CN105540640A - Preparation method of flower-shaped nanometer zinc oxide - Google Patents
Preparation method of flower-shaped nanometer zinc oxide Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 22
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 22
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 239000005457 ice water Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 3
- 238000000967 suction filtration Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 2
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims 4
- 238000001556 precipitation Methods 0.000 claims 2
- 230000029087 digestion Effects 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 23
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004246 zinc acetate Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- -1 WO 3 Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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Abstract
本发明公开了一种花状纳米氧化锌的制备方法；涉及一种纳米氧化锌的制备方法。本发明目的是制备一种具有高结晶度、高稳定性、大比表面积、无团聚等特性的纳米氧化锌。本发明利用廉价易得的松香作为表面活性剂制备了纳米级的氧化锌。本发明的方法如下：将松香的醇溶液加入到氢氧化钠溶液中，混合均匀，再在冰水浴和搅拌的条件下缓慢滴加乙酸锌溶液；然后室温下陈化，再进行水热反应，自然冷却结晶，抽滤，洗涤沉淀，烘干后煅烧，即得到花状纳米氧化锌。本发明所得产品无团聚，比表面积大，光催化活性高，且水热合成法工艺简单，生产成本低，可实现工业化生产。
The invention discloses a preparation method of flower-shaped nano-zinc oxide, and relates to a preparation method of nano-zinc oxide. The purpose of the invention is to prepare a nano-zinc oxide with high crystallinity, high stability, large specific surface area, no agglomeration and the like. The present invention uses cheap and easy-to-obtain rosin as a surfactant to prepare nanometer zinc oxide. The method of the present invention is as follows: the alcohol solution of rosin is added to the sodium hydroxide solution, mixed evenly, and then the zinc acetate solution is slowly added dropwise under the conditions of ice-water bath and stirring; then aged at room temperature, and then hydrothermal reaction is carried out, Natural cooling and crystallization, suction filtration, washing of precipitates, drying and calcination to obtain flower-shaped nano-zinc oxide. The product obtained by the invention has no agglomeration, large specific surface area, high photocatalytic activity, simple hydrothermal synthesis process, low production cost, and can realize industrialized production.
Description
技术领域technical field
本发明属于纳米材料的技术领域；涉及一种纳米氧化锌的制备方法；具体涉及一种具有比表面积大、催化活性高、稳定性强等特性的纳米氧化锌的制备方法。The invention belongs to the technical field of nanometer materials, relates to a preparation method of nanometer zinc oxide, and specifically relates to a preparation method of nanometer zinc oxide with characteristics such as large specific surface area, high catalytic activity and strong stability.
背景技术Background technique
随着现代化工业的迅速发展，大量含有有机毒物的工业废水排入到环境当中，致使水资源受到严重污染，威胁到了人类的生存与发展。特别是一些偶氮染料、多卤代烃及硝基芳香族化合物，它们结构稳定，毒性强，处理难度很大，使得传统的环境工程技术显效甚微。因此，目前迫切需要寻找新的、更合适有效的废水处理方法来弥补以往技术的不足。半导体金属氧化物光催化氧化技术的出现给人们带来了希望，它主要包括TiO2、ZnO、WO3、SnO2、Fe2O3等N型半导体材料。这其中，TiO2因其化学性质稳定，氧化能力强，无毒等特性而成为研究最成熟、应用最广泛的纳米光触媒材料。然而，随着对光催化降解有机毒物的深入研究，人们发现纳米ZnO在很多情况下比TiO2的光催化效果更好。与TiO2相比，ZnO具有以下优势：(1)能够吸收更大范围的紫外光；(2)TiO2是间接带隙半导体，电子跃迁几率较低，量子效率较低，催化反应进程也慢，难于处理那些浓度高、数量大的废水。相反，ZnO是直接带隙半导体，不存在这些问题。(3)在要保持较高的光催化活性的同时又要满足特定的理化性能要求的条件下很难将其均匀牢固地负载在其它载体上，而ZnO相对来说就易于在其它载体上吸附。所以ZnO可以代替TiO2成为更有发展前景的新型催化剂。