CN117645313A - Preparation method of double-spherical mesoscopic crystal zinc oxide capable of photoinduced terahertz wave emission - Google Patents
Preparation method of double-spherical mesoscopic crystal zinc oxide capable of photoinduced terahertz wave emission Download PDFInfo
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Abstract
Description
技术领域Technical field
本发明属于材料工程技术领域，具体属于一种光致发射太赫兹波的双球形介观晶体氧化锌制备方法。The invention belongs to the technical field of material engineering, and specifically belongs to a method for preparing double spherical mesoscopic crystal zinc oxide that photoemises terahertz waves.
背景技术Background technique
太赫兹波具有非常重要的潜在的应用价值，但是相比于电磁波和光波，太赫兹波更难以可控性的产生。太赫兹波的理论和应用研究之所以发展滞后主要是受制于太赫兹波的产生方法和技术。对于太赫兹波产生方法和技术的研究是整个太赫兹波技术研究的瓶颈领域，因此吸引了众多学者和研究人员的关注。如果能发展出像产生电磁波和光波一样的结构简单、成本低、可控性好、转换效率高的仪器方法，太赫兹波的应用研究将会得到极大的发展。Terahertz waves have very important potential application value, but compared with electromagnetic waves and light waves, terahertz waves are more difficult to generate controllably. The reason why the theoretical and applied research on terahertz waves lags behind is mainly restricted by the generation methods and technologies of terahertz waves. The study of terahertz wave generation methods and technologies is the bottleneck area of the entire terahertz wave technology research, and therefore has attracted the attention of many scholars and researchers. If an instrument method with simple structure, low cost, good controllability and high conversion efficiency can be developed to generate electromagnetic waves and light waves, the applied research of terahertz waves will be greatly developed.
利用具有压电性能的纳米材料来产生太赫兹辐射，其方法简单，适合制备出结构简单、价格便宜以及小巧便携的太赫兹发射源。这就如同例如发光材料的发光性能来产生光一样方便。通过其太赫兹波产生的机理可以看出，其产生波的频率和材料的结构形貌直接相关，为了获得不同波段的太赫兹波就需要可控性的合成制备出不同形貌的纳米压电材料。而材料对太赫兹波的产生功率和转换效率和其压电性能密切相关，这就需要对材料的成分、晶体结构等进行调节。The method of using nanomaterials with piezoelectric properties to generate terahertz radiation is simple and suitable for preparing a terahertz emission source with simple structure, low price, small size and portability. This is as convenient as e.g. the luminescent properties of luminescent materials used to generate light. It can be seen from the mechanism of terahertz wave generation that the frequency of the generated wave is directly related to the structural morphology of the material. In order to obtain terahertz waves in different bands, it is necessary to controllably synthesize nano piezoelectric nanoparticles with different morphologies. Material. The power and conversion efficiency of a material for terahertz waves are closely related to its piezoelectric properties, which requires adjustments to the composition and crystal structure of the material.
不同于简单形貌的纳米材料，具有介观晶体特性的纳米材料具有更复杂的生长过程，其形貌控制的难度也比简单形貌的纳米材料要大。然而现有技术中并没有可以对具有介观晶体特性的纳米材料进行生长制备的工艺方法。Different from nanomaterials with simple morphology, nanomaterials with mesoscopic crystal properties have a more complex growth process, and their morphology control is more difficult than nanomaterials with simple morphology. However, there is no process in the prior art that can grow and prepare nanomaterials with mesoscopic crystal properties.
发明内容Contents of the invention
为了解决现有技术中存在的问题，本发明提供一种光致发射太赫兹波的双球形介观晶体氧化锌制备方法，用于解决背景技术中的问题，本发明的一种水热合成方法制备出了具有双球外形形貌的氧化锌介观晶体。这种方法制备的氧化锌介观晶体具有形貌和介观晶体结构均匀性好，且在0.4THz,3.0THz,4.3THz三个波段具有太赫兹波发射性能。In order to solve the problems existing in the prior art, the present invention provides a method for preparing double spherical mesoscopic crystal zinc oxide that photoemises terahertz waves to solve the problems in the background technology. A hydrothermal synthesis method of the present invention Zinc oxide mesoscopic crystals with double-spherical morphology were prepared. The zinc oxide mesoscopic crystal prepared by this method has good uniformity in morphology and mesoscopic crystal structure, and has terahertz wave emission performance in the three wave bands of 0.4THz, 3.0THz, and 4.3THz.
