure on the plate.
- the modified titanium dioxide nanoparticles were dispersed in 10 mL of carbon tetrachloride, and 15 w/v% of Span 80 was used as a dispersing agent. Then, after applying a DC electric field of 1 V/cm for 60 s, the negatively charged titanium dioxide nanoparticles are self-assembled into a pearl chain structure on a flat plate of a conductive glass or the like.
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Abstract
Provided is a method for inducing titanium dioxide nano particles to form a pearl chain structure through self-assembly, comprising: coating the surfaces of titanium dioxide nano particles with a layer of a polymer through modification, then dispersing the modified titanium dioxide nano particles in a non-polar solvent, and subjecting the titanium dioxide nano particles to directed self-assembly by utilizing an external direct-current electric field so as to form a pearl chain structure. In the method, by performing surface modification on the titanium dioxide nano particles, and by using a direct-current electric field with a significantly decreased field intensity to control colloidal particles so as to form the pearl chain structure through self-assembly, an electrode is protected; the self-assembly speed can be increased, the self-assembly time can be shortened, and a relatively high preparation efficiency can be guaranteed; and the self-assembly can be completed in a non-polar solvent, thus widening the use range of the nano particles and the solvent. The pearl chain structure formed can be widely used in photoelectronic devices and sensors.
Description
本发明涉及一种自组装结构的制备，尤其是通过施加直流外电场来控制胶体颗粒自组装及制备图案化结构的方法，即对二氧化钛胶体颗粒通过施加直流外电场进行自组装，制备出珍珠链结构。The invention relates to the preparation of a self-assembled structure, in particular to a method for controlling self-assembly of colloidal particles and preparing a patterned structure by applying a direct external electric field, that is, self-assembly of titanium dioxide colloidal particles by applying a direct external electric field to prepare a pearl chain. structure.
纳米颗粒具有特异的表面效应、量子尺寸效应、小尺寸效应以及宏观量子隧道效应，因而在光电材料、微电子器件、生物传感器、催化剂等方面有着极为重要的应用。利用纳米颗粒优异的物理化学性质，以一种或者多种纳米颗粒为结构单元，通过自组装技术充分发挥纳米颗粒间的集聚效应，制备大尺寸、结构规整有序的2D阵列或3D阵列超晶体，或者具有特定功能的结构单元，则是促进纳米科技广泛应用的关键。Nanoparticles have specific surface effects, quantum size effects, small size effects, and macroscopic quantum tunneling effects, and thus have extremely important applications in photovoltaic materials, microelectronic devices, biosensors, and catalysts. Utilizing the excellent physical and chemical properties of nanoparticles, one or more kinds of nanoparticles are used as structural units, and the agglomeration effect between nanoparticles is fully utilized by self-assembly technology to prepare large-sized, well-structured 2D arrays or 3D array supercrystals. , or structural units with specific functions, is the key to promoting the wide application of nanotechnology.
二氧化钛作为一种重要的半导体材料，因其具有突出的化学稳定性、光电特性、生物相容性、抗腐蚀性等特点，已经广泛应用于涂料、光电池、气敏传感器、微电子器件、生物医用材料和光催化等领域。但是二氧化钛的应用，还需要克服一些困难。作为自组装材料和显示材料，纳米二氧化钛密度较大、分散性差，易团聚和沉降，实际使用很难达到理想的效果。As an important semiconductor material, titanium dioxide has been widely used in coatings, photovoltaic cells, gas sensors, microelectronic devices, and biomedicine because of its outstanding chemical stability, photoelectric properties, biocompatibility, and corrosion resistance. Materials and photocatalysis. However, the application of titanium dioxide still needs to overcome some difficulties. As self-assembled materials and display materials, nano-titanium dioxide has a high density, poor dispersibility, easy agglomeration and sedimentation, and it is difficult to achieve the desired effect in practical use.
纳米颗粒可以通过外界环境或外场的作用来实现可控的组装，最终得到有序的结构体。能够导向纳米颗粒进行自组装的外场主要分为：电场、磁场、流体力场、热场、声场、衬底表面能和压力等。通过外加电场直接自组装具有优势，能够使胶体颗粒快速自组装，而且易于控制、使用范围广而被普遍采用。Nanoparticles can be controlled by external environment or external field to achieve controlled assembly, resulting in an ordered structure. The external field capable of directing nanoparticles for self-assembly is mainly divided into electric field, magnetic field, fluid force field, thermal field, sound field, substrate surface energy and pressure. The direct self-assembly by the applied electric field has the advantage of being able to make the colloidal particles self-assemble quickly, and is easy to control and widely used, and is widely used.
