CN102134091A - Method for preparing micro structural zinc oxide by hydrothermal method - Google Patents
Method for preparing micro structural zinc oxide by hydrothermal method Download PDFInfo
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- CN102134091A CN102134091A CN 201110024679 CN201110024679A CN102134091A CN 102134091 A CN102134091 A CN 102134091A CN 201110024679 CN201110024679 CN 201110024679 CN 201110024679 A CN201110024679 A CN 201110024679A CN 102134091 A CN102134091 A CN 102134091A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 89
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 241000257465 Echinoidea Species 0.000 claims abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 132
- 239000012153 distilled water Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 230000007613 environmental effect Effects 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002063 nanoring Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
一种水热法制备微米结构氧化锌，以聚乙烯吡咯烷酮K-30为模板、二水醋酸锌为锌源、H2O2为氧化剂，通过控制反应物浓度、水热生长时间和反应温度制备成海胆状、锥状、六棱柱自组装实心球状和糖葫芦状四种微米结构的氧化锌材料。本发明具有方法简单、成本低、条件温和以及对环境无污染等优点。本发明制备的微米氧化锌材料纯度较高，晶体结构规整，材料形貌的可控性好，生产周期短，在燃料电池、光电转换材料以及化学传感器等方面有着巨大的应用前景。A hydrothermal method for preparing micron-structured zinc oxide, using polyvinylpyrrolidone K-30 as a template, zinc acetate dihydrate as a zinc source, and H2O2 as an oxidant, by controlling the concentration of reactants, hydrothermal growth time and reaction temperature . Zinc oxide materials with four micron structures in the shape of sea urchins, cones, hexagonal self-assembled solid spheres and candied haws. The invention has the advantages of simple method, low cost, mild conditions, no pollution to the environment and the like. The micron zinc oxide material prepared by the invention has high purity, regular crystal structure, good controllability of material appearance and short production cycle, and has great application prospects in fuel cells, photoelectric conversion materials, chemical sensors and the like.
Description
技术领域technical field
本发明属于半导体微米材料制备领域，具体涉及一种微米氧化锌材料的制备方法，特别涉及一种采用乳液辅助水热法制备四种特殊形貌氧化锌的方法。The invention belongs to the field of semiconductor micron material preparation, in particular to a method for preparing a micron zinc oxide material, in particular to a method for preparing zinc oxide with four special shapes by using an emulsion-assisted hydrothermal method.
背景技术Background technique
氧化锌是一种重要的宽禁带半导体材料，带宽可以达到3.37eV的纤锌矿晶体结构，具有优良的化学特性、热稳定性、光学性质和电学性质，可以在高密度下产生近紫外室温激子激光，因而在气体传感器、压电材料、催化剂、太阳能电池、生物医药等领域有着广泛的应用。氧化锌微米纳米结构单元的制备与组装及应用的研究异常活跃。由于氧化锌纳米材料在室温下具有高达60meV的激子束缚能，可用于制作短波长光电器件、如紫外激光器、高频滤波器、紫外光探测器和发光二极管等，制作发光器件可以获得更高的光增益，使氧化锌在大幅度提高光存储密度方面具有巨大的潜在应用价值。Zinc oxide is an important wide-bandgap semiconductor material with a wurtzite crystal structure whose bandwidth can reach 3.37eV. It has excellent chemical properties, thermal stability, optical properties and electrical properties, and can produce near-ultraviolet room temperature at high density. Exciton lasers are widely used in gas sensors, piezoelectric materials, catalysts, solar cells, biomedicine and other fields. The research on the preparation, assembly and application of zinc oxide micro-nano structural units is extremely active. Since zinc oxide nanomaterials have an exciton binding energy as high as 60meV at room temperature, they can be used to make short-wavelength optoelectronic devices, such as ultraviolet lasers, high-frequency filters, ultraviolet light detectors and light-emitting diodes, etc., making light-emitting devices can obtain higher The optical gain of ZnO has great potential application value in greatly improving the optical storage density.
目前已经制备出了氧化锌的纳米球、纳米线、纳米带、纳米片、纳米环、纳米棒等纳米结构。其涉及到的制备方法包括溶胶-凝胶法、水解法、反相乳液法、沉淀法、电化学沉积法和化学气相沉积(CVD)等。然而在微米氧化锌材料的制备过程中，普遍存在着过程繁琐、实验条件苛刻、反应温度高、重复性差、设备昂贵等缺点。因此，有关微米氧化锌材料的制备及其方法探究仍是目前人们关注的焦点。At present, zinc oxide nanospheres, nanowires, nanobelts, nanosheets, nanorings, nanorods and other nanostructures have been prepared. The preparation methods involved include sol-gel method, hydrolysis method, inverse emulsion method, precipitation method, electrochemical deposition method, chemical vapor deposition (CVD) and the like. However, in the preparation process of micron zinc oxide materials, there are generally disadvantages such as cumbersome process, harsh experimental conditions, high reaction temperature, poor repeatability, and expensive equipment. Therefore, the research on the preparation and method of micron zinc oxide materials is still the focus of attention.