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:
一种光致发射太赫兹波的双球形介观晶体氧化锌制备方法，包括以下步骤，A method for preparing double spherical mesoscopic crystal zinc oxide that photoemises terahertz waves, including the following steps:
步骤1，将聚氧丙烯聚氧乙烯共聚物加入到去离子水和无水乙醇的混合溶液中，搅拌后形成透明混合液体；Step 1: Add polyoxypropylene polyoxyethylene copolymer to a mixed solution of deionized water and absolute ethanol, and stir to form a transparent mixed liquid;
步骤2，在步骤1制备的透明混合液体中依次加入醋酸锌和六次甲基四胺，搅拌后加入乙二醇溶液，搅拌后形成澄清溶液；Step 2: Add zinc acetate and hexamethylenetetramine in sequence to the transparent mixed liquid prepared in step 1, add ethylene glycol solution after stirring, and form a clear solution after stirring;
步骤3，对步骤2的澄清溶液进行静置陈化处理；Step 3: Perform static aging treatment on the clarified solution in Step 2;
步骤4，将步骤3中陈化后的液体进行加热反应；Step 4: Heat the aged liquid in Step 3 for reaction;
步骤5，将反应后的产物进行离心分离，并进行清洗，干燥后形成双球形介观晶体氧化锌。Step 5: The reaction product is centrifuged, washed, and dried to form double spherical mesoscopic crystal zinc oxide.
优选的，步骤1中所用的聚氧丙烯聚氧乙烯共聚物，去离子水，无水乙醇的质量比为0.5-1.5：2.0-3.0：10-20。Preferably, the mass ratio of polyoxypropylene-polyoxyethylene copolymer, deionized water, and absolute ethanol used in step 1 is 0.5-1.5:2.0-3.0:10-20.
优选的，步骤1中，混合溶液的搅拌速度为600～900rad/min，搅拌时间为15～20min。Preferably, in step 1, the stirring speed of the mixed solution is 600-900 rad/min, and the stirring time is 15-20 min.
优选的，步骤2中加入的醋酸锌的质量百分比范围为2.5％～3％，加入的六次甲基四胺的质量百分比范围为1％～1.5％。Preferably, the mass percentage of zinc acetate added in step 2 ranges from 2.5% to 3%, and the mass percentage of hexamethylenetetramine added ranges from 1% to 1.5%.
优选的，步骤2中，搅拌速度为600～900rad/min，时间为30min。Preferably, in step 2, the stirring speed is 600-900rad/min and the stirring time is 30 minutes.
优选的，步骤3中，静置陈化处理的温度范围为20-30℃，静置陈化时间为7-8天。Preferably, in step 3, the temperature range of the static aging treatment is 20-30°C, and the static aging time is 7-8 days.
优选的，步骤4中，将陈化后的液体加入反应釜中，放在烘箱中进行加热反应。Preferably, in step 4, the aged liquid is added to the reaction kettle and placed in an oven for heating reaction.
优选的，步骤4中，加热反应的温度范围为100-120℃，反应时间范围为12-18小时。Preferably, in step 4, the temperature range of the heating reaction is 100-120°C, and the reaction time range is 12-18 hours.
优选的，步骤5中，清洗时的清洗试剂分别是乙醇和水，先用乙醇清洗2次，再用水洗2次。Preferably, in step 5, the cleaning reagents during cleaning are ethanol and water respectively. First, wash twice with ethanol, and then wash twice with water.
优选的，步骤5中，离心速度范围为6000-8000r/min。Preferably, in step 5, the centrifugation speed range is 6000-8000r/min.
