CN104445366A - Method for synthesizing spindlelike ZnO nanomaterial by adopting microwave-assisted extraction process - Google Patents
Method for synthesizing spindlelike ZnO nanomaterial by adopting microwave-assisted extraction process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 47
- 238000000874 microwave-assisted extraction Methods 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 150000003751 zinc Chemical class 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 33
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- 239000000243 solution Substances 0.000 claims description 108
- 239000008367 deionised water Substances 0.000 claims description 45
- 229910021641 deionized water Inorganic materials 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 36
- 239000012266 salt solution Substances 0.000 claims description 24
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000012546 transfer Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 12
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- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- -1 compound zinc salt Chemical class 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 129
- 239000011787 zinc oxide Substances 0.000 description 66
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
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- 239000004312 hexamethylene tetramine Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
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Abstract
本发明的提供了一种微波萃取合成纺锤花状结构ZnO纳米材料的方法，其特征在于：该方法以摩尔配比为Zn(NO3)2·6H2O：Zn(CH3COO)2·2H2O＝1:1的复合锌盐作为初始原料，溶解后制得前躯体溶液；将前躯体溶液放入微波消解·萃取·合成工作站的微波反应室中制得纺锤花状结构的ZnO纳米材料。本发明的方法采用复合锌盐作为初始原料，才使得微波萃取合成的制备工艺能够应用到纺锤花状结构ZnO纳米材料的制备中来，才能合成出所需要的目标产物。本发明的方法采用微波萃取合成的制备工艺，反应在液相环境中一次完成，反应时间短，周期快，安全性好，不需要复杂的后期处理。
The present invention provides a microwave extraction method for synthesizing ZnO nanomaterials with spindle flower structure, which is characterized in that: the molar ratio of the method is Zn(NO 3 ) 2 ·6H 2 O:Zn(CH 3 COO)2· 2H 2 O = 1:1 compound zinc salt as the initial raw material, after dissolution, the precursor solution is obtained; the precursor solution is put into the microwave reaction chamber of the microwave digestion, extraction and synthesis workstation to obtain the ZnO nanometer with spindle flower structure. Material. The method of the present invention adopts the composite zinc salt as the initial raw material, so that the preparation process of microwave extraction synthesis can be applied to the preparation of ZnO nanometer material with spindle flower structure, and the desired target product can be synthesized. The method of the invention adopts the preparation technology of microwave extraction synthesis, the reaction is completed once in the liquid phase environment, the reaction time is short, the cycle is fast, the safety is good, and complicated post-treatment is not required.
Description
技术领域technical field
本发明属于材料制备领域，涉及自锚式悬索桥，具体涉及ZnO纳米材料，具体涉及一种微波萃取合成纺锤花状结构ZnO纳米材料的方法。The invention belongs to the field of material preparation, and relates to a self-anchored suspension bridge, in particular to a ZnO nanometer material, in particular to a method for synthesizing a spindle flower-shaped structure ZnO nanometer material by microwave extraction.
背景技术Background technique
氧化锌(ZnO)是一种新型的Ⅱ-Ⅵ族直接禁带半导体材料，具有较大的禁带宽度(3.37eV)和激子束缚能(60meV)，因其禁带宽度对应紫外光的波长，并具有击穿电压高、维持电场能力强、电子噪声小、可承受功率高等优点，因此氧化锌在蓝光激光器、发光二极管、显示器件以及太阳能电池等方面有着广泛的应用前景。作为一种非常有前景的半导体材料，氧化锌引起了全世界范围的研究兴趣。由于纳米材料的性能、应用与他们的形貌结构密切相关，氧化锌纳米材料的形貌控制一直是该材料研究领域的热点。迄今为止，在一定的反应条件下，已成功制备出ZnO纳米棒、纳米线、纳米球、纳米片、四针状纳米ZnO、树枝状纳米ZnO、菊花状纳米ZnO等许多具有特殊形貌的晶体。Zinc oxide (ZnO) is a new type of Ⅱ-Ⅵ direct bandgap semiconductor material, which has a large bandgap (3.37eV) and exciton binding energy (60meV), because its bandgap corresponds to the wavelength of ultraviolet light , and has the advantages of high breakdown voltage, strong ability to maintain electric field, low electronic noise, and high power withstand. Therefore, zinc oxide has broad application prospects in blue lasers, light-emitting diodes, display devices, and solar cells. As a very promising semiconductor material, ZnO has attracted worldwide research interest. Since the performance and application of nanomaterials are closely related to their morphology and structure, the morphology control of ZnO nanomaterials has always been a hot spot in the field of material research. So far, under certain reaction conditions, ZnO nanorods, nanowires, nanospheres, nanosheets, tetrapod nano-ZnO, dendritic nano-ZnO, chrysanthemum-shaped nano-ZnO and many other crystals with special morphology have been successfully prepared. .
近年来，制备纳米氧化锌的方法主要有分子束外延、金属有机化学气相沉积、激光沉积法、溅射法、热蒸发法、溶胶-凝胶法、水热/溶剂热法等方法。这些方法可主要归结为气相合成法和液相合成法，其中气相合成法的成本较高、可控性较差且需要精密的实验条件，不适合大规模生产；液相法中，虽然水热法成本低廉、操作简单、环保，但也存在制备周期长、安全性差的缺点。为了实现工业化大规模生产的目标，有必要开发生产成本低、操作简单、安全性好、制备周期短的纳米氧化锌的制备工艺。In recent years, the methods for preparing nano-zinc oxide mainly include molecular beam epitaxy, metal-organic chemical vapor deposition, laser deposition, sputtering, thermal evaporation, sol-gel method, hydrothermal/solvothermal method and other methods. These methods can be mainly attributed to gas-phase synthesis and liquid-phase synthesis. Among them, the cost of gas-phase synthesis is high, the controllability is poor, and precise experimental conditions are required, so it is not suitable for large-scale production; in the liquid-phase method, although hydrothermal The method is low in cost, simple in operation, and environmentally friendly, but it also has the disadvantages of long preparation period and poor safety. In order to achieve the goal of industrialized large-scale production, it is necessary to develop a nano-zinc oxide preparation process with low production cost, simple operation, good safety, and short preparation cycle.
