WO2020215244A1 - Zinc oxide microcrystalline fiber and low-temperature template-free hydrothermal synthesis method therefor - Google Patents

Zinc oxide microcrystalline fiber and low-temperature template-free hydrothermal synthesis method therefor Download PDF

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WO2020215244A1
WO2020215244A1 PCT/CN2019/084073 CN2019084073W WO2020215244A1 WO 2020215244 A1 WO2020215244 A1 WO 2020215244A1 CN 2019084073 W CN2019084073 W CN 2019084073W WO 2020215244 A1 WO2020215244 A1 WO 2020215244A1
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zinc oxide
zinc
oxide microcrystalline
microcrystalline fiber
surfactant
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PCT/CN2019/084073
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French (fr)
Chinese (zh)
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尚颂民
赵家乐
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香港纺织及成衣研发中心有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides

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  • the invention belongs to the field of micro-nano material synthesis, and specifically relates to a zinc oxide microcrystalline fiber and a low-temperature template-free hydrothermal synthesis method thereof, that is, a low-temperature hydrothermal synthesis method of micron-level zinc oxide microcrystalline fiber is studied.
  • Zinc oxide is very important to today's industry and daily life. It is usually a white insoluble powder and can be widely used as a white pigment in many products such as textiles, rubber, plastics, ceramics, glass, cement, paint and ointment. At the same time, it is a well-known n-type semiconductor with a wide and direct band gap of about 3.37 eV, and a large free exciton binding energy (about 60 meV) at room temperature, which makes zinc oxide useful as thin film transistors and dyes Effective semiconductor material for sensitized solar cells, piezoelectric devices and glucose sensors.
  • Zinc oxide crystals have three structures: hexagonal wurtzite structure, cubic sphalerite structure, and relatively rare sodium chloride octahedral structure.
  • the wurtzite structure has the highest stability among the three and is therefore the most common.
  • Zinc oxide also has a variety of morphologies, such as: zinc oxide particles, bulk zinc oxide, zinc oxide film, zinc oxide nanowires, etc.
  • one-dimensional zinc oxide microcrystalline fibers have many electronic, optical and catalytic properties that are promising in modern industry, and are called "materials of the future". attention.
  • its price is as high as thousands of dollars per gram, so it is difficult to be widely used. It is usually synthesized by chemical vapor deposition, electrodeposition, electrospinning, and laser-assisted flow deposition, but these methods require complicated equipment such as a vacuum system, making the manufacturing process very expensive.
  • the hydrothermal method has provided a simple and economical method for the preparation of zinc oxide microcrystalline fibers.
  • the Chinese patent document with application publication number CN 104831354 A discloses a ZnO whisker and a method for preparing ZnO whisker based on hydrothermal technology.
  • the method includes the following steps: (1) Dispersant pretreatment process of divalent zinc salt solution: mixing the divalent zinc salt solution and dispersant at room temperature; (2) Settling process of the divalent zinc salt solution: go to step (1) ) Add a precipitant to the obtained divalent zinc salt solution, mix it evenly, adjust the pH of the mixed solution to 8-11 to obtain a precursor solution; (3) Hydrothermal reaction process of the precursor: generate step (2) The precursor solution is directly transferred to the hydrothermal reaction device and reacted hydrothermally at 150°C ⁇ 260°C for 5-15 hours; (4) The washing and drying process of the product: the product obtained after the hydrothermal reaction in step (3) After separation, washing and drying, a ZnO whisker product is obtained, and the length of the ZnO whisker is 50-80 microns.
  • the synthesis temperature of the above method is higher than 100°C, so an autoclave with an inner surface not adhered is required during the synthesis process, and such an autoclave for industrial use is also relatively expensive.
  • the zinc oxide microcrystalline fiber growth in the hydrothermal method requires template material, so an additional process is required to separate the zinc oxide microcrystalline fiber from the template. This not only increases the production time and cost, but also greatly reduces the output, making the zinc oxide microcrystalline fiber unaffordable in practical applications.
  • wet chemical methods including hydrothermal methods to produce zinc oxide microcrystalline fibers on a large scale.
  • the present invention provides a zinc oxide microcrystalline fiber and its low-temperature template-free hydrothermal synthesis method.
  • the method of the present invention for low-temperature template-free wet synthesis of zinc oxide microcrystalline fiber is relatively simple and can avoid expensive equipment such as autoclaves.
  • the use of Zinc oxide microcrystalline fiber does not require any template, which can greatly reduce the production cost of zinc oxide microcrystalline fiber, which is conducive to the large-scale production of zinc oxide microcrystalline fiber and its wide application in daily life.
  • the invention provides a method for low-temperature template-free hydrothermal synthesis of zinc oxide microcrystalline fibers, which includes the following steps:
  • Step 1 The divalent zinc salt is reacted with a strong base in water to obtain a first transparent solution containing Zn(OH) 4 2- ions; the divalent zinc salt is selected from zinc chloride, zinc acetate and zinc nitrate One or more
  • Step 2 The first transparent solution is reacted in a reactor with a non-sticky surface in the presence of a surfactant and the temperature does not exceed 100°C to obtain zinc oxide microcrystalline fibers;
  • the surfactant is selected from one or more of dodecyl sulfate and polyoxyethylene octyl phenyl ether with 9-10 oxyethylene units.
  • the method for synthesizing the zinc oxide microcrystalline fiber provided by the invention is simple and easy to implement, which is beneficial to industrialized production and popularization and application.