与现有技术相比，本发明具有以下有益的技术效果：Compared with the existing technology, the present invention has the following beneficial technical effects:
本发明提供一种光致发射太赫兹波的双球形介观晶体氧化锌制备方法，这种介观晶体氧化锌纳米颗粒能够在可见光激发下发射太赫兹波，可以成为制备光致发射太赫兹波器件的原材料，具有重要的应用价值。介观晶体是由大量的单晶体通过一定的方式排列组合生长到一起，每个单晶体之间的晶面夹角非常小。由于介观晶体的这种特殊晶体结构，为了获得形貌均匀一致的介观晶体，常常需要开发特定的制备方法。本发明提供了一种可制备形貌均匀性非常高的氧化锌介观晶体的方法，制备出的双球形介观晶体氧化锌纳米颗粒形貌均匀一致，并且在绿光激发下发射三种波段的太赫兹波，发射的太赫兹波段分别是：0.4THz，3.0THz，4.3THz。The present invention provides a method for preparing double spherical mesoscopic crystal zinc oxide that can photoemit terahertz waves. Such mesoscopic crystal zinc oxide nanoparticles can emit terahertz waves under visible light excitation and can be used to prepare photoemitting terahertz waves. The raw materials of devices have important application value. Mesoscopic crystals are composed of a large number of single crystals that are arranged and combined in a certain way to grow together. The angle between the crystal planes of each single crystal is very small. Due to the special crystal structure of mesoscopic crystals, in order to obtain mesoscopic crystals with uniform morphology, it is often necessary to develop specific preparation methods. The invention provides a method for preparing zinc oxide mesoscopic crystals with very high morphological uniformity. The prepared double spherical mesoscopic crystal zinc oxide nanoparticles have a uniform morphology and emit three wavebands under green light excitation. The terahertz waves emitted are: 0.4THz, 3.0THz, and 4.3THz.
附图说明Description of drawings
图1为双球形介观晶体氧化锌纳米颗粒大面积的扫描电镜照片。Figure 1 is a scanning electron microscope photo of a large area of double spherical mesoscopic crystalline zinc oxide nanoparticles.
图2为双球形介观晶体氧化锌纳米颗粒低倍的扫描电镜照片。Figure 2 is a low-magnification scanning electron microscope photo of double spherical mesoscopic crystalline zinc oxide nanoparticles.
图3为双球形介观晶体氧化锌纳米颗粒高倍的扫描电镜照片。Figure 3 is a high-magnification scanning electron microscope photo of double spherical mesoscopic crystalline zinc oxide nanoparticles.
图4为双球形介观晶体氧化锌纳米颗粒透射电镜照片。Figure 4 is a transmission electron microscope photo of double spherical mesoscopic crystalline zinc oxide nanoparticles.
图5为双球形介观晶体氧化锌纳米颗粒的电子衍射花样照片。Figure 5 is an electron diffraction pattern photo of double spherical mesoscopic crystalline zinc oxide nanoparticles.
图6为双球形介观晶体氧化锌纳米颗粒的X射线衍射图谱。Figure 6 shows the X-ray diffraction pattern of double spherical mesoscopic crystalline zinc oxide nanoparticles.
图7为双球形介观晶体氧化锌纳米颗粒在绿光激发下发射的太赫兹谱。Figure 7 shows the terahertz spectrum of double spherical mesoscopic crystalline zinc oxide nanoparticles emitted under green light excitation.
图8为ZnO双球结构生长过程示意图。Figure 8 is a schematic diagram of the growth process of ZnO double sphere structure.
图9为双球状ZnO生长过程示意图。Figure 9 is a schematic diagram of the growth process of double spherical ZnO.
图10为P123与Zn2+不同比例下ZnO形貌变化图。Figure 10 shows the morphology changes of ZnO at different ratios of P123 and Zn2+.
图11为不同静置陈化温度下ZnO形貌的变化。Figure 11 shows the changes in the morphology of ZnO under different static aging temperatures.
图12为不同静置陈化时间下的ZnO结构变化。Figure 12 shows the structural changes of ZnO under different standing aging times.
具体实施方式Detailed ways
下面结合具体的实施例对本发明做进一步的详细说明，所述是对本发明的解释而不是限定。The present invention will be further described in detail below with reference to specific examples, which are explanations rather than limitations of the present invention.