近年来，关于ZnO纳米材料的制备及应用已经得到了广泛的研究。现有技术中已经采用了微波辅助水热法制备出了花状的ZnO纳米材料。该方法是将混合溶液在型号为GALANZ WD800(B123)的微波炉中用800W的功率辐射8min，再超声30min，之后自然冷却，过滤，烘干在130℃下5h.这种方法不能采用密闭的反应环境，因此容易造成样品的污染，以及造成环境的危害，且在微波炉中并没有控制反应温度，说明此种方法不容易控制反应温度。在微波辅助水热后需进行超声使样品分散看来，说明该实验方法制备的样品容易团聚在一起形成大块状。In recent years, the preparation and application of ZnO nanomaterials have been extensively studied. In the prior art, flower-shaped ZnO nanomaterials have been prepared by a microwave-assisted hydrothermal method. The method is to irradiate the mixed solution with 800W power for 8 minutes in a microwave oven modeled as GALANZ WD800 (B123), then sonicate for 30 minutes, then cool naturally, filter, and dry at 130°C for 5 hours. This method cannot use a closed reaction environment, so it is easy to cause sample contamination and environmental hazards, and the reaction temperature is not controlled in the microwave oven, indicating that this method is not easy to control the reaction temperature. After microwave-assisted hydrothermal heating, ultrasonic waves are needed to disperse the samples, which shows that the samples prepared by this experimental method are easy to agglomerate together to form large blocks.
发明内容Contents of the invention
针对现有技术存在的问题，本发明的目的在于，提供一种不需要后期处理、操作简单、安全性好、制备周期短的纺锤花状结构ZnO纳米材料的微波萃取合成的制备方法。Aiming at the problems existing in the prior art, the object of the present invention is to provide a preparation method of microwave extraction synthesis of ZnO nanomaterials with spindle flower structure that does not require post-processing, is simple to operate, has good safety, and has a short preparation period.
为了实现上述技术任务，本发明采用如下技术方案予以实现：In order to realize above-mentioned technical task, the present invention adopts following technical scheme to realize:
一种微波萃取合成纺锤花状结构ZnO纳米材料的方法，该方法以硝酸锌和醋酸锌的复合锌盐作为初始原料，溶解后制得前躯体溶液；将前躯体溶液放入密封的微波反应室中微波加热制得纺锤花状结构的ZnO纳米材料。A method for microwave extraction and synthesis of ZnO nanomaterials with a spindle-like structure, the method uses a composite zinc salt of zinc nitrate and zinc acetate as an initial raw material, and dissolves to obtain a precursor solution; the precursor solution is put into a sealed microwave reaction chamber ZnO nanomaterials with spindle flower structure were prepared by medium microwave heating.
其中，所述的前躯体溶液中的复合锌盐的摩尔配比为：硝酸锌：醋酸锌＝(1～2):1。Wherein, the molar ratio of the composite zinc salt in the precursor solution is: zinc nitrate: zinc acetate=(1-2):1.
具体地，该方法按照以下步骤进行：Specifically, the method is carried out according to the following steps:
步骤一，按照摩尔配比为硝酸锌：醋酸锌＝(1～2):1配置复合锌盐，溶于去离子水中，在室温下持续搅拌均匀配制成复合锌盐溶液；Step 1, configure zinc nitrate according to the molar ratio: zinc acetate=(1～2):1 to configure a composite zinc salt, dissolve it in deionized water, and continuously stir at room temperature to prepare a composite zinc salt solution;
步骤二，将C6H12N4溶于去离子水支撑溶液，在搅拌的过程中将C6H12N4溶液缓慢滴入复合锌盐溶液中；Step 2, dissolving C 6 H 12 N 4 in the deionized water supporting solution, and slowly dropping the C 6 H 12 N 4 solution into the composite zinc salt solution during stirring;
步骤三，调节溶液的pH＝10～12，得到均匀稳定的前躯体溶液；Step 3, adjusting the pH of the solution to 10-12 to obtain a uniform and stable precursor solution;
步骤四，制备的前躯体溶液转移至微波反应室中，然后将微波反应室密封，使温度控制在100℃～160℃，保温15min～30min后冷却至室温；Step 4, transfer the prepared precursor solution to the microwave reaction chamber, then seal the microwave reaction chamber, control the temperature at 100°C to 160°C, keep it warm for 15min to 30min, and then cool to room temperature;
步骤五，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，烘干过滤后的产物，得到纺锤花状结构的ZnO纳米材料。In step five, the reaction product is repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate is 7, and the filtered product is dried to obtain a ZnO nanomaterial with a spindle flower structure.
为了制备目标产物，上述方法合适的条件如下In order to prepare the target product, the suitable conditions of the above method are as follows
所述的前躯体溶液中Zn2+浓度为0.01mol/L～0.05mol/L。The concentration of Zn 2+ in the precursor solution is 0.01mol/L-0.05mol/L.
所述的前躯体溶液中的摩尔比为C6H12N4：Zn2+＝(0～1.0)：1。The molar ratio in the precursor solution is C 6 H 12 N 4 :Zn 2+ =(0˜1.0):1.
所述的前躯体溶液在密封的微波反应室中的填充率为50％，该填充率下加热后的压力才能制备出本申请的目标化合物,在微波消解·萃取·合成工作站中实现上述密封加热加压。The filling rate of the precursor solution in the sealed microwave reaction chamber is 50%, and the pressure after heating under this filling rate can prepare the target compound of the application, and the above-mentioned sealed heating can be realized in the microwave digestion, extraction and synthesis workstation Pressurize.
步骤三中用氨水调节溶液的pH＝10～12，得到均匀稳定的前躯体溶液。In step 3, ammonia water is used to adjust the pH of the solution to 10-12 to obtain a uniform and stable precursor solution.