发明内容Contents of the invention
本发明所要解决的技术问题在于克服上述制备方法的缺点，提供一种操作简单安全、成本低、反应条件温和易控且重复性高、产品形貌和尺寸可控、晶体结构规整、单分散性好的微米结构氧化锌的制备方法。The technical problem to be solved by the present invention is to overcome the shortcomings of the above-mentioned preparation methods, and provide a simple and safe operation, low cost, mild and easy-to-control reaction conditions and high repeatability, controllable product morphology and size, regular crystal structure, and monodispersity. Preparation method of fine microstructured zinc oxide.
解决上述技术问题所采用的技术方案是：将质量分数为30％的H2O2加入蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-30，室温搅拌10分钟，加入二水醋酸锌，室温搅拌20分钟，加入物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶0.3658～36.58∶8.333～166.7∶466.7～625∶0.1667～25，室温搅拌，待溶液产生白色浑浊后继续搅拌5分钟，将白色浑浊溶液倒入内衬为聚四氟乙烯的水热反应釜中，密封水热反应釜，将水热反应釜放入温度为80～200℃的烘箱中反应0.5～24小时，离心分离，沉淀依次用蒸馏水、无水乙醇交替洗涤3次，60℃真空干燥24小时，制备成微米结构氧化锌。The technical solution adopted to solve the above technical problems is: add H2O2 with a mass fraction of 30% into distilled water, stir at room temperature for 5 minutes, add polyvinylpyrrolidone K - 30, stir at room temperature for 10 minutes, add zinc acetate dihydrate, Stir at room temperature for 20 minutes, add a NaOH aqueous solution with a concentration of 5 mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H2O2 with a mass fraction of 30%, distilled water, and NaOH is 1: 0.3658～36.58: 8.333～166.7: 466.7～625: 0.1667～25, stir at room temperature, continue to stir for 5 minutes after the solution becomes white turbid, pour the white turbid solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, Seal the hydrothermal reaction kettle, put the hydrothermal reaction kettle into an oven with a temperature of 80-200°C to react for 0.5-24 hours, centrifuge, wash the precipitate with distilled water and absolute ethanol alternately for 3 times, and vacuum dry at 60°C for 24 hours , prepared into micron structure zinc oxide.
本发明方法中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶0.3658～10.98∶8.333～166.7∶466.7～625∶3.333～25，制备成微米海胆状氧化锌，从球的中心生长出许多氧化锌微米棒，海胆状球的直径为30～100μm，棒的长度为15～50μm、直径为0.3～2μm。其中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比最佳为1∶3.658∶41.67∶591.7∶6.667。In the method of the present invention, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H2O2 with a mass fraction of 30%, distilled water and NaOH is 1 : 0.3658-10.98: 8.333-166.7: 466.7-625: 3.333 ~25, prepared into micron sea urchin-shaped zinc oxide, many zinc oxide microrods grow from the center of the ball, the diameter of the sea urchin-shaped ball is 30-100 μm, the length of the rod is 15-50 μm, and the diameter is 0.3-2 μm. Among them, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H 2 O 2 with a mass fraction of 30%, distilled water, and NaOH is 1:3.658:41.67:591.7:6.667.
本发明方法中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶18.29∶8.333～166.7∶466.7～625∶3.333～25，制备成微米锥状氧化锌，锥的长度为15～80μm、直径为0.5～10μm。其中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比最佳为1∶18.29∶41.67∶591.7∶6.667。In the method of the present invention, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H2O2 with a mass fraction of 30%, distilled water and NaOH is 1: 18.29: 8.333-166.7: 466.7-625: 3.333-25 , prepared into micron cone-shaped zinc oxide, the length of the cone is 15-80 μm, and the diameter is 0.5-10 μm. Among them, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H 2 O 2 with a mass fraction of 30%, distilled water, and NaOH is 1:18.29:41.67:591.7:6.667.
本发明方法中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶29.27～36.58∶8.333～166.7∶466.7～625∶3.333～25，制备成微米六棱柱自组装实心球状氧化锌，实心球的直径为80～120μm，六棱柱的长度为40～60μm、直径为2～5μm。其中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比最佳为1∶29.27∶41.67∶591.7∶6.667。In the method of the present invention, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H2O2 with a mass fraction of 30%, distilled water and NaOH is 1: 29.27-36.58 : 8.333-166.7: 466.7-625: 3.333 ~25, prepared as micron hexagonal prism self-assembled solid spherical zinc oxide, the diameter of the solid sphere is 80-120 μm, the length of the hexagonal prism is 40-60 μm, and the diameter is 2-5 μm. Among them, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H 2 O 2 with a mass fraction of 30%, distilled water, and NaOH is 1:29.27:41.67:591.7:6.667.