本发明提供了一种具有0.4THz,3.0THz,4.3THz三个波段发射太赫兹波的氧化锌介观晶体材料的制备方法，其目的在于提供更多种类和更多波段的太赫兹波发射材料，可用于制备产生相应波段的太赫兹波发生器件。The present invention provides a method for preparing a zinc oxide mesoscopic crystal material that emits terahertz waves in three bands: 0.4THz, 3.0THz, and 4.3THz. Its purpose is to provide more types and more bands of terahertz wave emitting materials. , can be used to prepare terahertz wave generating devices that generate corresponding wave bands.
本发明提供的用于制备双球形介观晶体氧化锌的技术方案为：The technical solution provided by the present invention for preparing double spherical mesoscopic crystal zinc oxide is:
步骤一：配置反应溶液。将聚氧丙烯聚氧乙烯共聚物(PEG-PPG-PEG,P123)加入到去离子水和无水乙醇的混合溶液中，剧烈搅拌一段时间形成透明的混合液体。Step 1: Prepare reaction solution. Add polyoxypropylene polyoxyethylene copolymer (PEG-PPG-PEG, P123) to the mixed solution of deionized water and absolute ethanol, and stir vigorously for a period of time to form a transparent mixed liquid.
步骤二：加入反应溶剂。向前步骤制备的透明液体中依次加入醋酸锌和六次甲基四胺，剧烈搅拌一段时间后加入乙二醇溶液，搅拌一段时间后形成澄清溶液。Step 2: Add reaction solvent. Add zinc acetate and hexamethylenetetramine in sequence to the transparent liquid prepared in the previous step, stir vigorously for a period of time, add the ethylene glycol solution, and form a clear solution after stirring for a period of time.
步骤三：静置陈化。将前步骤制备的透明液体放置一段时间静置陈化。Step 3: Leave to age. Leave the transparent liquid prepared in the previous step for a period of time to mature.
步骤四：反应制备。将陈化后的液体加入反应釜中，放在烘箱中加热反应一段时间。Step 4: Reaction preparation. Add the aged liquid into the reaction kettle and heat it in the oven for a period of time.
步骤五：清洗收集产物。将反应后的产物进行离心分离，并进行清洗。Step 5: Clean and collect the product. The reaction product is centrifuged and washed.
太赫兹波具有非常重要的潜在的应用价值，但是相比于电磁波和光波，太赫兹波更难以可控性的产生。太赫兹波的理论和应用研究之所以发展滞后主要是受制于太赫兹波的产生方法和技术。本发明制备了一种双球形介观晶体氧化锌纳米颗粒，这种介观晶体氧化锌纳米颗粒能够在可见光激发下发射太赫兹波，可以成为制备光致发射太赫兹波器件的原材料，具有重要的应用价值。虽然目前人们已经合成了各种形貌的氧化锌纳米材料，但是大部分氧化锌纳米材料是单晶或者多晶结构，介观晶体氧化锌合成制备难度较高。介观晶体是由大量的单晶体通过一定的方式排列组合生长到一起，每个单晶体之间的晶面夹角非常小。由于介观晶体的这种特殊晶体结构，为了获得形貌均匀一致的介观晶体，常常需要开发特定的制备方法。本发明提供了一种可制备形貌均匀性非常高的氧化锌介观晶体的方法，制备出的双球形介观晶体氧化锌纳米颗粒形貌均匀一致，并且在绿光激发下发射三种波段的太赫兹波，发射的太赫兹波段分别是：0.4THz，3.0THz，4.3THz。能够制备双球形介观晶体氧化锌纳米颗粒，且能够在绿光激发下发射0.4THz、3.0THz、4.3THz三个波段太赫兹波的氧化锌材料还没有相关的报道。Terahertz waves have very important potential application value, but compared with electromagnetic waves and light waves, terahertz waves are more difficult to generate controllably. The reason why the theoretical and applied research on terahertz waves lags behind is mainly restricted by the generation methods and technologies of terahertz waves. The invention prepares a double spherical mesoscopic crystalline zinc oxide nanoparticle. This mesoscopic crystalline zinc oxide nanoparticle can emit terahertz waves under visible light excitation, and can become a raw material for preparing photoemitting terahertz wave devices. It has important application value. Although zinc oxide nanomaterials of various morphologies have been synthesized, most zinc oxide nanomaterials have single crystal or polycrystalline structures, and the synthesis and preparation of mesoscopic crystalline zinc oxide is relatively difficult. Mesoscopic crystals are composed of a large number of single crystals that are arranged and combined in a certain way to grow together. The angle between the crystal planes of each single crystal is very small. Due to the special crystal structure of mesoscopic crystals, in order to obtain mesoscopic crystals with uniform morphology, it is often necessary to develop specific preparation methods. The invention provides a method for preparing zinc oxide mesoscopic crystals with very high morphological uniformity. The prepared double spherical mesoscopic crystal zinc oxide nanoparticles have a uniform morphology and emit three wavebands under green light excitation. The terahertz waves emitted are: 0.4THz, 3.0THz, and 4.3THz. There are no relevant reports on zinc oxide materials that can prepare double spherical mesoscopic crystal zinc oxide nanoparticles and can emit terahertz waves in three bands of 0.4THz, 3.0THz, and 4.3THz under green light excitation.