一个优选的例子，上述方法按照以下步骤进行：A preferred example, the above method is carried out according to the following steps:
步骤一，按照摩尔配比为硝酸锌：醋酸锌＝4:3配置复合锌盐，溶于去离子水中，在室温下持续搅拌均匀配制成复合锌盐溶液；Step 1, according to the molar ratio, zinc nitrate: zinc acetate = 4:3 to configure a composite zinc salt, dissolved in deionized water, and continuously stirred at room temperature to prepare a composite zinc salt solution;
步骤二，将C6H12N4溶于去离子水支撑溶液，在搅拌的过程中将C6H12N4溶液缓慢滴入复合锌盐溶液中，使得前躯体溶液中的摩尔比为C6H12N4：Zn2+＝0.5：1；Step 2, dissolving C 6 H 12 N 4 in the deionized water support solution, slowly dripping the C 6 H 12 N 4 solution into the complex zinc salt solution during stirring, so that the molar ratio in the precursor solution is C 6 H 12 N 4 :Zn 2+ =0.5:1;
步骤三，用氨水调节溶液的pH＝12，得到均匀稳定的前躯体溶液；Step 3, adjusting the pH of the solution to 12 with ammonia water to obtain a uniform and stable precursor solution;
步骤四，制备的前躯体溶液转移至微波反应室中，然后将微波反应室密封，放入微波消解·萃取·合成工作站中，使温度控制在100℃，保温30min后冷却至室温；Step 4, transfer the prepared precursor solution to the microwave reaction chamber, then seal the microwave reaction chamber, put it into the microwave digestion·extraction·synthesis workstation, control the temperature at 100°C, keep it warm for 30min, and then cool to room temperature;
步骤五，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，烘干过滤后的产物，得到纺锤花状结构的ZnO纳米材料。In step five, the reaction product is repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate is 7, and the filtered product is dried to obtain a ZnO nanomaterial with a spindle flower structure.
另一个优选的例子，上述方法按照以下步骤进行：Another preferred example, the above method is carried out according to the following steps:
步骤一，按照摩尔配比为硝酸锌：醋酸锌＝1:1配置复合锌盐，溶于去离子水中，在室温下持续搅拌均匀配制成复合锌盐溶液；Step 1, according to the molar ratio of zinc nitrate: zinc acetate = 1:1 to configure a composite zinc salt, dissolved in deionized water, and continuously stirred at room temperature to prepare a composite zinc salt solution;
步骤二，将C6H12N4溶于去离子水支撑溶液，在搅拌的过程中将C6H12N4溶液缓慢滴入复合锌盐溶液中，使得前躯体溶液中的摩尔比为C6H12N4：Zn2+＝0.5：1；Step 2, dissolving C 6 H 12 N 4 in the deionized water support solution, slowly dripping the C 6 H 12 N 4 solution into the complex zinc salt solution during stirring, so that the molar ratio in the precursor solution is C 6 H 12 N 4 :Zn 2+ =0.5:1;
步骤三，用氨水调节溶液的pH＝11，得到均匀稳定的前躯体溶液；Step 3, adjusting the pH of the solution to 11 with ammonia water to obtain a uniform and stable precursor solution;
步骤四，制备的前躯体溶液转移至微波反应室中，然后将微波反应室密封，放入微波消解·萃取·合成工作站中，使温度控制在160℃，保温15min后冷却至室温；Step 4, transfer the prepared precursor solution to the microwave reaction chamber, then seal the microwave reaction chamber, put it into the microwave digestion·extraction·synthesis workstation, control the temperature at 160°C, keep it warm for 15min and then cool to room temperature;
步骤五，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，烘干过滤后的产物，得到纺锤花状结构的ZnO纳米材料。In step five, the reaction product is repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate is 7, and the filtered product is dried to obtain a ZnO nanomaterial with a spindle flower structure.
上述方法中，目标产物所述的纺锤花状结构的ZnO纳米材料单晶的直径约为100～1200nm，长度约为1～5μm。In the above method, the diameter of the ZnO nanomaterial single crystal with spindle flower structure described in the target product is about 100-1200 nm, and the length is about 1-5 μm.
本发明的方法与现有的方法相比，具有如下有益技术效果：Compared with existing methods, the method of the present invention has the following beneficial technical effects:
本发明的方法采用复合锌盐作为初始原料，才使得微波萃取合成的制备工艺能够应用到纺锤花状结构ZnO纳米材料的制备中来，才能合成出所需要的目标产物。本发明的方法采用微波萃取合成的制备工艺，反应在液相环境中一次完成，反应时间短，周期快，安全性好，不需要复杂的后期处理。The method of the present invention adopts the composite zinc salt as the initial raw material, so that the preparation process of microwave extraction synthesis can be applied to the preparation of ZnO nanometer material with spindle flower structure, and the desired target product can be synthesized. The method of the invention adopts the preparation technology of microwave extraction synthesis, the reaction is completed once in the liquid phase environment, the reaction time is short, the cycle is fast, the safety is good, and complicated post-treatment is not required.
附图说明Description of drawings
图1是本发明实施例1、实施例2、实施例3的X射线衍射图谱。Fig. 1 is the X-ray diffraction pattern of embodiment 1, embodiment 2, embodiment 3 of the present invention.
图2是本发明为实施例1所制备的花状结构ZnO纳米材料的典型正面扫描电子显微镜照片。FIG. 2 is a typical front scanning electron micrograph of the flower-like structure ZnO nanomaterial prepared in Example 1 of the present invention.
图3本发明为实施例2所制备的花状结构ZnO纳米材料的典型正面扫描电子显微镜照片。FIG. 3 is a typical front scanning electron micrograph of the flower-like structure ZnO nanomaterial prepared in Example 2 of the present invention.
图4本发明为实施例3所制备的花状结构ZnO纳米材料的典型正面扫描电子显微镜照片。FIG. 4 is a typical front scanning electron micrograph of the flower-like structure ZnO nanomaterial prepared in Example 3 of the present invention.
图5是本发明为实施例4所制备的花状结构ZnO纳米材料的典型正面扫描电子显微镜照片。FIG. 5 is a typical front scanning electron micrograph of the flower-like structure ZnO nanomaterial prepared in Example 4 of the present invention.
图6本发明为实施例5所制备的花状结构ZnO纳米材料的典型正面扫描电子显微镜照片。FIG. 6 is a typical front scanning electron micrograph of the flower-like structure ZnO nanomaterial prepared in Example 5 of the present invention.
图7本发明为实施例6所制备的花状结构ZnO纳米材料的典型正面扫描电子显微镜照片。FIG. 7 is a typical front scanning electron micrograph of the flower-like structure ZnO nanomaterial prepared in Example 6 of the present invention.
图8为对比例1得到的ZnO纳米材料典型正面扫描电子显微镜照片。FIG. 8 is a typical front scanning electron micrograph of the ZnO nanomaterial obtained in Comparative Example 1.
图9为对比例2得到的ZnO纳米材料典型正面扫描电子显微镜照片。FIG. 9 is a typical front scanning electron micrograph of the ZnO nanomaterial obtained in Comparative Example 2.