纳米颗粒自组装是指金属纳米颗粒或半导体纳米颗粒等胶体颗粒通过偶极-偶极相互作用、表面张力和疏水作用形成特定功能(光学、电学、磁学和力学性能)结构的过程。导向自组装是一个通过有形的模板或场，以直接的形式影响自组装体系的聚集过程，通常使用的外场包括电场、磁场、流体力场、热场、声场、衬底表面能、压力等。电场导向的原理是：由于介电性质和周围的媒介体不匹配，大多数的纳米颗粒都可以在外电场下被极化，运动着的电荷也很容易受到外场的影响，有利于纳米颗粒在电场中的极化。围绕着纳米颗粒的外电场会使颗粒发生极化从而产生偶极，从而纳米颗粒之间会产生非常强的而且具有各向异性的偶极-偶极相互作用。如果这种偶极-偶极之间的相互作用足够强，能够克服颗粒的布朗运动，就会产生偶极的链，随着时间的增加链会变长变粗，最后会交联在一起形成能量最低的结构，如体心正方，六方和面心立方等堆积结构。具体结构的产生取决于纳米颗粒的材料、浓度、大小以及电场强度等因素。Nanoparticle self-assembly refers to the process of forming specific functional (optical, electrical, magnetic, and mechanical properties) structures by colloidal particles such as metal nanoparticles or semiconductor nanoparticles through dipole-dipole interaction, surface tension, and hydrophobic interaction. Guided self-assembly is a process of agglomeration of self-assembled systems in a direct form through a tangible template or field. The external fields commonly used include electric fields, magnetic fields, fluid force fields, thermal fields, sound fields, surface energy of substrates, and pressure. The principle of electric field guidance is that most of the nanoparticles can be polarized under an external electric field due to the mismatch between the dielectric properties and the surrounding medium. The moving charge is also susceptible to the external field, which is beneficial to the electric field of the nanoparticles. Polarization in the middle. The external electric field surrounding the nanoparticles causes the particles to polarize to create dipoles, resulting in very strong and anisotropic dipole-dipole interactions between the nanoparticles. If the interaction between the dipole-dipoles is strong enough to overcome the Brownian motion of the particles, a chain of dipoles will be produced. As time increases, the chains become longer and thicker and eventually crosslink together. The structure with the lowest energy, such as body-centered square, hexagonal and face-centered cubics. The generation of a specific structure depends on factors such as the material, concentration, size, and electric field strength of the nanoparticles.
对于外加电场控制二氧化钛自组装成珍珠链结构的制备，现有技术主要是通过施加交流电场来控制二氧化钛粒子的自组装，一般需要将二氧化钛分散在去离子水、丙酮等极性溶剂
中，电场强度需要>106V·cm-1，频率需要>～10kHz。For the preparation of the self-assembled titanium oxide structure by the external electric field control, the prior art mainly controls the self-assembly of the titanium dioxide particles by applying an alternating electric field, and generally needs to disperse the titanium dioxide in a polar solvent such as deionized water or acetone, the electric field strength. Need >10 6 V·cm -1 , frequency needs >10 kHz.
该方法的局限性主要体现在两方面：一是纳米颗粒需要分散在极性大的溶剂中，限制了纳米颗粒和溶剂的使用范围；二是电场强度较大，容易击穿破坏器件。The limitations of this method are mainly reflected in two aspects: First, the nanoparticles need to be dispersed in a solvent with a large polarity, which limits the range of use of the nanoparticles and the solvent; second, the electric field strength is large, and it is easy to break down and damage the device.
发明内容Summary of the invention
本发明的目的是提供一种降低电场强度、能在非极性溶剂中诱导二氧化钛纳米颗粒自组装形成珍珠链结构的方法。It is an object of the present invention to provide a method for reducing the electric field strength and enabling the self-assembly of titanium dioxide nanoparticles to form a pearl chain structure in a non-polar solvent.