实施例1Example 1
将0.1g聚氧丙烯聚氧乙烯共聚物(PEG-PPG-PEG,P123)加入到0.23g去离子水和1.5g无水乙醇的混合溶液中，剧烈搅拌15min直至形成透明的混合液体，搅拌速度为600rad/min，向透明的液体中依次加入0.05g醋酸锌和0.023g的六次甲基四胺，剧烈搅拌30min后加入23mL乙二醇溶液，搅拌30min直至形成澄清溶液，静置陈化一周，静置陈化温度为25℃；将反应釜放在烘箱中110度加热15h。将反应得到的白色产物在7000r/min的转速下用乙醇清洗2次，用去离子水清洗2次，干燥后待用。Add 0.1g polyoxypropylene polyoxyethylene copolymer (PEG-PPG-PEG, P123) to a mixed solution of 0.23g deionized water and 1.5g absolute ethanol, and stir vigorously for 15 minutes until a transparent mixed liquid is formed. Stir speed At 600rad/min, add 0.05g zinc acetate and 0.023g hexamethylenetetramine in sequence to the transparent liquid, stir vigorously for 30 minutes, then add 23mL ethylene glycol solution, stir for 30 minutes until a clear solution is formed, and let it stand for a week. , the static aging temperature is 25°C; place the reaction kettle in the oven and heat it at 110°C for 15h. The white product obtained by the reaction was washed twice with ethanol and twice with deionized water at a rotation speed of 7000 r/min, and dried before use.
通过以上方式制备的双球形介观晶体氧化锌纳米颗粒的形貌见图1，图2，图3的扫描电镜照片。图1显示本发明所制备的大量的氧化锌纳米颗粒形貌非常均匀一致。图2显示本发明所制备的氧化锌纳米颗粒都具有双球形的独特形貌。图3显示本发明所制备的氧化锌纳米介观晶体是有大量的小晶粒配列聚集形成。图4透射电镜图片进一步显示发明所制备的氧化锌纳米介观晶体是有大量的小晶粒配列聚集形成。图5双球形氧化锌纳米颗粒的电子衍射花样展示了典型的介观晶体结构。图6中的X射线衍射图谱证实纳米颗粒是氧化锌成分，并且不含其它成分。The morphology of the double spherical mesoscopic crystalline zinc oxide nanoparticles prepared by the above method is shown in the scanning electron microscope photos of Figure 1, Figure 2, and Figure 3. Figure 1 shows that the morphology of a large number of zinc oxide nanoparticles prepared by the present invention is very uniform. Figure 2 shows that the zinc oxide nanoparticles prepared in the present invention all have a unique double-spherical morphology. Figure 3 shows that the zinc oxide nano mesocrystals prepared by the present invention are formed by the arrangement and aggregation of a large number of small crystal grains. The transmission electron microscope picture in Figure 4 further shows that the zinc oxide nano mesocrystals prepared by the invention are formed by the arrangement and aggregation of a large number of small grains. Figure 5 The electron diffraction pattern of double spherical zinc oxide nanoparticles shows a typical mesoscopic crystal structure. The X-ray diffraction pattern in Figure 6 confirms that the nanoparticles are composed of zinc oxide and do not contain other components.