图10为对比例3得到的ZnO纳米材料典型正面扫描电子显微镜照片。FIG. 10 is a typical front scanning electron micrograph of the ZnO nanomaterial obtained in Comparative Example 3.
图11为对比例4得到的ZnO纳米材料典型正面扫描电子显微镜照片。FIG. 11 is a typical front scanning electron micrograph of the ZnO nanomaterial obtained in Comparative Example 4.
图12为对比例5得到的ZnO纳米材料典型正面扫描电子显微镜照片。FIG. 12 is a typical front scanning electron micrograph of the ZnO nanomaterial obtained in Comparative Example 5.
以下结合附图和实施例对本发明的具体内容作进一步详细地说明。The specific content of the present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments.
具体实施方式Detailed ways
本申请中的微波消解·萃取·合成工作站采用MDS-10型微波消解·萃取·合成工作站。微波萃取合成方法指的是用微波作为对反应物的加热源，属于液相反应法的范畴。微波是频率在300MHz～300GHz之间的电磁波，具有波长短、频率高和穿透性强的优点，因微波的能量可以直接传递给分子，不必加热所有材料，而使得微波反应体系具有以下优点：加热速度快、受热均匀且无温度梯度，克服了水热法的反应容器受热不均匀的缺点；反应简单灵敏、节能高效，克服了水热法制备周期长的缺点；温度可控性好，并且操作简单、安全性好、反应体系密封而无污染，适合大规模生产。The microwave digestion, extraction and synthesis workstation in this application adopts the MDS-10 microwave digestion, extraction and synthesis workstation. The microwave extraction synthesis method refers to the use of microwaves as a heating source for the reactants, which belongs to the category of liquid phase reaction methods. Microwave is an electromagnetic wave with a frequency between 300MHz and 300GHz. It has the advantages of short wavelength, high frequency and strong penetration. Because the energy of microwave can be directly transmitted to molecules, it is not necessary to heat all materials, so the microwave reaction system has the following advantages: The heating speed is fast, the heating is uniform and there is no temperature gradient, which overcomes the disadvantage of uneven heating of the reaction vessel of the hydrothermal method; the reaction is simple and sensitive, energy-saving and efficient, and overcomes the disadvantage of the long preparation period of the hydrothermal method; the temperature controllability is good, and The operation is simple, the safety is good, the reaction system is sealed without pollution, and it is suitable for large-scale production.
为了制备本申请的目标化合物纺锤花状结构ZnO纳米材料，本申请的发明人做了大量实验，在前期工作中，将微波萃取合成方法引入，并不能够制得到理想的锤花状结构ZnO纳米材料目标产物，后期经过大量探索性实验，最终才确定了本申请的两种锌盐在本申请的特定配比下作为复合锌盐，才能够制备得到所需要的目标产物。In order to prepare the target compound of the present application, the spindle flower-like structure ZnO nanomaterial, the inventor of the present application has done a lot of experiments. In the previous work, the microwave extraction synthesis method was introduced, and the ideal hammer flower-like structure ZnO nanometer material could not be obtained. The target product of the material, after a lot of exploratory experiments in the later stage, finally determined that the two zinc salts of the present application can be used as the composite zinc salt under the specific ratio of the present application, and the desired target product can be prepared.
本发明的纺锤花状结构ZnO纳米材料的形成机理是：ZnO晶体的形成包括成核和生长两过程，将氨水滴加到混合前驱体溶液中形成大量的络合离子Zn(NH3)4 2+。Zn(NH3)4 2+是ZnO晶体生长的基元。在微波萃取合成初期，生长基元Zn(NH3)4 2+首先形成能调整核子几何配置状态的多个核子多孪生中心核，温度维持在90℃时,当过饱和度超过临界值时，多孪晶ZnO核中的单核子迅速长大且沿着c-axis择优取向生长。随后,当温度达到升高时，极性和非极性表面更快长大。一般来说,越快速的增长的面,越快的消失。正如我们所知,ZnO晶体的(0001)方向的最大增长率。因此,ZnO极性面快速消失在微波萃取合成过程中,导致ZnO晶体沿(0001)c-axis方向生长结束。因此,纺锤花状的ZnO纳米材料生成。The formation mechanism of the spindle-like structure ZnO nanomaterial of the present invention is: the formation of ZnO crystals includes two processes of nucleation and growth, ammonia water is added dropwise to the mixed precursor solution to form a large amount of complex ions Zn(NH 3 ) 4 2 + . Zn(NH 3 ) 4 2+ is the basic unit of ZnO crystal growth. In the initial stage of microwave extraction synthesis, the growth unit Zn(NH 3 ) 4 2+ first forms multiple nucleon multi-twin center nuclei that can adjust the geometric configuration of nucleons. When the temperature is maintained at 90 ° C, when the supersaturation exceeds the critical value, The single nucleon in the multi-twinned ZnO core grows rapidly and grows along the c-axis preferred orientation. Subsequently, the polar and non-polar surfaces grew faster when the temperature was increased. Generally speaking, the faster the growing surface, the faster the disappearing. As we know, the (0001) direction of ZnO crystals has the largest growth rate. Therefore, the polar face of ZnO rapidly disappeared during the microwave extraction synthesis process, resulting in the end of the ZnO crystal growth along the (0001)c-axis direction. Therefore, spindle-shaped ZnO nanomaterials were generated.
遵从上述技术方案，以下给出本发明的具体实施例，需要说明的是本发明并不局限于以下具体实施例，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。Comply with above-mentioned technical solution, the specific embodiment of the present invention is given below, it should be noted that the present invention is not limited to following specific embodiment, all equivalent transformations done on the basis of the technical solution of the present application all fall within the scope of protection of the present invention .