为达到上述目的，本发明采用以下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种诱导二氧化钛纳米颗粒自组装形成珍珠链结构的方法，具体为：二氧化钛纳米颗粒经过改性在其表面包覆一层聚合物，然后将改性的二氧化钛纳米颗粒分散于非极性溶剂中，利用外加直流电场，使二氧化钛纳米颗粒定向自组装成珍珠链结构。A method for inducing self-assembly of titanium dioxide nanoparticles to form a pearl chain structure, specifically: the titanium dioxide nanoparticles are modified to coat a surface of the polymer, and then the modified titanium dioxide nanoparticles are dispersed in a non-polar solvent, The titanium dioxide nanoparticles are self-assembled into a pearl chain structure by using an external DC electric field.
进一步地，所述二氧化钛纳米颗粒在改性前为10～100nm，在改性后为200～500nm。Further, the titanium dioxide nanoparticles are 10 to 100 nm before the modification and 200 to 500 nm after the modification.
进一步地，所述聚合物为聚甲基丙烯酸甲酯。Further, the polymer is polymethyl methacrylate.
进一步地，所述氧化钛纳米颗粒改性具体为：将二氧化钛纳米颗粒分散于苯乙烯和二乙烯基苯中，加入表面活性剂，之后通过化学合成在二氧化钛纳米颗粒表面覆盖一层聚甲基丙烯酸甲酯。Further, the titanium oxide nanoparticles are modified by dispersing the titanium dioxide nanoparticles in styrene and divinylbenzene, adding a surfactant, and then chemically synthesizing the surface of the titanium dioxide nanoparticles with a layer of polymethacrylic acid. Methyl ester.
进一步地，所述氧化钛纳米颗粒改性具体为：将二氧化钛纳米颗粒分散于苯乙烯和二乙烯基苯中超声，然后倒入聚乙烯吡咯烷酮的甲醇溶液中超声，分散好后倒入烧瓶中，在氮气保护下，将偶氮二异丁腈加入其中，搅拌、升温进行反应，随后将甲基丙烯酸甲酯加入烧瓶中，继续反应，反应结束后，产物经洗涤、干燥，得到改性的二氧化钛纳米颗粒。Further, the titanium oxide nanoparticles are modified by: dispersing the titanium dioxide nanoparticles in styrene and divinylbenzene, and then ultrasonically pouring into a solution of polyvinylpyrrolidone in methanol, dispersing and pouring into a flask. Under the protection of nitrogen, azobisisobutyronitrile is added thereto, stirred and heated to carry out a reaction, and then methyl methacrylate is added to the flask to continue the reaction. After the reaction is finished, the product is washed and dried to obtain a modified titanium oxide. Nanoparticles.
进一步地，所述非极性溶剂为烷烃、苯、甲苯、二甲醚、乙酸乙酯、四氢呋喃、氯仿、二氯甲烷或四氯化碳。Further, the non-polar solvent is an alkane, benzene, toluene, dimethyl ether, ethyl acetate, tetrahydrofuran, chloroform, dichloromethane or carbon tetrachloride.
进一步地，所述烷烃为正己烷、环己烷、异辛烷、正十一烷或正十二烷。Further, the alkane is n-hexane, cyclohexane, isooctane, n-undecane or n-dodecane.
进一步地，所述直流电场的强度是1～6000V/cm。Further, the intensity of the direct current electric field is 1 to 6000 V/cm.
进一步地，该方法为：将二氧化钛纳米颗粒分散于苯乙烯和二乙烯基苯中超声，然后倒入聚乙烯吡咯烷酮的甲醇溶液中超声，分散好后倒入烧瓶中，在氮气保护下，将偶氮二异丁腈加入其中，搅拌、升温进行反应，随后将甲基丙烯酸甲酯加入烧瓶中，继续反应，反应结束后，产物经洗涤、干燥，得到改性的二氧化钛纳米颗粒；将改性的二氧化钛纳米颗粒分散于非极性溶剂中，并加入分散剂，以二氧化钛纳米颗粒为组装单元，通过在两个电极之间施加直流电场，使二氧化钛纳米颗粒在平板导电玻璃上定向自组装成珍珠链结构。Further, the method comprises: dispersing the titanium dioxide nanoparticles in styrene and divinylbenzene, and then ultrasonically pouring into a solution of polyvinylpyrrolidone in methanol, dispersing, pouring into a flask, and under the protection of nitrogen, Nitrogen diisobutyronitrile is added thereto, stirred and heated to carry out a reaction, and then methyl methacrylate is added to the flask to continue the reaction. After the reaction is finished, the product is washed and dried to obtain modified titanium dioxide nanoparticles; The titanium dioxide nanoparticles are dispersed in a non-polar solvent, and a dispersant is added, and the titanium dioxide nanoparticles are used as an assembly unit, and the titanium dioxide nanoparticles are self-assembled into a pearl chain on the flat conductive glass by applying a direct current electric field between the two electrodes. structure.