With the rapid development of modern industry, a large amount of industrial wastewater containing organic poisons is discharged into the environment, causing serious pollution of water resources and threatening the survival and development of human beings. In particular, some azo dyes, polyhalogenated hydrocarbons and nitroaromatic compounds have stable structures, strong toxicity, and great difficulty in handling, making traditional environmental engineering techniques ineffective. Therefore, there is an urgent need to find new, more suitable and effective wastewater treatment methods to make up for the shortcomings of previous technologies. The emergence of semiconductor metal oxide photocatalytic oxidation technology has brought hope to people, it mainly includes N-type semiconductor materials such as TiO 2 , ZnO, WO 3 , SnO 2 , Fe 2 O 3 . Among them, TiO 2 has become the most mature and widely used nano-photocatalyst material because of its stable chemical properties, strong oxidation ability, and non-toxicity. However, with the in-depth research on photocatalytic degradation of organic poisons, it has been found that nano-ZnO has better photocatalytic effect than TiO2 in many cases. Compared with TiO 2 , ZnO has the following advantages: (1) It can absorb a wider range of ultraviolet light; (2) TiO 2 is an indirect band gap semiconductor, with lower electron transition probability, lower quantum efficiency, and slower catalytic reaction process , it is difficult to treat those wastewater with high concentration and large quantity. In contrast, ZnO is a direct bandgap semiconductor and does not suffer from these problems. (3) It is difficult to uniformly and firmly support it on other supports while maintaining high photocatalytic activity while meeting specific physical and chemical performance requirements, while ZnO is relatively easy to adsorb on other supports . So ZnO can replace TiO 2 to become a more promising new catalyst.
目前，纳米级ZnO的制备方法主要可分为三类：固相法、液相法、气相法。与其它方法相比，液相法具有简单易行、反应体系均匀、纳米粒子的平均粒度分布较窄、反应温度低的特点，是制备优良纳米ZnO材料的首选方法。但是，纳米ZnO由于其巨大的表面能，导致颗粒很容易团聚在一起，使其形貌和尺寸发生改变，严重影响最终产品的性能。此外，其在紫外光照射的条件下还会发生严重的光腐蚀。故要解决上述问题，必须对其制备条件进行严格控制──将不同的表面活性剂引入纳米ZnO的制备过程中是很多学者选择的方法。因此，寻找出合适的表面活性剂是当前亟待解决的问题，是制备粒径更小、分散性更好纳米ZnO材料的关键所在。At present, the preparation methods of nano-ZnO can be mainly divided into three categories: solid-phase method, liquid-phase method, and gas-phase method. Compared with other methods, the liquid phase method has the characteristics of simplicity, uniform reaction system, narrow average particle size distribution of nanoparticles, and low reaction temperature. It is the preferred method for preparing excellent nano-ZnO materials. However, due to the huge surface energy of nano-ZnO, the particles are easy to agglomerate, which changes the shape and size of the nano-ZnO, which seriously affects the performance of the final product. In addition, it will also undergo severe photocorrosion under the condition of ultraviolet light irradiation. Therefore, in order to solve the above problems, the preparation conditions must be strictly controlled—introducing different surfactants into the preparation process of nano-ZnO is the method chosen by many scholars. Therefore, finding a suitable surfactant is an urgent problem to be solved at present, and it is the key to prepare nano-ZnO materials with smaller particle size and better dispersion.
发明内容Contents of the invention
本发明公开了一种花状纳米氧化锌的制备方法；目的是制备一种具有高结晶度、高稳定性、大比表面积、无团聚等特性的纳米氧化锌。The invention discloses a method for preparing flower-shaped nano-zinc oxide; the purpose is to prepare a nano-zinc oxide with high crystallinity, high stability, large specific surface area, no agglomeration and the like.
本发明的一种花状纳米氧化锌的制备方法是按下述步骤进行的：将松香的醇溶液加入到氢氧化钠溶液中，混合均匀，再在冰水浴和搅拌的条件下缓慢滴加乙酸锌溶液；然后室温下陈化，再进行水热反应，自然冷却结晶，抽滤，洗涤沉淀，烘干后煅烧，即得到花状纳米氧化锌。The preparation method of a flower-shaped nano-zinc oxide of the present invention is carried out according to the following steps: adding the alcohol solution of rosin to the sodium hydroxide solution, mixing evenly, and slowly adding zinc acetate dropwise under the conditions of ice-water bath and stirring Solution; then aged at room temperature, then subjected to hydrothermal reaction, naturally cooled and crystallized, filtered with suction, washed and precipitated, dried and then calcined to obtain flower-shaped nano-zinc oxide.