本发明方法中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶0.3658～18.29∶8.333～166.7∶466.7～625∶0.1667～1.667，制备成微米糖葫芦状氧化锌，一个花状氧化锌球中间***一个锥状氧化锌，球的直径为3～20μm，锥的长度为10～50μm、直径为0.5～10μm。其中，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比最佳为1∶3.658∶41.67∶616.7∶1.667。In the method of the present invention, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H2O2 with a mass fraction of 30%, distilled water, and NaOH is 1 : 0.3658～18.29: 8.333～166.7: 466.7～625: 0.1667 ~1.667, prepared into micron candied haws-shaped zinc oxide, a cone-shaped zinc oxide ball is inserted in the middle of a flower-shaped zinc oxide ball, the diameter of the ball is 3-20 μm, the length of the cone is 10-50 μm, and the diameter is 0.5-10 μm. Among them, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H 2 O 2 with a mass fraction of 30%, distilled water, and NaOH is optimally 1:3.658:41.67:616.7:1.667.
本发明采用水热法制备成海胆状、六棱柱自组装实心球状、锥状、糖葫芦状微米结构氧化锌，具有方法简单、成本低、条件温和以及对环境无污染等优点。本发明制备的微米氧化锌材料纯度较高，晶体结构规整，材料形貌的可控性好，生产周期短，在燃料电池、光电转换材料以及化学传感器等方面有着巨大的应用前景。The invention adopts hydrothermal method to prepare sea urchin-shaped, hexagonal prism self-assembled solid spherical, cone-shaped, and candied haws-shaped micron-structured zinc oxide, which has the advantages of simple method, low cost, mild conditions, and no pollution to the environment. The micron zinc oxide material prepared by the invention has high purity, regular crystal structure, good controllability of material appearance and short production cycle, and has great application prospects in fuel cells, photoelectric conversion materials, chemical sensors and the like.
附图说明Description of drawings
图1是本发明实施例1制备的微米海胆状氧化锌的扫描电镜图。Figure 1 is a scanning electron micrograph of the micron sea urchin-shaped zinc oxide prepared in Example 1 of the present invention.
图2是本发明实施例2制备的微米海胆状氧化锌的扫描电镜图。Fig. 2 is a scanning electron micrograph of micron sea urchin-shaped zinc oxide prepared in Example 2 of the present invention.
图3是本发明实施例3制备的微米海胆状氧化锌的扫描电镜图。Fig. 3 is a scanning electron micrograph of micron sea urchin-shaped zinc oxide prepared in Example 3 of the present invention.
图4是本发明实施例4制备的微米锥状氧化锌的扫描电镜图。Fig. 4 is a scanning electron micrograph of the micron cone-shaped zinc oxide prepared in Example 4 of the present invention.
图5是本发明实施例5制备的微米锥状氧化锌的扫描电镜图。Fig. 5 is a scanning electron micrograph of the micron cone-shaped zinc oxide prepared in Example 5 of the present invention.
图6是本发明实施例6制备的微米锥状氧化锌的扫描电镜图。Fig. 6 is a scanning electron micrograph of the micron cone-shaped zinc oxide prepared in Example 6 of the present invention.
图7是本发明实施例7制备的微米六棱柱自组装实心球状氧化锌的扫描电镜图。Fig. 7 is a scanning electron micrograph of micron hexagonal prism self-assembled solid spherical zinc oxide prepared in Example 7 of the present invention.
图8是本发明实施例8制备的微米六棱柱自组装实心球状氧化锌的扫描电镜图。Fig. 8 is a scanning electron micrograph of micron hexagonal prism self-assembled solid spherical zinc oxide prepared in Example 8 of the present invention.
图9是本发明实施例9制备的微米六棱柱自组装实心球状氧化锌的扫描电镜图。Fig. 9 is a scanning electron micrograph of micron hexagonal prism self-assembled solid spherical zinc oxide prepared in Example 9 of the present invention.
图10是本发明实施例10制备的微米糖葫芦状氧化锌的扫描电镜图。Fig. 10 is a scanning electron micrograph of micron candied haws-shaped zinc oxide prepared in Example 10 of the present invention.
图11是本发明实施例11制备的微米糖葫芦状氧化锌的扫描电镜图。Fig. 11 is a scanning electron micrograph of micron candied haws-shaped zinc oxide prepared in Example 11 of the present invention.
图12是本发明实施例12制备的微米糖葫芦状氧化锌的扫描电镜图。Fig. 12 is a scanning electron micrograph of micron candied haws-shaped zinc oxide prepared in Example 12 of the present invention.