制备的双球形介观晶体氧化锌纳米颗粒的太赫兹发射性能见图7所示。采用514.5nm的氩离子激光作为激发源激发氧化锌纳米颗粒时，可产生三个波段的太赫兹波，分别是0.4THz、3.0THz及4.3THz。The terahertz emission performance of the prepared double spherical mesoscopic crystalline zinc oxide nanoparticles is shown in Figure 7. When 514.5nm argon ion laser is used as the excitation source to excite zinc oxide nanoparticles, three bands of terahertz waves can be generated, namely 0.4THz, 3.0THz and 4.3THz.
本发明的制备反应原理如下：在六次甲基四胺提供的碱性环境中，前驱体Zn2+首先以沉淀颗粒的形式出现，形成杂乱无章的纳米团聚物分散在溶液中。The preparation reaction principle of the present invention is as follows: in the alkaline environment provided by hexamethylenetetramine, the precursor Zn 2+ first appears in the form of precipitated particles, forming chaotic nanometer agglomerates dispersed in the solution.
纳米团聚物在溶液中发生自组装形成不规整的纳米片层，随着表面结晶程度的增强，纳米片层逐渐形成具有一定厚度的圆柱形结构，如图8(a)所示。Nanoaggregates self-assemble in solution to form irregular nanosheets. As the degree of surface crystallization increases, the nanosheets gradually form a cylindrical structure with a certain thickness, as shown in Figure 8(a).
圆柱形中心逐渐向内凹陷如图8(b)红框内所示。反应时间继续加长，沿着中心凹陷的圆柱形结构两侧，纳米团聚物开始聚集形成两个半球式结构，如图8(c)所示。The center of the cylindrical shape gradually dents inward, as shown in the red box in Figure 8(b). As the reaction time continues to increase, nanoagglomerates begin to aggregate along both sides of the cylindrical structure with a concave center to form two hemispherical structures, as shown in Figure 8(c).
两个半球逐渐生长，半球中间的圆柱形结构逐渐向内凹陷消失不见如图8(d)。The two hemispheres gradually grow, and the cylindrical structure in the middle of the hemisphere gradually sinks inward and disappears as shown in Figure 8(d).
随着反应时间的加长，柱状体最终完全消失不见，两个半球依靠圆柱体边缘结合在一起，形成的结构如图8(e)所示。As the reaction time increases, the columnar body finally disappears completely, and the two hemispheres are combined together by the edge of the cylinder, forming a structure as shown in Figure 8(e).
当双球结构形成后，双球中的纳米团聚物由介观物质向晶体发生转变，形貌也由纳米颗粒转变为纳米片，最终形成如图8(f)所示的结构。When the double sphere structure is formed, the nanoagglomerates in the double sphere transform from mesoscopic substances to crystals, and the morphology also changes from nanoparticles to nanosheets, finally forming the structure shown in Figure 8(f).
根据实验中观察到的生长过程实验现象，推导的生长过程如图9所示。Based on the experimental phenomena of the growth process observed in the experiment, the deduced growth process is shown in Figure 9.
实施例2Example 2
将0.05g聚氧丙烯聚氧乙烯共聚物(PEG-PPG-PEG,P123)加入到0.3g去离子水和2.0g无水乙醇的混合溶液中，剧烈搅拌20min直至形成透明的混合液体，搅拌速度为900rad/min；向透明的液体中依次加入0.058g醋酸锌和0.0235g的六次甲基四胺，剧烈搅拌20min后加入乙二醇溶液，乙二醇溶液的质量是无水乙醇的质量100倍，搅拌30min直至形成澄清溶液，静置陈化一周，静置陈化温度为25℃，将反应釜放在烘箱中100度加热18h。将反应得到的白色产物在6000r/min的转速下用乙醇清洗2次，用去离子水清洗2次，干燥后待用。Add 0.05g polyoxypropylene polyoxyethylene copolymer (PEG-PPG-PEG, P123) to a mixed solution of 0.3g deionized water and 2.0g absolute ethanol, and stir vigorously for 20 minutes until a transparent mixed liquid forms. Stir speed It is 900rad/min; add 0.058g zinc acetate and 0.0235g hexamethylenetetramine in sequence to the transparent liquid, stir vigorously for 20 minutes and then add the ethylene glycol solution. The mass of the ethylene glycol solution is the mass of absolute ethanol 100 times, stir for 30 minutes until a clear solution is formed, let it stand for one week, and the stand and aging temperature is 25°C. Place the reaction kettle in an oven and heat it at 100 degrees for 18 hours. The white product obtained by the reaction was washed twice with ethanol and twice with deionized water at a rotation speed of 6000 r/min, and dried before use.