本发明具有以下有益效果：The invention has the following beneficial effects:
本发明通过对二氧化钛纳米颗粒进行表面改性，利用低于6000V/cm的直流外电场来控
制胶体颗粒自组装成珍珠链结构，能够显著降低电场强度，保证较安全的电压，保护电极；并提高自组装速度，缩短自组装时间，保证制备效率较高，形成的珍珠链结构，可广泛应用在光电子器件以及传感器中；而且可在非极性溶剂中完成自组装，扩宽了纳米颗粒和溶剂的使用范围。The invention controls the surface of the titanium dioxide nanoparticles by using a direct current external electric field of less than 6000V/cm.
The colloidal particles self-assemble into a pearl chain structure, which can significantly reduce the electric field strength, ensure a safe voltage, protect the electrode, improve the self-assembly speed, shorten the self-assembly time, ensure high preparation efficiency, and form a pearl chain structure. It is used in optoelectronic devices and sensors; it can also be self-assembled in non-polar solvents, broadening the use of nanoparticles and solvents.
图1是实施例1自组装的装置示意图；1 is a schematic view of a self-assembly apparatus of Embodiment 1;
图2是实施例1二氧化钛纳米自组装成珍珠链结构的原理图；2 is a schematic diagram of the self-assembly of titanium dioxide nano-assembly into a pearl chain structure of Example 1;
图3是实施例1未加电压时的显微镜图；Figure 3 is a micrograph of the first embodiment when no voltage is applied;
图4是实施例1施加电压后的显微镜图。4 is a micrograph of a first embodiment after a voltage is applied.
下面结合具体实施例对本发明做进一步的说明：The present invention will be further described below in conjunction with specific embodiments:
实施例1Example 1
1二氧化钛的改性：1 modification of titanium dioxide:
将0.2g二氧化钛纳米颗粒分散于0.3g苯乙烯和0.015g二乙烯基苯中超声20min，然后倒入2w/v％聚乙烯吡咯烷酮的甲醇溶液中超声20min，分散好后倒入三口烧瓶中，在氮气保护下，将0.01g偶氮二异丁腈加入其中，搅拌速度为350r/min，升温至65℃后，通氮气并搅拌反应6h；Disperse 0.2 g of titanium dioxide nanoparticles in 0.3 g of styrene and 0.015 g of divinylbenzene for 20 min, then pour into 2w/v% polyvinylpyrrolidone in methanol for 20 min, disperse and pour into a three-necked flask. Under nitrogen protection, 0.01 g of azobisisobutyronitrile was added thereto, the stirring speed was 350 r/min, and the temperature was raised to 65 ° C, and the reaction was stirred for 6 hours under nitrogen;
随后将0.03g甲基丙烯酸甲酯缓慢加入烧瓶中，维持搅拌速度，在65℃反应12h后结束，反应混合物用去离子、乙醇重复洗涤三次，经真空干燥后，得到白色固体粉末，即改性的二氧化钛纳米颗粒；Subsequently, 0.03 g of methyl methacrylate was slowly added to the flask, the stirring speed was maintained, and the reaction was completed after reacting at 65 ° C for 12 hours. The reaction mixture was repeatedly washed three times with deionized and ethanol, and dried under vacuum to obtain a white solid powder. Titanium dioxide nanoparticles;
表1改性前后二氧化钛的粒径大小以及相应的分散液的变化Table 1 The particle size of titanium dioxide before and after modification and the corresponding dispersion changes
未改性的二氧化钛颗粒吸附阳离子，胶粒带正电，其分散液的Zeta电位、迁移率为正，而改性后的二氧化钛颗粒在表面包覆了一层聚合物，可以吸附阴离子，其分散液的Zeta电位、迁移率为负，说明了聚合物改性二氧化钛成功。The unmodified titanium dioxide particles adsorb the cation, the colloidal particles are positively charged, and the zeta potential and mobility of the dispersion are positive, and the modified titanium dioxide particles are coated with a layer of polymer on the surface, which can adsorb anions and disperse them. The zeta potential and mobility of the liquid are negative, indicating the success of the polymer modified titanium dioxide.