具体实施方式Detailed ways
下面结合附图和实施例对本发明进一步详细说明，但本发明不限于这些实施例。The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments, but the present invention is not limited to these embodiments.
实施例1Example 1
以制备微米海胆状氧化锌材料为例，其具体制备方法如下：Taking the preparation of micron sea urchin-like zinc oxide material as an example, the specific preparation method is as follows:
将质量分数为30％的H2O25g加入到71g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌0.439g，室温搅拌20分钟，加入4mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶3.658∶41.67∶591.7∶6.667，室温搅拌，待溶液产生白色浑浊后继续搅拌5分钟，将白色浑浊溶液倒入内衬为聚四氟乙烯的水热反应釜中，密封水热反应釜，将水热反应釜放入温度为180℃的烘箱中反应24小时，离心分离，沉淀依次用蒸馏水、无水乙醇交替洗涤3次，60℃真空干燥24小时。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图1。Add 5 g of H 2 O 2 with a mass fraction of 30% to 71 g of distilled water, stir at room temperature for 5 minutes, add polyvinylpyrrolidone K-300.12 g, stir at room temperature for 10 minutes, add 0.439 g of zinc acetate dihydrate, and stir at room temperature for 20 minutes, Add 4mL of NaOH aqueous solution with a substance concentration of 5mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH is 1:3.658:41.67: 591.7:6.667, stir at room temperature, continue to stir for 5 minutes after the solution becomes white turbid, pour the white turbid solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, seal the hydrothermal reaction kettle, put the hydrothermal reaction kettle put into an oven with a temperature of 180°C for 24 hours, centrifuged, and the precipitate was alternately washed with distilled water and absolute ethanol three times, and dried in vacuum at 60°C for 24 hours. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 1 .
由图1可见，所得产物是微米海胆状氧化锌，从球的中心生长出许多氧化锌微米棒，海胆状球的直径为60～100μm，棒的长度为30～50μm、直径为1.5～2μm。As can be seen from Figure 1, the resulting product is micron sea urchin-shaped zinc oxide, and many zinc oxide micro-rods grow from the center of the ball. The diameter of the sea urchin-shaped ball is 60-100 μm, the length of the rod is 30-50 μm, and the diameter is 1.5-2 μm.
实施例2Example 2
在实施例1中，将质量分数为30％的H2O21g加入到56g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌0.0439g，室温搅拌20分钟，加入2mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶0.3658∶8.333∶466.7∶3.333，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图2。In Example 1, 1 g of H 2 O 2 with a mass fraction of 30% was added to 56 g of distilled water, stirred at room temperature for 5 minutes, 0.12 g of polyvinylpyrrolidone K-30 was added, stirred at room temperature for 10 minutes, and 0.0439 g of zinc acetate dihydrate was added , stirred at room temperature for 20 minutes, added 2 mL of NaOH aqueous solution with a concentration of 5 mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH was 1: 0.3658: 8.333: 466.7: 3.333, the other steps are the same as those in the corresponding examples to prepare zinc oxide with micron structure. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 2 .
由图2可见，所得产物是微米海胆状氧化锌，从球的中心生长出许多氧化锌微米棒，海胆状球的直径为40～80μm，棒的长度为20～40μm、直径为1～1.5μm。It can be seen from Figure 2 that the obtained product is micron sea urchin-shaped zinc oxide, and many micron rods of zinc oxide grow from the center of the ball. The diameter of the sea urchin-shaped ball is 40-80 μm, the length of the rod is 20-40 μm, and the diameter is 1-1.5 μm .
实施例3Example 3
在实施例1中，将质量分数为30％的H2O216g加入到60g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.096g，室温搅拌10分钟，加入二水醋酸锌1.054g，室温搅拌20分钟，加入12mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶10.98∶166.7∶625∶25，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图3。In Example 1, 16 g of H 2 O 2 with a mass fraction of 30% was added to 60 g of distilled water, stirred at room temperature for 5 minutes, 0.096 g of polyvinylpyrrolidone K-30 was added, stirred at room temperature for 10 minutes, and 1.054 g of zinc acetate dihydrate was added , stirred at room temperature for 20 minutes, added 12mL of NaOH aqueous solution with a substance concentration of 5mol/L, the mass ratio of polyvinylpyrrolidone K-30 and zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH was 1: 10.98: 166.7: 625: 25, and other steps are the same as those in the corresponding examples to prepare zinc oxide with a micron structure. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 3 .
由图3可见，所得产物是微米海胆状氧化锌，从球的中心生长出许多氧化锌微米棒，海胆状球的直径为30～60μm，棒的长度为15～30μm、直径为0.3～1μm。As can be seen from Figure 3, the resulting product is micron sea urchin-shaped zinc oxide, and many zinc oxide micro-rods grow from the center of the ball. The diameter of the sea urchin-shaped ball is 30-60 μm, the length of the rod is 15-30 μm, and the diameter is 0.3-1 μm.