实施例1：Example 1:
本实施例给出一种微波萃取合成纺锤花状结构ZnO纳米材料的方法，具体按照以下步骤进行：This embodiment provides a method for microwave extraction and synthesis of ZnO nanomaterials with a spindle flower-like structure, specifically according to the following steps:
步骤一，按摩尔比2:1称取0.3564g的六水合硝酸锌和0.1317g的二水合醋酸锌，将两种锌源混合置于烧杯A中，并用60ml去离子水溶解，形成Zn2+浓度为0.03mol/L的透明溶液；Step 1: Weigh 0.3564g of zinc nitrate hexahydrate and 0.1317g of zinc acetate dihydrate at a molar ratio of 2:1, mix the two zinc sources into beaker A, and dissolve them with 60ml of deionized water to form Zn 2+ A transparent solution with a concentration of 0.03mol/L;
步骤二，本实施例中不加入C6H12N4溶液；Step 2, no C 6 H 12 N 4 solution was added in this embodiment;
步骤三，将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，并用含量为25％～28％的氨水调节溶液的pH＝10，得到均匀稳定的前躯体溶液；Step 3: Stir the mixed zinc salt solution in the beaker A at a constant speed at room temperature, and adjust the pH of the solution to 10 with ammonia water with a content of 25% to 28%, to obtain a uniform and stable precursor solution;
步骤四，用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在120℃下反应20min；Step 4: Use a graduated cylinder to weigh 50ml of the precursor solution and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 type microwave digestion, extraction and synthesis In the workstation, select the temperature control mode and react at 120°C for 20 minutes;
步骤五，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物。Step 5, the reaction product was repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate was 7, and the filtered product was dried in an electric blast drying oven at 60°C.
最后采用XRD和SEM对产物的形态和结构进行表征，表征结果如图1和图2所示，从图1中可以看出，样品均为六方纤锌矿结构的ZnO，即纺锤花装ZnO。从图2可以看出，所制备的花状结构ZnO纳米材料形态均一、分布均匀，锥状纳米单晶的直径约为200～500nm，长度约为1～2μm。Finally, XRD and SEM were used to characterize the morphology and structure of the product. The characterization results are shown in Figure 1 and Figure 2. It can be seen from Figure 1 that the samples are all ZnO with a hexagonal wurtzite structure, that is, ZnO with spindle flowers. It can be seen from Figure 2 that the prepared ZnO nanomaterials with flower-like structure are uniform in shape and evenly distributed, the diameter of the cone-shaped nano single crystal is about 200-500 nm, and the length is about 1-2 μm.
实施例2：Example 2:
本实施例给出一种微波萃取合成纺锤花状结构ZnO纳米材料的方法，具体按照以下步骤进行：This embodiment provides a method for microwave extraction and synthesis of ZnO nanomaterials with a spindle flower-like structure, specifically according to the following steps:
步骤一，按摩尔比1:1称取0.0891g的六水合硝酸锌和0.0659g的二水合醋酸锌，将两种锌源混合置于烧杯A中，并用20ml去离子水溶解，形成透明溶液；Step 1, weigh 0.0891g of zinc nitrate hexahydrate and 0.0659g of zinc acetate dihydrate at a molar ratio of 1:1, mix the two zinc sources into beaker A, and dissolve them with 20ml of deionized water to form a transparent solution;
步骤二，称取0.084g的六次甲基四胺置于烧杯B中，用20ml去离子水溶解，形成透明溶液；Step 2, weigh 0.084g of hexamethylenetetramine and place it in beaker B, dissolve it with 20ml of deionized water to form a transparent solution;
将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，将烧杯B中六次甲基四胺溶液缓慢滴入烧杯A中，两次分别用10ml的去离子水洗涤烧杯B,并将洗涤液缓慢滴入烧杯A中，配置成的均匀稳定混合的溶液的成Zn2+浓度为0.01mol/L，C6H12N4的浓度为0.01mol/L，其中摩尔比为C6H12N4：Zn2+＝1：1；Stir the zinc salt solution mixed in beaker A at a constant speed at room temperature, slowly drop the hexamethylenetetramine solution in beaker B into beaker A, wash beaker B with 10ml of deionized water twice, and wash the washing liquid Slowly drop it into beaker A, the concentration of Zn 2+ and C 6 H 12 N 4 in the uniform and stable mixed solution is 0.01 mol/L, and the concentration of C 6 H 12 N 4 is 0.01 mol/L, and the molar ratio is C 6 H 12 N 4 : Zn 2+ =1:1;
步骤三，将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，并用含量为25％～28％的氨水调节溶液的pH＝11，得到均匀稳定的前躯体溶液；Step 3: Stir the mixed zinc salt solution in the beaker A at a constant speed at room temperature, and adjust the pH of the solution to 11 with ammonia water with a content of 25% to 28%, to obtain a uniform and stable precursor solution;
步骤四，用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在160℃下反应15min；Step 4: Use a graduated cylinder to weigh 50ml of the precursor solution and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 type microwave digestion, extraction and synthesis In the workstation, select the temperature control mode and react at 160°C for 15 minutes;
步骤五，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物。Step 5, the reaction product was repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate was 7, and the filtered product was dried in an electric blast drying oven at 60°C.
最后采用XRD和SEM对产物的形态和结构进行表征，表征结果如图1和图3所示，从图1中可以看出，样品均为六方纤锌矿结构的ZnO，即纺锤花装ZnO。从图3可以看出，所制备的花状结构ZnO纳米材料形态均一、分布均匀，锥状纳米单晶的直径约为200～1000nm，长度约为1～2μm。Finally, XRD and SEM were used to characterize the morphology and structure of the product. The characterization results are shown in Figure 1 and Figure 3. It can be seen from Figure 1 that the samples are all ZnO with a hexagonal wurtzite structure, that is, ZnO with spindle flowers. It can be seen from Fig. 3 that the prepared ZnO nanomaterials with flower-like structure are uniform in shape and evenly distributed, the diameter of the cone-shaped nano single crystal is about 200-1000 nm, and the length is about 1-2 μm.