进一步限定：所述松香的醇溶液的质量浓度为0.1～0.2g/mL，松香的醇溶液中的醇为乙醇。将10～20mL松香的醇溶液加入到36～90mL浓度为2～5mol/L的NaOH溶液，乙酸锌溶液用量为30～40mL，乙酸锌溶液的浓度为0.8～1.0mol/L。所述乙酸锌溶液的滴速为1.5～2mL/min。所述陈化时间为2～3h。所述水热反应是在75℃条件下反应5～12h。所述自然冷却结晶时间为1～2h。所述的洗涤沉淀是将沉淀物先用无水乙醇洗涤2～3次再用去离子水洗涤2～3次。在40～80℃条件下烘干。所述的煅烧是在空气条件下以3～10℃/min的升温速率加热至205～300℃，保温1～3小时，再继续升温至500～650℃，保温1～3小时。Further definition: the mass concentration of the rosin alcohol solution is 0.1-0.2 g/mL, and the alcohol in the rosin alcohol solution is ethanol. Add 10-20mL of rosin alcohol solution to 36-90mL NaOH solution with a concentration of 2-5mol/L, the dosage of zinc acetate solution is 30-40mL, and the concentration of zinc acetate solution is 0.8-1.0mol/L. The dropping rate of the zinc acetate solution is 1.5-2 mL/min. The aging time is 2-3 hours. The hydrothermal reaction is carried out at 75° C. for 5-12 hours. The natural cooling crystallization time is 1-2 hours. The washing of the precipitate is to wash the precipitate with absolute ethanol for 2 to 3 times and then with deionized water for 2 to 3 times. Dry at 40-80°C. The calcination is carried out by heating to 205-300° C. at a heating rate of 3-10° C./min under air conditions, keeping the temperature for 1-3 hours, and then continuing to raise the temperature to 500-650° C. and keeping the temperature for 1-3 hours.
本发明的方法工艺简单，设备要求不高，松香、乙醇等原料价格低廉易得，而且易于回收，故生产成本低，可大规模工业化生产。The method of the invention has the advantages of simple process, low equipment requirements, low price and easy availability of raw materials such as rosin and ethanol, and easy recycling, so the production cost is low and large-scale industrial production is possible.
本发明方法使用的松香为天然产物，环境友好，不会引起污染。The rosin used in the method of the invention is a natural product, is environmentally friendly and does not cause pollution.
本发明方法获得的纳米氧化锌颗粒基本无团聚，分散性好。The nano-zinc oxide particles obtained by the method of the invention basically have no agglomeration and good dispersibility.
本发明方法获得的花状纳米氧化锌由大量纳米棒自组装而成，形貌规整、均一，平均粒径90纳米左右，比表面积大。The flower-shaped nano-zinc oxide obtained by the method of the invention is self-assembled by a large number of nano-rods, has regular and uniform appearance, an average particle diameter of about 90 nanometers, and a large specific surface area.
由本发明的花状纳米氧化锌的XRD纳米图谱可知其衍射峰很尖锐，说明结晶度很高，且未出现杂质峰，说明纯度很高。From the XRD nano-spectrum of the flower-shaped nano-zinc oxide of the present invention, it can be seen that its diffraction peaks are very sharp, indicating that the crystallinity is very high, and no impurity peaks appear, indicating that the purity is very high.
本发明方法获得的花状纳米氧化锌光催化活性高。用0.1g本发明方法制得的花状纳米氧化锌在18W紫外灯的照射下催化降解100mL浓度为5mg/L的亚甲基蓝溶液，持续搅拌2.5h，降解率将近100％。The flower-shaped nano-zinc oxide obtained by the method of the invention has high photocatalytic activity. Using 0.1 g of the flower-shaped nano-zinc oxide prepared by the method of the present invention, under the irradiation of an 18W ultraviolet lamp, 100 mL of a methylene blue solution with a concentration of 5 mg/L is catalytically degraded, and the stirring is continued for 2.5 hours, and the degradation rate is nearly 100%.
附图说明Description of drawings
图1是具体实施方式一所得产品的扫描电子显微镜照片。Fig. 1 is a scanning electron micrograph of the product obtained in Embodiment 1.