实施例4Example 4
以制备微米锥状氧化锌材料为例，其具体制备方法如下：Taking the preparation of micron cone-shaped zinc oxide material as an example, the specific preparation method is as follows:
将质量分数为30％的H2O25g加入到71g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌2.195g，室温搅拌20分钟，加入4mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶18.29∶41.67∶591.7∶6.667，室温搅拌，待溶液产生白色浑浊后继续搅拌5分钟，将白色浑浊溶液倒入内衬为聚四氟乙烯的水热反应釜中，密封水热反应釜，将水热反应釜放入温度为180℃的烘箱中反应24小时，离心分离，沉淀依次用蒸馏水、无水乙醇交替洗涤3次，60℃真空干燥24小时。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图4。Add 5 g of H 2 O 2 with a mass fraction of 30% to 71 g of distilled water, stir at room temperature for 5 minutes, add polyvinylpyrrolidone K-300.12 g, stir at room temperature for 10 minutes, add 2.195 g of zinc acetate dihydrate, and stir at room temperature for 20 minutes, Add 4mL of NaOH aqueous solution with a substance concentration of 5mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH is 1:18.29:41.67: 591.7:6.667, stir at room temperature, continue to stir for 5 minutes after the solution becomes white turbid, pour the white turbid solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, seal the hydrothermal reaction kettle, put the hydrothermal reaction kettle put into an oven with a temperature of 180°C for 24 hours, centrifuged, and the precipitate was alternately washed with distilled water and absolute ethanol three times, and dried in vacuum at 60°C for 24 hours. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 4 .
由图4可见，所得产物是微米锥状氧化锌，锥的长度为15～30μm、直径为0.5～1μm。It can be seen from Fig. 4 that the obtained product is micron cone-shaped zinc oxide, the length of the cone is 15-30 μm, and the diameter is 0.5-1 μm.
实施例5Example 5
在实施例4中，将质量分数为30％的H2O21g加入到56g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌2.195g，室温搅拌20分钟，加入2mL物质的量浓度为5mo1/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶18.29∶8.333∶466.7∶3.333，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图5。In Example 4, 1 g of H 2 O 2 with a mass fraction of 30% was added to 56 g of distilled water, stirred at room temperature for 5 minutes, 0.12 g of polyvinylpyrrolidone K-30 was added, stirred at room temperature for 10 minutes, and 2.195 g of zinc acetate dihydrate was added , stirred at room temperature for 20 minutes, added 2mL of NaOH aqueous solution with a substance concentration of 5mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH was 1: 18.29: 8.333: 466.7: 3.333, and other steps are the same as those in the corresponding examples to prepare zinc oxide with micron structure. The obtained product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 5 .
由图5可见，所得产物是微米锥状氧化锌，锥的长度为50～80μm、直径为5～10μm。It can be seen from Fig. 5 that the obtained product is micron cone-shaped zinc oxide, the length of the cone is 50-80 μm, and the diameter is 5-10 μm.
实施例6Example 6
在实施例4中，将质量分数为30％的H2O216g加入到60g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.096g，室温搅拌10分钟，加入二水醋酸锌1.756g，室温搅拌20分钟，加入12mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶18.29∶166.7∶625∶25，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图6。In Example 4, 16 g of H 2 O 2 with a mass fraction of 30% was added to 60 g of distilled water, stirred at room temperature for 5 minutes, 0.096 g of polyvinylpyrrolidone K-30 was added, stirred at room temperature for 10 minutes, and 1.756 g of zinc acetate dihydrate was added , stirred at room temperature for 20 minutes, added 12mL of NaOH aqueous solution with a substance concentration of 5mol/L, the mass ratio of polyvinylpyrrolidone K-30 and zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH was 1: 18.29: 166.7: 625: 25, and other steps are the same as those in the corresponding examples to prepare zinc oxide with micron structure. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 6 .
由图6可见，所得产物是微米锥状氧化锌，锥的长度为30～60μm、直径为3～10μm。It can be seen from Fig. 6 that the obtained product is micron cone-shaped zinc oxide, the length of the cone is 30-60 μm, and the diameter is 3-10 μm.