实施例3：Example 3:
本实施例给出一种微波萃取合成纺锤花状结构ZnO纳米材料的方法，具体按照以下步骤进行：This embodiment provides a method for microwave extraction and synthesis of ZnO nanomaterials with a spindle flower-like structure, specifically according to the following steps:
步骤一，按摩尔比4:3称取0.5091g的六水合硝酸锌和0.2822g的二水合醋酸锌，将两种锌源混合置于烧杯A中，并用20ml去离子水溶解，形成透明溶液；Step 1, weigh 0.5091g of zinc nitrate hexahydrate and 0.2822g of zinc acetate dihydrate at a molar ratio of 4:3, mix the two sources of zinc into beaker A, and dissolve them with 20ml of deionized water to form a transparent solution;
步骤二，称取0.21g的六次甲基四胺置于烧杯B中，用20ml去离子水溶解，形成透明溶液；Step 2, weigh 0.21g of hexamethylenetetramine and place it in beaker B, dissolve it with 20ml of deionized water to form a transparent solution;
将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，将烧杯B中六次甲基四胺溶液缓慢滴入烧杯A中，两次分别用10ml的去离子水洗涤烧杯B,并将洗涤液缓慢滴入烧杯A中，配置成的均匀稳定混合的溶液的成Zn2+浓度为0.05mol/L，C6H12N4的浓度为0.025mol/L，其中摩尔比为C6H12N4：Zn2+＝0.5：1；Stir the zinc salt solution mixed in beaker A at a constant speed at room temperature, slowly drop the hexamethylenetetramine solution in beaker B into beaker A, wash beaker B with 10ml of deionized water twice, and wash the washing liquid Slowly drop it into beaker A, the concentration of Zn 2+ and C 6 H 12 N 4 in the uniform and stable mixed solution is 0.05mol/L and 0.025mol/L, and the molar ratio is C 6 H 12 N 4 : Zn 2+ =0.5:1;
步骤三，将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，并用含量(即质量分数)为25％～28％的氨水调节溶液的pH＝12，得到均匀稳定的前躯体溶液；Step 3: Stir the mixed zinc salt solution in the beaker A at a constant speed at room temperature, and adjust the pH of the solution to 12 with ammonia water with a content (ie mass fraction) of 25% to 28%, to obtain a uniform and stable precursor solution;
步骤四，用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在100℃下反应30min；Step 4: Use a graduated cylinder to weigh 50ml of the precursor solution and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 type microwave digestion, extraction and synthesis In the workstation, select the temperature control mode and react at 100°C for 30 minutes;
步骤五，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物。Step 5, the reaction product was repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate was 7, and the filtered product was dried in an electric blast drying oven at 60°C.
最后采用XRD和SEM对产物的形态和结构进行表征，表征结果如图1和图4所示，从图1中可以看出，样品均为六方纤锌矿结构的ZnO，即纺锤花装ZnO。从图4可以看出，所制备的花状结构ZnO纳米材料形态均一、分布均匀，锥状纳米单晶的直径约为200～1000nm，长度约为2～4μm。Finally, the morphology and structure of the product were characterized by XRD and SEM. The characterization results are shown in Figure 1 and Figure 4. It can be seen from Figure 1 that the samples are all ZnO with hexagonal wurtzite structure, that is, ZnO with spindle flower. It can be seen from Figure 4 that the prepared ZnO nanomaterials with flower-like structure are uniform in shape and evenly distributed, the diameter of the cone-shaped nano single crystal is about 200-1000 nm, and the length is about 2-4 μm.
实施例4：Example 4:
本实施例的制备过程与实施例1相似,区别之处在于，按摩尔比1:1称取0.2677g的六水合硝酸锌和0.1976g的二水合醋酸锌，将两种锌源混合置于烧杯A中，并用60ml去离子水溶解，形成Zn2+浓度为0.03mol/L的透明溶液；最后采用SEM对产物的形态进行表征，表征结果图5所示：从图5可以看出，所制备的花状结构ZnO纳米材料形态均一、分布均匀，锥状纳米单晶的直径约为200～700nm，长度约为1～3μm。The preparation process of this example is similar to that of Example 1, the difference is that 0.2677g of zinc nitrate hexahydrate and 0.1976g of zinc acetate dihydrate are weighed at a molar ratio of 1:1, and the two zinc sources are mixed and placed in a beaker A, and dissolved with 60ml deionized water to form a transparent solution with a Zn concentration of 0.03mol/L; finally use SEM to characterize the morphology of the product, and the characterization results are shown in Figure 5: as can be seen from Figure 5, the prepared The flower-like structure ZnO nanomaterials are uniform in shape and evenly distributed, the diameter of the cone-shaped nano single crystal is about 200-700nm, and the length is about 1-3μm.
实施例5：Example 5:
本实施例的制备过程与实施例2相似，区别之处在于，称取0.042g的六次甲基四胺，配置成的均匀稳定混合的溶液的成Zn2+浓度为0.01mol/L，C6H12N4的浓度为0.005mol/L，其中摩尔比为C6H12N4：Zn2+＝0.5：1；最后采用SEM对产物的形态进行表征，表征结果图6所示：从图6可以看出，所制备的花状结构ZnO纳米材料形态均一、分布均匀，锥状纳米单晶的直径约为400～1200nm，长度约为1～4μm。The preparation process of this embodiment is similar to that of Example 2, the difference is that, the hexamethylenetetramine of 0.042g is weighed, and the Zn concentration of the uniformly and stably mixed solution configured is 0.01mol/L, C The concentration of 6 H 12 N 4 is 0.005 mol/L, and the molar ratio is C 6 H 12 N 4 : Zn 2+ =0.5:1; finally, SEM is used to characterize the morphology of the product, and the characterization results are shown in Figure 6: from It can be seen from Fig. 6 that the prepared ZnO nanomaterials with flower-like structure are uniform in shape and evenly distributed, the diameter of the cone-shaped nano single crystal is about 400-1200 nm, and the length is about 1-4 μm.
实施例6：Embodiment 6:
本实施例制备过程与实施例3相似，区别之处在于，按摩尔比1：1称取4455g的六水合硝酸锌和0.3293g的二水合醋酸锌配置成Zn2+浓度为0.05mol/L的混合锌盐溶液；最后采用SEM对产物的形态进行表征，表征结果图7所示：从图7可以看出，所制备的花状结构ZnO纳米材料形态均一、分布均匀，锥状纳米单晶的直径约为100～1000nm，长度约为1～5μm。The preparation process of this example is similar to that of Example 3, the difference is that 4455g of zinc nitrate hexahydrate and 0.3293g of zinc acetate dihydrate were weighed at a molar ratio of 1:1 to form a Zn 2+ concentration of 0.05mol/L Mix the zinc salt solution; finally use SEM to characterize the morphology of the product, and the characterization results are shown in Figure 7: As can be seen from Figure 7, the prepared flower-like structure ZnO nanomaterials are uniform in shape and uniform in distribution, and the shape of the cone-shaped nano-single crystal The diameter is about 100-1000 nm, and the length is about 1-5 μm.
在确定本发明的工艺过程的试验中，锌盐的选择试验得到的产物形貌不符合本发明对产物的形貌要求，现抽取如下几个对比例进行说明。In the test for determining the technological process of the present invention, the morphology of the product obtained by the zinc salt selection test does not meet the requirements of the present invention for the morphology of the product, and the following comparative examples are now extracted for illustration.