图2是具体实施方式一未加松香所得产品的扫描电子显微镜照片。Fig. 2 is the scanning electron micrograph of the product obtained without adding rosin in the specific embodiment one.
图3是具体实施方式三所得产品的透射电子显微镜照片。Fig. 3 is a transmission electron micrograph of the product obtained in Embodiment 3.
图4是具体实施方式三所得产品的X射线衍射分析图。Fig. 4 is the X-ray diffraction analysis diagram of the product obtained in Embodiment 3.
图5是具体实施方式一～四所得产品取0.1g在18W紫外灯照射下催化降解100mL浓度为5mg/L的亚甲基蓝溶液的降解率；图5中■表示具体实施方式一，●表示具体实施方式二，▲表示具体实施方式三，▼表示具体实施方式四。Fig. 5 is the degradation rate of the methylene blue solution of 5 mg/L in catalytic degradation of 100mL concentration under the irradiation of 18W ultraviolet lamp to get 0.1g of the obtained product of specific embodiment one to four; among Fig. 5, ■ represents specific embodiment one, ● represents specific embodiment 2. ▲ represents the third embodiment, and ▼ represents the fourth embodiment.
具体实施方式detailed description
具体实施方式一：本实施方式中花状纳米氧化锌的制备方法是按下述步骤进行的：Specific embodiment one: the preparation method of flower-shaped nano-zinc oxide in the present embodiment is carried out according to the following steps:
将10g松香溶于100mL无水乙醇，制成0.1g/mL的松香的醇溶液。Dissolve 10 g of rosin in 100 mL of absolute ethanol to make a 0.1 g/mL alcoholic solution of rosin.
将5g乙酸锌溶于30mL去离子水中得到乙酸锌溶液。5 g of zinc acetate was dissolved in 30 mL of deionized water to obtain a zinc acetate solution.
将20mL松香的醇溶液加入到90mL浓度为2mol/L由氢氧化钠与去离子水配置的氢氧化钠溶液中，搅拌混合均匀，再在冰水浴和搅拌的条件下缓慢滴加乙酸锌溶液，控制滴速为1.5mL/min；然后室温下陈化2h，倒入内衬聚四氟乙烯的高压水热反应釜，置于75℃烘箱中进行水热反应12h，自然冷却结晶1h，抽滤，沉淀物先用无水乙醇洗涤3次再用去离子水洗涤3次，在80℃下烘干，置于烧结炉中进行煅烧，先升温速度为10℃/min，在300℃保温1h，再继续升温至600℃，再保温1h，即得到花状纳米氧化锌。Add 20mL of rosin alcohol solution to 90mL of 2mol/L sodium hydroxide solution prepared by sodium hydroxide and deionized water, stir and mix evenly, then slowly add zinc acetate solution dropwise under ice-water bath and stirring conditions, Control the drop rate to 1.5mL/min; then age at room temperature for 2 hours, pour into a high-pressure hydrothermal reactor lined with polytetrafluoroethylene, place in a 75°C oven for hydrothermal reaction for 12 hours, cool and crystallize naturally for 1 hour, and suction filter , the precipitate was washed 3 times with absolute ethanol and then 3 times with deionized water, dried at 80°C, placed in a sintering furnace for calcination, first the heating rate was 10°C/min, and kept at 300°C for 1h. Continue to raise the temperature to 600° C., and keep it warm for 1 hour to obtain flower-shaped nano zinc oxide.
由图1和图2可知，没有加入松香所制备的纳米氧化锌，花簇直径为10m，各个氧化锌棒间团聚较重；加入松香制备的氧化锌，其花簇直径在5m，花簇上的氧化锌纳米棒没有团聚现象。可见松香的引入明显使得氧化锌的形貌变得规整有序，纳米花簇的直径变小。It can be seen from Figure 1 and Figure 2 that the diameter of the flower clusters is 10m without the addition of rosin, and the agglomeration between each zinc oxide rod is relatively heavy; the diameter of the flower clusters of the zinc oxide prepared by adding rosin is 5m, and the diameter of the flower clusters is 5m. The ZnO nanorods did not agglomerate. It can be seen that the introduction of rosin obviously makes the morphology of zinc oxide regular and orderly, and the diameter of nanoflower clusters becomes smaller.