实施例7Example 7
以制备微米六棱柱自组装实心球状氧化锌材料为例，其具体制备方法如下：Taking the preparation of micron hexagonal prism self-assembled solid spherical zinc oxide material as an example, the specific preparation method is as follows:
将质量分数为30％的H2O25g加入到71g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌3.512g，室温搅拌20分钟，加入4mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H202、蒸馏水、Na0H的质量比为1∶29.27∶41.67∶591.7∶6.667，室温搅拌，待溶液产生白色浑浊后继续搅拌5分钟，将白色浑浊溶液倒入内衬为聚四氟乙烯的水热反应釜中，密封水热反应釜，将水热反应釜放入温度为180℃的烘箱中反应24小时，离心分离，沉淀依次用蒸馏水、无水乙醇交替洗涤3次，60℃真空干燥24小时。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图7。Add 5 g of H 2 O 2 with a mass fraction of 30% to 71 g of distilled water, stir at room temperature for 5 minutes, add polyvinylpyrrolidone K-300.12 g, stir at room temperature for 10 minutes, add 3.512 g of zinc acetate dihydrate, and stir at room temperature for 20 minutes, Add 4mL of NaOH aqueous solution with a substance concentration of 5mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, 30% H 2 0 2 , distilled water, and NaOH is 1:29.27:41.67: 591.7:6.667, stir at room temperature, continue to stir for 5 minutes after the solution becomes white turbid, pour the white turbid solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, seal the hydrothermal reaction kettle, put the hydrothermal reaction kettle put into an oven with a temperature of 180°C for 24 hours, centrifuged, and the precipitate was alternately washed with distilled water and absolute ethanol three times, and dried in vacuum at 60°C for 24 hours. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 7 .
由图7可见，所得产物是微米六棱柱自组装实心球状氧化锌，实心球的直径为100～120μm，六棱柱的长度为40～60μm、直径为3～5μm。It can be seen from Figure 7 that the obtained product is micron hexagonal prism self-assembled solid spherical zinc oxide, the diameter of the solid sphere is 100-120 μm, the length of the hexagonal prism is 40-60 μm, and the diameter is 3-5 μm.
实施例8Example 8
在实施例7中，将质量分数为30％的H2O21g加入到56g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌3.512g，室温搅拌20分钟，加入2mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶29.27∶8.333∶466.7∶3.333，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图8。In Example 7, 1 g of H 2 O 2 with a mass fraction of 30% was added to 56 g of distilled water, stirred at room temperature for 5 minutes, polyvinylpyrrolidone K-300.12 g was added, stirred at room temperature for 10 minutes, and 3.512 g of zinc acetate dihydrate was added , stirred at room temperature for 20 minutes, added 2 mL of NaOH aqueous solution with a concentration of 5 mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH was 1: 29.27: 8.333: 466.7: 3.333, and other steps are the same as those in the corresponding examples to prepare zinc oxide with micron structure. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 8 .
由图8可见，所得产物是微米六棱柱自组装实心球状氧化锌，实心球的直径为80～100μm，六棱柱的长度为40～50μm、直径为3～4μm。It can be seen from Figure 8 that the obtained product is micron hexagonal prism self-assembled solid spherical zinc oxide, the diameter of the solid sphere is 80-100 μm, the length of the hexagonal prism is 40-50 μm, and the diameter is 3-4 μm.
实施例9Example 9
在实施例7中，将质量分数为30％的H2O216g加入60g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.096g，室温搅拌10分钟，加入二水醋酸锌3.512g，室温搅拌20分钟，加入12mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶36.58∶166.7∶625∶25，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图9。In Example 7, 16 g of H 2 O 2 with a mass fraction of 30% was added to 60 g of distilled water, stirred at room temperature for 5 minutes, 0.096 g of polyvinylpyrrolidone K-30 was added, stirred at room temperature for 10 minutes, 3.512 g of zinc acetate dihydrate was added, Stir at room temperature for 20 minutes, add 12 mL of NaOH aqueous solution with a substance concentration of 5 mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H 2 O 2 with a mass fraction of 30%, distilled water, and NaOH is 1 : 36.58: 166.7: 625: 25, and the other steps are the same as those in the corresponding examples to prepare zinc oxide with a micron structure. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 9 .
由图9可见，所得产物是微米六棱柱自组装实心球状氧化锌，实心球的直径为90～110μm，六棱柱的长度为45～55μm、直径为2～4μm。It can be seen from Figure 9 that the obtained product is micron hexagonal prism self-assembled solid spherical zinc oxide, the diameter of the solid sphere is 90-110 μm, the length of the hexagonal prism is 45-55 μm, and the diameter is 2-4 μm.