对比例1：Comparative example 1:
1)称取0.1782g的六水合硝酸锌置于烧杯A中，并用60ml去离子水溶解，形成Zn2+浓度为0.01mol/L的透明溶液；1) Weigh 0.1782g of zinc nitrate hexahydrate and place it in beaker A, and dissolve it with 60ml of deionized water to form a transparent solution with a Zn concentration of 0.01mol/L;
2)将烧杯A中锌盐溶液在室温下持续匀速搅拌，并用含量为25％～28％的氨水调节溶液的pH＝11，得到均匀稳定的前躯体溶液；2) Stir the zinc salt solution in the beaker A at a constant speed at room temperature, and adjust the pH of the solution to 11 with ammonia water with a content of 25% to 28%, to obtain a uniform and stable precursor solution;
3)用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在160℃下反应20min；3) Weigh 50ml of the precursor solution with a measuring cylinder and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 microwave digestion, extraction and synthesis workstation , select the temperature control mode, and react at 160°C for 20 minutes;
4)将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物，最后采用SEM对产物的形态进行表征，如图8所示，所制备的ZnO纳米材料为有一定长径比的分散的ZnO纳米棒。4) Wash and filter the product obtained from the reaction repeatedly with deionized water and absolute ethanol until the pH of the filtrate = 7, dry the filtered product in an electric blast drying oven at 60°C, and finally use SEM to analyze the morphology of the product Characterization, as shown in Figure 8, the prepared ZnO nanomaterials are dispersed ZnO nanorods with a certain aspect ratio.
对比例2：Comparative example 2:
1)按摩尔比2:3称取0.0713g的六水合硝酸锌和0.0790g的二水合醋酸锌，将两种锌源混合置于烧杯A中,并用20ml去离子水溶解，形成透明溶液；1) Weigh 0.0713g of zinc nitrate hexahydrate and 0.0790g of zinc acetate dihydrate at a molar ratio of 2:3, mix the two zinc sources into beaker A, and dissolve them with 20ml of deionized water to form a transparent solution;
2)称取0.0840g的六次甲基四胺置于烧杯B中，分别用20ml去离子水溶解，形成透明溶液；2) Weigh 0.0840g of hexamethylenetetramine into beaker B, dissolve with 20ml of deionized water respectively to form a transparent solution;
3)将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，将烧杯B中六次甲基四胺溶液缓慢滴入烧杯A中，两次分别用10ml的去离子水洗涤烧杯B,并将洗涤液缓慢滴入烧杯A中，配置成的均匀稳定混合的溶液的成Zn2+浓度为0.01mol/L，C6H12N4的浓度为0.01mol/L，其中摩尔比为C6H12N4：Zn2+＝1：1；3) Mix the zinc salt solution in beaker A at room temperature and continue stirring at a constant speed, slowly drop the hexamethylenetetramine solution in beaker B into beaker A, wash beaker B with 10ml of deionized water twice, and The washing solution is slowly dropped into beaker A, and the uniform and stable mixed solution prepared has a Zn 2+ concentration of 0.01mol/L and a C 6 H 12 N 4 concentration of 0.01mol/L, wherein the molar ratio is C 6 H 12 N 4 :Zn 2+ =1:1;
4)将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，并用含量为25％～28％的氨水调节溶液的pH＝10，得到均匀稳定的前躯体溶液；4) Stir the zinc salt solution mixed in the beaker A at a constant speed at room temperature, and adjust the pH of the solution to 10 with ammonia water with a content of 25% to 28%, to obtain a uniform and stable precursor solution;
5)用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在160℃下反应20min；5) Weigh 50ml of the precursor solution with a measuring cylinder and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 microwave digestion, extraction and synthesis workstation , select the temperature control mode, and react at 160°C for 20 minutes;
6)将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物，最后采用SEM对产物的形态进行表征，如图9所示，所制备的ZnO纳米材料，有些为分散的ZnO纳米棒堆积结构，有些成短棒状花状结构。6) Wash and filter the reaction product repeatedly with deionized water and absolute ethanol until the pH of the filtrate = 7, dry the filtered product in an electric blast drying oven at 60°C, and finally use SEM to analyze the morphology of the product Characterization, as shown in Figure 9, some of the prepared ZnO nanomaterials have a dispersed ZnO nanorod stacking structure, and some have a short rod-like flower-like structure.
另外，在确定本发明的工艺参数过程的试验中，一些参数的选择试验得到的产物形貌不符合本发明对产物的形貌要求，现抽取如下几个对比例进行说明：In addition, in the test of determining the process parameter process of the present invention, the product appearance obtained by the selection test of some parameters does not meet the appearance requirements of the present invention for the product, and now the following comparative examples are taken for illustration:
对比例3：Comparative example 3:
1)按摩尔比1:1称取0.0891g的六水合硝酸锌和0.0659g的二水合醋酸锌，将两种锌源混合置于烧杯A中，并用60ml去离子水溶解，形成Zn2+浓度为0.01mol/L的透明溶液；1) Weigh 0.0891g of zinc nitrate hexahydrate and 0.0659g of zinc acetate dihydrate at a molar ratio of 1:1, mix the two zinc sources into beaker A, and dissolve them with 60ml of deionized water to form a Zn 2+ concentration 0.01mol/L transparent solution;
2)将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，并用含量为25％～28％的氨水调节溶液的pH＝9，得到均匀稳定的前躯体溶液；2) Stir the zinc salt solution mixed in the beaker A at a constant speed at room temperature, and adjust the pH of the solution to 9 with ammonia water with a content of 25% to 28%, to obtain a uniform and stable precursor solution;
3)用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在160℃下反应20min；3) Weigh 50ml of the precursor solution with a measuring cylinder and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 microwave digestion, extraction and synthesis workstation , select the temperature control mode, and react at 160°C for 20 minutes;
4)将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物，最后采用SEM对产物的形态进行表征，，如图10所示，所制备的ZnO纳米材料为形貌均匀、有一定长径比的分散的ZnO纳米棒。4) Wash and filter the product obtained from the reaction repeatedly with deionized water and absolute ethanol until the pH of the filtrate = 7, dry the filtered product in an electric blast drying oven at 60°C, and finally use SEM to analyze the morphology of the product Characterization, as shown in Figure 10, the prepared ZnO nanomaterials are dispersed ZnO nanorods with uniform morphology and a certain aspect ratio.