用0.1g本实施方式方法制得的花状纳米氧化锌在18W紫外灯的照射下催化降解100mL浓度为5mg/L的亚甲基蓝溶液，持续搅拌2.5h，降解率将近100％(参见图5)。Using 0.1 g of the flower-shaped nano-zinc oxide prepared by the method of this embodiment, under the irradiation of an 18W ultraviolet lamp, 100 mL of a methylene blue solution with a concentration of 5 mg/L is catalytically degraded, and the stirring is continued for 2.5 h, and the degradation rate is nearly 100% (see FIG. 5 ).
具体实施方式二：本实施方式与具体实施方式一不同的是：将20mL松香的醇溶液加入到60mL浓度为3mol/L的氢氧化钠溶液中。其它步骤和参数与具体实施方式一相同。Embodiment 2: This embodiment differs from Embodiment 1 in that: 20 mL of rosin alcohol solution is added to 60 mL of sodium hydroxide solution with a concentration of 3 mol/L. Other steps and parameters are the same as in the first embodiment.
用0.1g本实施方式方法制得的花状纳米氧化锌在18W紫外灯的照射下催化降解100mL浓度为5mg/L的亚甲基蓝溶液，持续搅拌2.5h，降解率将近100％(参见图5)。Using 0.1 g of the flower-shaped nano-zinc oxide prepared by the method of this embodiment, under the irradiation of an 18W ultraviolet lamp, 100 mL of a methylene blue solution with a concentration of 5 mg/L is catalytically degraded, and the stirring is continued for 2.5 h, and the degradation rate is nearly 100% (see FIG. 5 ).
具体实施方式三：本实施方式与具体实施方式一不同的是：将20mL松香的醇溶液加入到45mL浓度为4mol/L的氢氧化钠溶液中。其它步骤和参数与具体实施方式一相同。Embodiment 3: This embodiment is different from Embodiment 1 in that: 20 mL of rosin alcohol solution is added to 45 mL of sodium hydroxide solution with a concentration of 4 mol/L. Other steps and parameters are the same as in the first embodiment.
由图3可看出，氧化锌所形成的的纳米棒长度为400纳米，宽度在90纳米左右。It can be seen from FIG. 3 that the nanorods formed by zinc oxide have a length of 400 nanometers and a width of about 90 nanometers.
由图4可看出煅烧后的产品为纯净的氧化锌，不含其它杂质，结晶度高。It can be seen from Fig. 4 that the calcined product is pure zinc oxide, does not contain other impurities, and has high crystallinity.
用0.1g本实施方式方法制得的花状纳米氧化锌在18W紫外灯的照射下催化降解100mL浓度为5mg/L的亚甲基蓝溶液，持续搅拌2.5h，降解率将近100％(参见图5)。Using 0.1 g of the flower-shaped nano-zinc oxide prepared by the method of this embodiment, under the irradiation of an 18W ultraviolet lamp, 100 mL of a methylene blue solution with a concentration of 5 mg/L is catalytically degraded, and the stirring is continued for 2.5 h, and the degradation rate is nearly 100% (see FIG. 5 ).
具体实施方式四：本实施方式与具体实施方式一不同的是：将20mL松香的醇溶液加入到36mL浓度为5mol/L的氢氧化钠溶液中。其它步骤和参数与具体实施方式一相同。Embodiment 4: This embodiment is different from Embodiment 1 in that: 20 mL of rosin alcohol solution is added to 36 mL of sodium hydroxide solution with a concentration of 5 mol/L. Other steps and parameters are the same as in the first embodiment.
用0.1g本实施方式方法制得的花状纳米氧化锌在18W紫外灯的照射下催化降解100mL浓度为5mg/L的亚甲基蓝溶液，持续搅拌2.5h，降解率将近100％(参见图5)。Using 0.1 g of the flower-shaped nano-zinc oxide prepared by the method of this embodiment, under the irradiation of an 18W ultraviolet lamp, 100 mL of a methylene blue solution with a concentration of 5 mg/L is catalytically degraded, and the stirring is continued for 2.5 h, and the degradation rate is nearly 100% (see FIG. 5 ).