2自组装结构：2 self-assembled structure:
图1是本发明方法的装置结构示意图，即通过施加直流外电场的装置示意图，1是二氧
化钛分散液，2是盖玻片，3是玻璃，4是ITO电极，图2是二氧化钛纳米自组装成珍珠链结构的原理图，利用外加直流电场，以二氧化钛纳米颗粒为组装单元，通过在两个电极之间施加电场来实现对随机分散的二氧化钛纳米颗粒的组装及其图案化排列。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of a device of the method of the present invention, i.e., a schematic diagram of a device for applying a direct external electric field, 1 being a dioxane
Titanium dispersion, 2 is a cover glass, 3 is glass, 4 is ITO electrode, Fig. 2 is a schematic diagram of titanium dioxide nano self-assembly into a pearl chain structure, using an external DC electric field, using titanium dioxide nanoparticles as an assembly unit, An electric field is applied between the two electrodes to achieve assembly and patterning of randomly dispersed titanium dioxide nanoparticles.
将0.005g改性的二氧化钛纳米颗粒分散在5mL正十一烷中，10w/v％Span80作分散剂，然后施加1～6000V/cm的直流电场10s后，带负电荷的二氧化钛纳米颗粒在平板导电玻璃等平板上定向自组装成珍珠链结构。图3是未加电压时，二氧化钛纳米颗粒随机分散在正十一烷中；图4是施加电压后，二氧化钛纳米颗粒自组装成珍珠链结构。0.005 g of the modified titanium dioxide nanoparticles were dispersed in 5 mL of n-undecane, 10 w/v% of Span 80 as a dispersing agent, and then a DC electric field of 1 to 6000 V/cm was applied for 10 s, and the negatively charged titanium dioxide nanoparticles were electrically conductive on the plate. Directly self-assembled into a pearl chain structure on a flat plate such as glass. 3 is a random dispersion of titanium dioxide nanoparticles in n-undecane when no voltage is applied; FIG. 4 is a self-assembly of titanium dioxide nanoparticles into a pearl chain structure after voltage application.
实施例2Example 2
1二氧化钛的改性：1 modification of titanium dioxide:
将0.5g二氧化钛纳米颗粒分散于0.5g苯乙烯和0.04g二乙烯基苯中超声30min，然后倒入3w/v％聚乙烯吡咯烷酮的甲醇溶液中超声30min，分散好后倒入三口烧瓶中，在氮气保护下，将0.02g偶氮二异丁腈加入其中，搅拌速度为500r/min，升温至60℃后，通氮气并搅拌反应8h；0.5 g of titanium dioxide nanoparticles were dispersed in 0.5 g of styrene and 0.04 g of divinylbenzene for 30 min, then poured into a methanol solution of 3 w/v% polyvinylpyrrolidone for 30 min, dispersed, and poured into a three-necked flask. Under nitrogen protection, 0.02 g of azobisisobutyronitrile was added thereto, the stirring speed was 500 r/min, and the temperature was raised to 60 ° C, and the reaction was stirred for 8 hours under nitrogen;
随后将0.05g甲基丙烯酸甲酯缓慢加入烧瓶中，维持搅拌速度，在60℃反应15h后结束，反应混合物用去离子、乙醇重复洗涤三次，经真空干燥后，得到白色固体粉末，即改性的二氧化钛纳米颗粒；Subsequently, 0.05 g of methyl methacrylate was slowly added to the flask, the stirring speed was maintained, and the reaction was completed after reacting at 60 ° C for 15 hours. The reaction mixture was repeatedly washed three times with deionized and ethanol, and dried under vacuum to obtain a white solid powder. Titanium dioxide nanoparticles;
2自组装结构：2 self-assembled structure:
将0.01g改性的二氧化钛纳米颗粒分散在15mL正十二烷中，20w/v％Span80作分散剂，然后施加6000V/cm的直流电场5s后，带负电荷的二氧化钛纳米颗粒在平板导电玻璃等平板上定向自组装成珍珠链结构。0.01 g of modified titanium dioxide nanoparticles were dispersed in 15 mL of n-dodecane, 20 w/v% of Span 80 as a dispersing agent, and then a DC electric field of 6000 V/cm was applied for 5 s, and negatively charged titanium dioxide nanoparticles were used in flat conductive glass. Directly self-assembled into a pearl chain structure on the plate.