实施例10Example 10
以制备微米糖葫芦状氧化锌材料为例，其具体制备方法如下：Taking the preparation of micron candied haws-shaped zinc oxide material as an example, the specific preparation method is as follows:
将质量分数为30％的H2O25g加入到74g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌0.439g，室温搅拌20分钟，加入1mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶3.658∶41.67∶616.7∶1.667，室温搅拌，待溶液产生白色浑浊后继续搅拌5分钟，将白色浑浊溶液倒入内衬为聚四氟乙烯的水热反应釜中，密封水热反应釜，将水热反应釜放入温度为180℃的烘箱中反应24小时，离心分离，沉淀依次用蒸馏水、无水乙醇交替洗涤3次，60℃真空干燥24小时。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图10。Add 5 g of H 2 O 2 with a mass fraction of 30% to 74 g of distilled water, stir at room temperature for 5 minutes, add polyvinylpyrrolidone K-300.12 g, stir at room temperature for 10 minutes, add 0.439 g of zinc acetate dihydrate, and stir at room temperature for 20 minutes, Add 1 mL of NaOH aqueous solution with a substance concentration of 5 mol/L, and the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, 30% H 2 O 2 , distilled water, and NaOH is 1:3.658:41.67: 616.7:1.667, stir at room temperature, continue to stir for 5 minutes after the solution becomes white turbid, pour the white turbid solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, seal the hydrothermal reaction kettle, put the hydrothermal reaction kettle put into an oven with a temperature of 180°C for 24 hours, centrifuged, and the precipitate was alternately washed with distilled water and absolute ethanol three times, and dried in vacuum at 60°C for 24 hours. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 10 .
由图10可见，所得产物是微米糖葫芦状氧化锌，一个花状氧化锌球中间***一个锥状氧化锌，球的直径为3～6μm，锥的长度为10～20μm、直径为0.5～1.5μm。It can be seen from Figure 10 that the obtained product is micron candied haws-shaped zinc oxide, a flower-shaped zinc oxide ball is inserted into a cone-shaped zinc oxide, the diameter of the ball is 3-6 μm, the length of the cone is 10-20 μm, and the diameter is 0.5-1.5 μm .
实施例11Example 11
在实施例10中，将质量分数为30％的H2O21g加入到56g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.12g，室温搅拌10分钟，加入二水醋酸锌0.0439g，室温搅拌20分钟，加入0.1mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶0.3658∶8.333∶466.7∶0.1667，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图11。In Example 10, 1 g of H 2 O 2 with a mass fraction of 30% was added to 56 g of distilled water, stirred at room temperature for 5 minutes, 0.12 g of polyvinylpyrrolidone K-30 was added, stirred at room temperature for 10 minutes, and 0.0439 g of zinc acetate dihydrate was added , stirred at room temperature for 20 minutes, added 0.1 mL of NaOH aqueous solution with a substance concentration of 5 mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H2O2 with a mass fraction of 30%, distilled water, and NaOH The ratio is 1:0.3658:8.333:466.7:0.1667, and other steps are the same as those in the corresponding examples to prepare zinc oxide with micron structure. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 11 .
由图10可见，所得产物是微米糖葫芦状氧化锌，一个花状氧化锌球中间***一个锥状氧化锌，球的直径为5～10μm，锥的长度为20～30μm、直径为2～5μm。As can be seen from Figure 10, the obtained product is micron candied haws-shaped zinc oxide, a cone-shaped zinc oxide ball is inserted in the middle of a flower-shaped zinc oxide ball, the diameter of the ball is 5-10 μm, the length of the cone is 20-30 μm, and the diameter is 2-5 μm.
实施例12Example 12
在实施例10中，将质量分数为30％的H2O216g加入到60g蒸馏水中，室温搅拌5分钟，加入聚乙烯吡咯烷酮K-300.096g，室温搅拌10分钟，加入二水醋酸锌1.756g，室温搅拌20分钟，加入0.8mL物质的量浓度为5mol/L的NaOH水溶液，聚乙烯吡咯烷酮K-30与二水醋酸锌、质量分数为30％的H2O2、蒸馏水、NaOH的质量比为1∶18.29∶166.7∶625∶1.667，其他步骤与相应实施例相同，制备成微米结构氧化锌。所得产物用Quanta 200型环境扫描电镜进行表征，结果见图12。In Example 10, 16 g of H 2 O 2 with a mass fraction of 30% was added to 60 g of distilled water, stirred at room temperature for 5 minutes, 0.096 g of polyvinylpyrrolidone K-30 was added, stirred at room temperature for 10 minutes, and 1.756 g of zinc acetate dihydrate was added , stir at room temperature for 20 minutes, add 0.8mL of NaOH aqueous solution with a substance concentration of 5mol/L, the mass ratio of polyvinylpyrrolidone K-30 to zinc acetate dihydrate, H2O2 with a mass fraction of 30%, distilled water, and NaOH The ratio is 1:18.29:166.7:625:1.667, and the other steps are the same as those in the corresponding examples to prepare zinc oxide with a micron structure. The resulting product was characterized by a Quanta 200 environmental scanning electron microscope, and the results are shown in FIG. 12 .
由图12可见，所得产物是微米糖葫芦状氧化锌，一个花状氧化锌球中间***一个锥状氧化锌，球的直径为10～20μm，锥的长度为30～50μm、直径为5～10μm。As can be seen from Figure 12, the obtained product is micron candied haws-shaped zinc oxide, a cone-shaped zinc oxide ball is inserted in the middle of a flower-shaped zinc oxide ball, the diameter of the ball is 10-20 μm, the length of the cone is 30-50 μm, and the diameter is 5-10 μm.