具体实施方式五：本实施方式与具体实施方式一不同的是：将陈化后的溶液倒入内衬聚四氟乙烯的高压水热反应釜，置于75℃烘箱中5h。其它步骤和参数与具体实施方式一相同。Embodiment 5: This embodiment is different from Embodiment 1 in that: the aged solution is poured into a high-pressure hydrothermal reactor lined with polytetrafluoroethylene, and placed in an oven at 75°C for 5 hours. Other steps and parameters are the same as in the first embodiment.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029696A (en) * | 2017-05-12 | 2017-08-11 | 济南大学 | A kind of method that use green solvent prepares zinc oxide mesopore material at room temperature |
| CN107128965A (en) * | 2017-05-31 | 2017-09-05 | 上海紫东薄膜材料股份有限公司 | A kind of preparation method of the nano zine oxide with barrier ultraviolet light and blue light |
| CN107737942A (en) * | 2017-10-23 | 2018-02-27 | 南京工程学院 | A kind of Zero-valent Iron/flower shape zinc oxide nano composite material and preparation method thereof |
| CN108344793A (en) * | 2018-02-08 | 2018-07-31 | 亿纳谱（天津）医学检验中心有限公司 | A kind of matrix and preparation method thereof, the mass spectral analysis detection method of metabolic molecule |
| CN111392765A (en) * | 2020-05-08 | 2020-07-10 | 天津翔龙电子有限公司 | Process for preparing ZnO nano-particles by hydrothermal method |
| CN114084901A (en) * | 2021-11-25 | 2022-02-25 | 广州先护特农业科技有限公司 | Nano antibacterial material and preparation method and application thereof |
| CN114409923A (en) * | 2021-11-25 | 2022-04-29 | 华南农业大学 | Multifunctional self-healing antibacterial hydrogel and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118903A (en) * | 2014-07-31 | 2014-10-29 | 济南大学 | Method for preparing three-dimensional flower-shaped zinc oxide nano material |
| CN104229864A (en) * | 2014-09-09 | 2014-12-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Low-temperature preparation method of morphology-controllable zinc oxide nano materials |
| CN104445367A (en) * | 2014-11-13 | 2015-03-25 | 华侨大学 | Preparation method of nanoflower-shaped zinc oxide |
-
2016
- 2016-01-26 CN CN201610051964.8A patent/CN105540640B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118903A (en) * | 2014-07-31 | 2014-10-29 | 济南大学 | Method for preparing three-dimensional flower-shaped zinc oxide nano material |
| CN104229864A (en) * | 2014-09-09 | 2014-12-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Low-temperature preparation method of morphology-controllable zinc oxide nano materials |
| CN104445367A (en) * | 2014-11-13 | 2015-03-25 | 华侨大学 | Preparation method of nanoflower-shaped zinc oxide |
Non-Patent Citations (2)
| Title |
|---|
| 余方丹: "木质素基两性表面活性剂对ZnO纳米晶控制制备", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 陈素文: "《松香松节油深度加工技术与利用》", 31 January 1997 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029696A (en) * | 2017-05-12 | 2017-08-11 | 济南大学 | A kind of method that use green solvent prepares zinc oxide mesopore material at room temperature |
| CN107128965A (en) * | 2017-05-31 | 2017-09-05 | 上海紫东薄膜材料股份有限公司 | A kind of preparation method of the nano zine oxide with barrier ultraviolet light and blue light |
| CN107737942A (en) * | 2017-10-23 | 2018-02-27 | 南京工程学院 | A kind of Zero-valent Iron/flower shape zinc oxide nano composite material and preparation method thereof |
| CN107737942B (en) * | 2017-10-23 | 2020-05-19 | 南京工程学院 | A zero-valent iron/flower-like zinc oxide nanocomposite material and preparation method thereof |
| CN108344793A (en) * | 2018-02-08 | 2018-07-31 | 亿纳谱（天津）医学检验中心有限公司 | A kind of matrix and preparation method thereof, the mass spectral analysis detection method of metabolic molecule |
| CN108344793B (en) * | 2018-02-08 | 2023-08-25 | 浙江亿纳谱生命科技有限公司 | Matrix, preparation method thereof and mass spectrometry detection method of metabolic molecules |
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| CN114084901B (en) * | 2021-11-25 | 2023-11-24 | 广州先护特农业科技有限公司 | Nano antibacterial material and preparation method and application thereof |
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