实施例3Example 3
将0.15g聚氧丙烯聚氧乙烯共聚物(PEG-PPG-PEG,P123)加入到0.25g去离子水和1.0g无水乙醇的混合溶液中，剧烈搅拌15min直至形成透明的混合液体，搅拌速度为800rad/min，向透明的液体中依次加入0.04g醋酸锌和0.020g的六次甲基四胺，剧烈搅拌35min后加入乙二醇溶液，乙二醇溶液的质量是无水乙醇的质量100倍，搅拌30min直至形成澄清溶液，静置陈化八天，静置陈化温度为30℃，将反应釜放在烘箱中120度加热12h。将反应得到的白色产物在7000r/min的转速下用乙醇清洗2次，用去离子水清洗2次，干燥后待用。Add 0.15g polyoxypropylene polyoxyethylene copolymer (PEG-PPG-PEG, P123) to the mixed solution of 0.25g deionized water and 1.0g absolute ethanol, and stir vigorously for 15 minutes until a transparent mixed liquid forms. Stir speed At 800rad/min, add 0.04g zinc acetate and 0.020g hexamethylenetetramine in sequence to the transparent liquid, stir vigorously for 35 minutes and then add the ethylene glycol solution. The mass of the ethylene glycol solution is 100 the mass of absolute ethanol. times, stir for 30 minutes until a clear solution is formed, and stand for eight days. The stand-still aging temperature is 30°C. Place the reaction kettle in an oven and heat it at 120 degrees for 12 hours. The white product obtained by the reaction was washed twice with ethanol and twice with deionized water at a rotation speed of 7000 r/min, and dried before use.
实施例4Example 4
将0.1g聚氧丙烯聚氧乙烯共聚物(PEG-PPG-PEG,P123)加入到0.20g去离子水和1.5g无水乙醇的混合溶液中，剧烈搅拌18min直至形成透明的混合液体，搅拌速度为600rad/min，向透明的液体中依次加入0.041g醋酸锌和0.021g的六次甲基四胺，剧烈搅拌30min后加入乙二醇溶液，乙二醇溶液的质量是无水乙醇的质量100倍，搅拌30min直至形成澄清溶液，静置陈化八天，静置陈化温度为20℃；将反应釜放在烘箱中110度加热18h。将反应得到的白色产物在7000r/min的转速下用乙醇清洗2次，用去离子水清洗2次，干燥后待用。Add 0.1g polyoxypropylene polyoxyethylene copolymer (PEG-PPG-PEG, P123) to the mixed solution of 0.20g deionized water and 1.5g absolute ethanol, stir vigorously for 18 minutes until a transparent mixed liquid is formed, stirring speed At 600rad/min, add 0.041g zinc acetate and 0.021g hexamethylenetetramine in sequence to the transparent liquid. Stir vigorously for 30 minutes and then add the ethylene glycol solution. The mass of the ethylene glycol solution is 100 the mass of absolute ethanol. times, stir for 30 minutes until a clear solution is formed, and stand for eight days. The stand-still aging temperature is 20°C; place the reaction kettle in an oven and heat it at 110 degrees for 18 hours. The white product obtained by the reaction was washed twice with ethanol and twice with deionized water at a rotation speed of 7000 r/min, and dried before use.