实施例13Example 13
在实施例1～12中，将白色浑浊溶液倒入内衬为聚四氟乙烯的水热反应釜中，密封水热反应釜，将水热反应釜放入温度为80℃的烘箱中反应20小时，其他步骤与相应实施例相同，制备成微米结构氧化锌。In Examples 1 to 12, pour the white turbid solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, seal the hydrothermal reaction kettle, and put the hydrothermal reaction kettle into an oven with a temperature of 80°C to react for 20 Hours, other steps are the same as the corresponding examples, to prepare zinc oxide with micron structure.
实施例14Example 14
在实施例1～12中，将白色浑浊溶液倒入内衬为聚四氟乙烯的水热反应釜中，密封水热反应釜，将水热反应釜放入温度为200℃的烘箱中反应0.5小时，其他步骤与相应实施例相同，制备成微米结构氧化锌。In Examples 1 to 12, pour the white turbid solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, seal the hydrothermal reaction kettle, and put the hydrothermal reaction kettle into an oven with a temperature of 200°C for 0.5 Hours, other steps are the same as the corresponding examples, to prepare zinc oxide with micron structure.
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| CN102912436A (en) * | 2011-08-05 | 2013-02-06 | 国家纳米科学中心 | Preparation method of conical zinc oxide sub-micron rods and array thereof |
| CN103781723A (en) * | 2012-07-13 | 2014-05-07 | 首尔大学校产学协力团 | 3D nanoparticle assembly structure and gas sensor using it |
| CN104326504A (en) * | 2014-10-13 | 2015-02-04 | 李大枝 | Preparation method for urchin-like nanometer zinc oxide |
| CN104607194A (en) * | 2015-01-29 | 2015-05-13 | 陕西科技大学 | A kind of sea urchin-shaped modified nano-ZnO photocatalyst and its preparation method and application |
| CN107359244A (en) * | 2016-12-20 | 2017-11-17 | 凯里学院 | Perovskite solar cell electron transfer layer based on three-dimensional sea urchin shape ZnO superstructure arrays and its preparation method and application |
| CN109364927A (en) * | 2018-11-26 | 2019-02-22 | 中国华能集团清洁能源技术研究院有限公司 | A kind of preparation method of prismatic copper oxide-zinc oxide catalyst |
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| CN1245777A (en) * | 1999-09-08 | 2000-03-01 | 中国科学院广州化学研究所 | Preparation method of zinc oxide microparticles with specific form |
| CN1539741A (en) * | 2003-04-21 | 2004-10-27 | 中国科学院理化技术研究所 | Rod-shaped zinc oxide particles and its preparation method and use |
| US7491423B1 (en) * | 2005-05-02 | 2009-02-17 | Sandia Corporation | Directed spatial organization of zinc oxide nanostructures |
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| CN1539741A (en) * | 2003-04-21 | 2004-10-27 | 中国科学院理化技术研究所 | Rod-shaped zinc oxide particles and its preparation method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102912436A (en) * | 2011-08-05 | 2013-02-06 | 国家纳米科学中心 | Preparation method of conical zinc oxide sub-micron rods and array thereof |
| CN102912436B (en) * | 2011-08-05 | 2015-07-22 | 国家纳米科学中心 | Preparation method of conical zinc oxide sub-micron rods and array thereof |
| CN103781723A (en) * | 2012-07-13 | 2014-05-07 | 首尔大学校产学协力团 | 3D nanoparticle assembly structure and gas sensor using it |
| CN103781723B (en) * | 2012-07-13 | 2015-12-02 | 首尔大学校产学协力团 | 3D nanoparticle assembly structure and gas sensor using it |
| US9222190B2 (en) | 2012-07-13 | 2015-12-29 | Snu R&Db Foundation | 3-dimensional nanoparticle assembly structure and gas sensor using same |
| CN104326504A (en) * | 2014-10-13 | 2015-02-04 | 李大枝 | Preparation method for urchin-like nanometer zinc oxide |
| CN104607194A (en) * | 2015-01-29 | 2015-05-13 | 陕西科技大学 | A kind of sea urchin-shaped modified nano-ZnO photocatalyst and its preparation method and application |
| CN107359244A (en) * | 2016-12-20 | 2017-11-17 | 凯里学院 | Perovskite solar cell electron transfer layer based on three-dimensional sea urchin shape ZnO superstructure arrays and its preparation method and application |
| CN109364927A (en) * | 2018-11-26 | 2019-02-22 | 中国华能集团清洁能源技术研究院有限公司 | A kind of preparation method of prismatic copper oxide-zinc oxide catalyst |
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