对比例4：Comparative example 4:
1)按摩尔比1:1称取0.5346g的六水合硝酸锌和0.3951g的二水合醋酸锌，将两种锌源混合置于烧杯A中，并用20ml去离子水溶解，形成透明溶液；1) Weigh 0.5346g of zinc nitrate hexahydrate and 0.3951g of zinc acetate dihydrate at a molar ratio of 1:1, mix the two zinc sources into beaker A, and dissolve them with 20ml of deionized water to form a transparent solution;
2)称取0.1680g的六次甲基四胺置于烧杯B中；并分别用20ml去离子水溶解，形成透明溶液；2) Weigh 0.1680g of hexamethylenetetramine and place it in beaker B; and dissolve it with 20ml of deionized water respectively to form a transparent solution;
3)将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，将烧杯B中六次甲基四胺溶液缓慢滴入烧杯A中，两次分别用10ml的去离子水洗涤烧杯B,并将洗涤液缓慢滴入烧杯A中，配置成的均匀稳定混合的溶液的成Zn2+浓度为0.06mol/L，C6H12N4的浓度为0.02mol/L，其中摩尔比为C6H12N4：Zn2+＝1：3；3) Mix the zinc salt solution in beaker A at room temperature and continue stirring at a constant speed, slowly drop the hexamethylenetetramine solution in beaker B into beaker A, wash beaker B with 10ml of deionized water twice, and The washing solution is slowly dropped into the beaker A, and the uniform and stable mixed solution prepared has a Zn 2+ concentration of 0.06mol/L and a C 6 H 12 N 4 concentration of 0.02mol/L, wherein the molar ratio is C 6 H 12 N 4 : Zn 2+ = 1: 3;
4)用含量为25％～28％的氨水调节步骤2)所得溶液的pH＝9，得到均匀稳定的前躯体溶液；4) adjusting the pH of the solution obtained in step 2) to 9 with ammonia water having a content of 25% to 28%, to obtain a uniform and stable precursor solution;
5)用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在160℃下反应15min；5) Weigh 50ml of the precursor solution with a measuring cylinder and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 microwave digestion, extraction and synthesis workstation , select the temperature control mode, and react at 160°C for 15 minutes;
6)将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物，最后采用SEM对产物的形态进行表征，，如图11所示，所制备的ZnO纳米材料为形貌均匀、有一定长径比的分散的ZnO纳米棒。6) Wash and filter the reaction product repeatedly with deionized water and absolute ethanol until the pH of the filtrate = 7, dry the filtered product in an electric blast drying oven at 60°C, and finally use SEM to analyze the morphology of the product Characterization, as shown in Figure 11, the prepared ZnO nanomaterials are dispersed ZnO nanorods with uniform morphology and a certain aspect ratio.
对比例5：Comparative example 5:
1)按摩尔比1:1称取0.4455g的六水合硝酸锌和0.3293g的二水合醋酸锌，将两种锌源混合置于烧杯A中，并用20ml去离子水溶解，形成透明溶液；1) Weigh 0.4455g of zinc nitrate hexahydrate and 0.3293g of zinc acetate dihydrate at a molar ratio of 1:1, mix the two zinc sources into beaker A, and dissolve them with 20ml of deionized water to form a transparent solution;
2)称取0.5040g的六次甲基四胺置于烧杯B中；并分别用20ml去离子水溶解，形成透明溶液；2) Weigh 0.5040g of hexamethylenetetramine and place it in beaker B; and dissolve it with 20ml of deionized water respectively to form a transparent solution;
3)将烧杯A中混合锌盐溶液在室温下持续匀速搅拌，将烧杯B中六次甲基四胺溶液缓慢滴入烧杯A中，两次分别用10ml的去离子水洗涤烧杯B,并将洗涤液缓慢滴入烧杯A中，配置成的均匀稳定混合的溶液的成Zn2+浓度为0.05mol/L，C6H12N4的浓度为0.06mol/L,其中摩尔比为C6H12N4：Zn2+＝1.2：1；3) Mix the zinc salt solution in beaker A at room temperature and continue stirring at a constant speed, slowly drop the hexamethylenetetramine solution in beaker B into beaker A, wash beaker B with 10ml of deionized water twice, and The washing solution is slowly dropped into beaker A, and the uniform and stable mixed solution prepared has a Zn 2+ concentration of 0.05 mol/L and a C 6 H 12 N 4 concentration of 0.06 mol/L, wherein the molar ratio is C 6 H 12 N 4 :Zn 2+ =1.2:1;
4)用含量为25％～28％的氨水调节步骤2)所得溶液的pH＝8，得到均匀稳定的前躯体溶液；4) adjusting the pH of the solution obtained in step 2) to 8 with ammonia water having a content of 25% to 28%, to obtain a uniform and stable precursor solution;
5)用量筒称取50ml前躯体溶液转移至微波反应室中并密封，其均匀稳定的混合前驱体溶液在反应釜的填充度为50％，放入MDS-10型微波消解·萃取·合成工作站中，选择温控模式，在160℃下反应25min；5) Weigh 50ml of the precursor solution with a measuring cylinder and transfer it to the microwave reaction chamber and seal it. The filling degree of the uniform and stable mixed precursor solution in the reaction kettle is 50%, and put it into the MDS-10 microwave digestion, extraction and synthesis workstation , select the temperature control mode, and react at 160°C for 25 minutes;
6)将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直至滤液pH＝7，在60℃的电热鼓风干燥箱中烘干过滤后的产物，最后采用SEM对产物的形态进行表征，，如图12所示，所制备的ZnO纳米材料为两头为尖锥状，中间成棒状的直径不均匀的分散的ZnO纳米棒。6) Wash and filter the reaction product repeatedly with deionized water and absolute ethanol until the pH of the filtrate = 7, dry the filtered product in an electric blast drying oven at 60°C, and finally use SEM to analyze the morphology of the product Characterization, as shown in FIG. 12 , the prepared ZnO nanomaterials are dispersed ZnO nanorods with pointed cones at both ends and rods in the middle.
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| CN114031107A (en) * | 2021-11-30 | 2022-02-11 | 华东理工大学 | A kind of zinc oxide with controllable morphology, preparation method and application thereof |
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