实施例3Example 3
1二氧化钛的改性：1 modification of titanium dioxide:
将0.2g二氧化钛纳米颗粒分散于0.4g苯乙烯和0.03g二乙烯基苯中超声15min，然后倒入4w/v％聚乙烯吡咯烷酮的甲醇溶液中超声15min，分散好后倒入三口烧瓶中，在氮气保护下，将0.01g偶氮二异丁腈加入其中，搅拌速度为400r/min，升温至70℃后，通氮气并搅拌反应5h；Disperse 0.2g of titanium dioxide nanoparticles in 0.4g of styrene and 0.03g of divinylbenzene for 15min, then pour into 4w/v% polyvinylpyrrolidone in methanol for 15min, disperse and pour into a three-necked flask. Under nitrogen protection, 0.01 g of azobisisobutyronitrile was added thereto, the stirring speed was 400 r / min, and the temperature was raised to 70 ° C, and the reaction was stirred for 5 hours under nitrogen;
随后将0.04g甲基丙烯酸甲酯缓慢加入烧瓶中，维持搅拌速度，在70℃反应10h后结束，反应混合物用去离子、乙醇重复洗涤三次，经真空干燥后，得到白色固体粉末，即改性的二氧化钛纳米颗粒；Subsequently, 0.04 g of methyl methacrylate was slowly added to the flask, the stirring speed was maintained, and the reaction was completed after reacting at 70 ° C for 10 hours. The reaction mixture was repeatedly washed three times with deionized and ethanol, and dried under vacuum to obtain a white solid powder. Titanium dioxide nanoparticles;
2自组装结构：2 self-assembled structure:
将0.005g改性的二氧化钛纳米颗粒分散在10mL四氯化碳中，15w/v％Span80作分散剂，
然后施加1V/cm的直流电场60s后，带负电荷的二氧化钛纳米颗粒在平板导电玻璃等平板上定向自组装成珍珠链结构。0.005 g of the modified titanium dioxide nanoparticles were dispersed in 10 mL of carbon tetrachloride, and 15 w/v% of Span 80 was used as a dispersing agent.
Then, after applying a DC electric field of 1 V/cm for 60 s, the negatively charged titanium dioxide nanoparticles are self-assembled into a pearl chain structure on a flat plate of a conductive glass or the like.
实施例4Example 4
按照实施例1的步骤进行，将分散溶剂由正十一烷改为甲苯。Following the procedure of Example 1, the dispersion solvent was changed from n-undecane to toluene.
实施例5Example 5
按照实施例1的步骤进行，将分散溶剂由正十一烷改为乙酸乙酯。Following the procedure of Example 1, the dispersion solvent was changed from n-undecane to ethyl acetate.
实施例6Example 6
按照实施例1的步骤进行，将分散溶剂由正十一烷改为氯仿。Following the procedure of Example 1, the dispersion solvent was changed from n-undecane to chloroform.
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。
The above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of changes or substitutions within the technical scope of the present invention. All should be covered by the scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims (9)
- 一种诱导二氧化钛纳米颗粒自组装形成珍珠链结构的方法，其特征在于，所述方法为：二氧化钛纳米颗粒经过改性在其表面包覆一层聚合物，然后将改性的二氧化钛纳米颗粒分散于非极性溶剂中，利用外加直流电场，使二氧化钛纳米颗粒定向自组装成珍珠链结构。A method for inducing self-assembly of titanium dioxide nanoparticles to form a pearl chain structure, characterized in that: the titanium dioxide nanoparticles are modified to coat a surface thereof with a layer of polymer, and then the modified titanium dioxide nanoparticles are dispersed in In the non-polar solvent, the titanium dioxide nanoparticles are self-assembled into a pearl chain structure by applying a direct current electric field.
- 根据权利要求1所述的方法，其特征在于，所述二氧化钛纳米颗粒在改性前为10～100nm，在改性后为200～500nm。The method according to claim 1, wherein the titanium dioxide nanoparticles are 10 to 100 nm before modification and 200 to 500 nm after modification.