实施例5Example 5
将0.12g聚氧丙烯聚氧乙烯共聚物(PEG-PPG-PEG,P123)加入到0.28g去离子水和1.5g无水乙醇的混合溶液中，剧烈搅拌16min直至形成透明的混合液体，搅拌速度为900rad/min；向透明的液体中依次加入0.057g醋酸锌和0.028g的六次甲基四胺，剧烈搅拌40min后加入乙二醇溶液，乙二醇溶液的质量是无水乙醇的质量100倍，搅拌30min直至形成澄清溶液，静置陈化一周，静置陈化温度为25℃；将反应釜放在烘箱中120度加热15h。将反应得到的白色产物在8000r/min的转速下用乙醇清洗2次，用去离子水清洗2次，干燥后待用。Add 0.12g polyoxypropylene polyoxyethylene copolymer (PEG-PPG-PEG, P123) to the mixed solution of 0.28g deionized water and 1.5g absolute ethanol, and stir vigorously for 16 minutes until a transparent mixed liquid is formed. Stir speed It is 900rad/min; add 0.057g zinc acetate and 0.028g hexamethylenetetramine in sequence to the transparent liquid, stir vigorously for 40 minutes and then add the ethylene glycol solution. The mass of the ethylene glycol solution is the mass of absolute ethanol 100 times, stir for 30 minutes until a clear solution is formed, let it stand for one week, and the stand and aging temperature is 25°C; place the reaction kettle in an oven and heat it at 120 degrees for 15 hours. The white product obtained by the reaction was washed twice with ethanol and twice with deionized water at a rotation speed of 8000 r/min, and dried before use.
表面活性剂与Zn2+比值对ZnO形貌的影响，改变表面活性剂P123与Zn2+的比列，当P123与Zn2+的比例分别为(2:1)、(1:1)和(1:2)时，分别对其得到的氧化锌产物进行分析表征。将三种产物进行不同放大倍数的扫描电镜测试，得到的SEM图片如图10所示。The effect of the ratio of surfactant to Zn 2+ on the morphology of ZnO, changing the ratio of surfactant P123 to Zn 2+ , when the ratio of P123 to Zn 2+ is (2:1), (1:1) and (1:2), the zinc oxide products obtained were analyzed and characterized. The three products were subjected to scanning electron microscopy testing at different magnifications, and the obtained SEM pictures are shown in Figure 10.
图10为P123与Zn2+不同比例下ZnO形貌变化图，图10中(a,b)比值为2:1时的SEM图，(c,d)比值为1:1时的SEM图，(e,f)比值为1:2的SEM图。Figure 10 shows the morphology changes of ZnO at different ratios of P123 and Zn2+. In Figure 10 (a, b) are SEM images when the ratio is 2:1, (c, d) are SEM images when the ratio is 1:1, (e ,f) SEM image with a ratio of 1:2.
陈化温度对ZnO形貌的影响，将P123与Zn2+比值为2:1，混合均匀、颜色澄清的反应溶液放置在不同的温度下陈化一周，将得到的白色产物干燥表征，得到如图11所示的SEM图。The effect of aging temperature on the morphology of ZnO, the ratio of P123 to Zn2+ is 2:1, the reaction solution with uniform mixing and clear color is placed at different temperatures for one week, and the obtained white product is dried and characterized, as shown in Figure 11 SEM image shown.
图11为不同静置陈化温度下ZnO形貌的变化，图11中(a,b)温度为15℃，(c,d)温度为25℃，(e,f)温度为35℃，(g,h)温度为45℃。Figure 11 shows the changes in the morphology of ZnO under different static aging temperatures. In Figure 11 (a, b) the temperature is 15°C, (c, d) the temperature is 25°C, (e, f) the temperature is 35°C, ( g, h) The temperature is 45°C.
静置陈化时间对ZnO形貌的影响，将P123与Zn2+比值为2:1，混合均匀、颜色澄清的反应物溶液放置在25℃下静置陈化不同的时间，将得到的产物干燥进行表征分析，得到的SEM图片如图12所示。图12中不同静置陈化时间下的ZnO结构变化，(a-f)静置陈化时间分别为0,3,5,7,9,10天。The effect of static aging time on the morphology of ZnO. The ratio of P123 to Zn2+ is 2:1. The reactant solution with a uniform mix and clear color is placed at 25°C for different aging times. The resulting product is dried. Characterization analysis, the obtained SEM picture is shown in Figure 12. In Figure 12, the structural changes of ZnO under different static aging times, (a-f) static aging times are 0, 3, 5, 7, 9, and 10 days respectively.
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