- 根据权利要求1所述的方法，其特征在于，所述聚合物为聚甲基丙烯酸甲酯。The method of claim 1 wherein said polymer is polymethyl methacrylate.
- 根据权利要求1所述的方法，其特征在于，所述氧化钛纳米颗粒改性具体为：将二氧化钛纳米颗粒分散于苯乙烯和二乙烯基苯中，加入表面活性剂，之后通过化学合成在二氧化钛纳米颗粒表面覆盖一层聚甲基丙烯酸甲酯。The method according to claim 1, wherein the titanium oxide nanoparticles are modified by dispersing titanium dioxide nanoparticles in styrene and divinylbenzene, adding a surfactant, and then chemically synthesizing in titanium dioxide. The surface of the nanoparticles is covered with a layer of polymethyl methacrylate.
- 根据权利要求4所述的方法，其特征在于，所述氧化钛纳米颗粒改性具体为：将二氧化钛纳米颗粒分散于苯乙烯和二乙烯基苯中超声，然后倒入聚乙烯吡咯烷酮的甲醇溶液中超声，分散好后倒入烧瓶中，在氮气保护下，将偶氮二异丁腈加入其中，搅拌、升温进行反应，随后将甲基丙烯酸甲酯加入烧瓶中，继续反应，反应结束后，产物经洗涤、干燥，得到改性的二氧化钛纳米颗粒。The method according to claim 4, wherein the modification of the titanium oxide nanoparticles is specifically: dispersing the titanium dioxide nanoparticles in styrene and divinylbenzene, and then pouring into a methanol solution of polyvinylpyrrolidone. After ultrasonication, the mixture was poured into a flask, and azobisisobutyronitrile was added thereto under nitrogen atmosphere, and the reaction was stirred and heated, and then methyl methacrylate was added to the flask to continue the reaction. After the reaction, the product was obtained. After washing and drying, modified titanium dioxide nanoparticles are obtained.
- 根据权利要求1所述的方法，其特征在于，所述非极性溶剂为烷烃、苯、甲苯、二甲醚、乙酸乙酯、四氢呋喃、氯仿、二氯甲烷或四氯化碳。The method according to claim 1, wherein the non-polar solvent is an alkane, benzene, toluene, dimethyl ether, ethyl acetate, tetrahydrofuran, chloroform, dichloromethane or carbon tetrachloride.
- 根据权利要求6所述的方法，其特征在于，所述烷烃为正己烷、环己烷、异辛烷、正十一烷或正十二烷。The method of claim 6 wherein the alkane is n-hexane, cyclohexane, isooctane, n-undecane or n-dodecane.
- 根据权利要求1所述的方法，其特征在于，所述直流电场的强度是1～6000V/cm。The method of claim 1 wherein said DC electric field has an intensity of from 1 to 6000 V/cm.
- 根据权利要求1所述的方法，其特征在于，将二氧化钛纳米颗粒分散于苯乙烯和二乙烯基苯中超声，然后倒入聚乙烯吡咯烷酮的甲醇溶液中超声，分散好后倒入烧瓶中，在氮气保护下，将偶氮二异丁腈加入其中，搅拌、升温进行反应，随后将甲基丙烯酸甲酯加入烧瓶中，继续反应，反应结束后，产物经洗涤、干燥，得到改性的二氧化钛纳米颗粒；将改性的二氧化钛纳米颗粒分散于非极性溶剂中，并加入分散剂，以二氧化钛纳米颗粒为组装单元，通过在两个电极之间施加直流电场，使二氧化钛纳米颗粒在平板导电玻璃上定向自组装成珍珠链结构。 The method according to claim 1, wherein the titanium dioxide nanoparticles are dispersed in styrene and divinylbenzene, and then ultrasonicated, poured into a methanol solution of polyvinylpyrrolidone, dispersed, and poured into a flask. Under the protection of nitrogen, azobisisobutyronitrile is added thereto, stirred and heated to carry out a reaction, and then methyl methacrylate is added to the flask to continue the reaction. After the reaction is finished, the product is washed and dried to obtain a modified titanium dioxide nanometer. Particles; dispersing the modified titanium dioxide nanoparticles in a non-polar solvent, adding a dispersant, using titanium dioxide nanoparticles as an assembly unit, and applying a direct current electric field between the two electrodes to make the titanium dioxide nanoparticles on the flat conductive glass Oriented self-assembly into a pearl chain structure.
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