  • the present invention adopts a template-free hydrothermal method to synthesize zinc oxide (ZnO) microcrystalline fibers, and the method mainly uses zinc precursors, alkalis and surfactants as raw materials.
  • the zinc precursor in the method of the present invention is mainly in the form of a divalent zinc salt, and the zinc ion (II)-containing salt is specifically one of zinc chloride (II), zinc acetate (II) and zinc nitrate (II) Or more, preferably zinc chloride (ZnCl 2 ) or zinc acetate (zinc acetate).
  • zinc acetate is usually Zn(CH 3 COO) 2 ⁇ 2H 2 O
  • zinc nitrate is Zn(NO 3 ) 2 ⁇ 6H 2 O.
  • the divalent zinc salt is first dissolved in water, and then a strong base can be added to react under constant stirring to obtain a first transparent solution containing Zn(OH) 4 2- ion.
  • water has two roles in the reaction: first, water acts as a solvent, which is low cost and environmentally friendly; second, water reacts with zinc precursors and alkali to form a soluble intermediate complex Zn(OH ) 4 2- ion.
  • pure water such as distilled water and deionized water is usually used in laboratory operations.
  • the alkali in the method of the present invention is a strongly alkaline or strongly corrosive substance (abbreviated as a strong alkali), and the strong alkali is preferably selected from one or more of sodium hydroxide and potassium hydroxide, more preferably hydroxide sodium.
  • 0.02-0.07 moles (mol) of a divalent zinc salt and a strong base are reacted in 50-200 ml of water, and the concentrations of the divalent zinc salt and the strong base in the water are respectively 0.15- 1.2M and 6 ⁇ 10M, the concentration of strong base is preferably 7M ⁇ 9M; generally, a certain amount of divalent zinc salt is dissolved in water at room temperature, and then the strong base is added under stirring conditions until it reaches 6M ⁇ 10M. Concentration, reaction to obtain a first transparent solution containing Zn(OH) 4 2- ions. Wherein, the amount of the divalent zinc salt is preferably 0.035 to 0.055 mol.
  • the present invention does not have special restrictions on the dissolution, stirring conditions, or alkali addition method, etc., as long as a transparent Zn(OH) 4 2- solution is generated.
  • the embodiment of the present invention mixes it with a surfactant in a reactor with a non-stick surface, and reacts at a low temperature not exceeding 100°C to obtain Zinc oxide microcrystalline fiber.
  • the surfactant is selected from one or more of dodecyl sulfate and polyoxyethylene octyl phenyl ether with 9-10 oxyethylene units; the surfactant
  • the role of ZnO is to prevent the formation of agglomerated particles during the synthesis of zinc oxide microcrystalline fibers, and to make ZnO nano-seeds continue to grow into micro-rods. It has a significant effect on the growth of ZnO from nano-seeds to microcrystalline fibers influences.
  • the dodecyl sulfate mainly refers to sodium lauryl sulfate.
  • the polyoxyethylene octyl phenyl ether with 9-10 oxyethylene units is a nonionic surfactant, which has a hydrophilic polyoxyethylene chain (with an average of 9.5 oxyethylene units) and is hydrophobic
  • the group is an aromatic hydrocarbon group, specifically 4-(1,1,3,3-tetramethylbutyl)phenyl.
  • the English name of the polyoxyethylene octyl phenyl ether is Triton X-100, the molecular formula is C 14 H 22 O(C 2 H 4 O) n , and the structural formula is as follows; the present invention preferably adopts a surfactant of this structure:
  • the surfactant is added to the reactor in the form of an aqueous surfactant solution; the concentration of the aqueous surfactant solution is 20-50 ml/500-2000 ml, that is, 20-50 ml surfactant is dissolved In 500 ml to 2000 ml of water, the surfactant aqueous solution is prepared.
  • the volume of the surfactant can be 25-45 ml, and the volume of water is preferably 800-1500 ml, more preferably 900-1300 ml.
  • the prepared Zn(OH) 4 2- solution and the prepared surfactant aqueous solution are preferably mixed in a non-sticky surface reactor such as a polypropylene container at a volume ratio of 1:6-10.
  • a non-sticky surface reactor such as a polypropylene container at a volume ratio of 1:6-10.
  • 100-300 ml of Zn(OH) 4 2- solution and 600-1000 ml of surfactant solution are mixed in a polypropylene container.
  • the mixture in the non-sticky surface reactor is maintained under normal pressure and the temperature does not exceed 100° C. to perform a hydrothermal reaction.
  • Zn(OH) 4 2- is decomposed into zinc oxide seeds, and the zinc oxide seeds are grown under hydrothermal conditions, and the growth process is controlled by the surfactant, thereby obtaining zinc oxide microcrystalline fibers.
  • the overall reaction formula involved is as follows:
  • the reaction temperature of the hydrothermal process is preferably 80-100°C, such as 80°C, 90°C, 100°C and the like.
  • the invention provides a method for synthesizing zinc oxide microcrystalline fibers by a normal-pressure low-temperature and template-free wet method, which has no stickiness on the surface, no reaction to raw materials, and sufficient thermal stability to withstand low-temperature ( ⁇ 100°C) hydrothermal reaction. Both can be used as the reactor in the method of the present invention; industrial reactors with non-sticky surfaces, such as metal vessels with non-stick Teflon coating, or made of polypropylene, polybutene, polymethylpentene or Teflon (poly Tetrafluoroethylene) and other polymer containers.
  • the synthesis process of the present invention is atmospheric pressure, so there is no need for an autoclave during the synthesis process, and no need for expensive equipment such as a vacuum heating system, which is beneficial to the large-scale production of zinc oxide microcrystalline fibers.
  • the zinc precursor, surfactant, alkali and other raw materials of the present invention have abundant sources and low cost; no template material is required in the synthesis process, and no additional process is required to separate the zinc oxide microcrystalline fiber from the template.
  • the present invention can easily change the specific morphology of the zinc oxide microcrystalline fiber by changing the synthesis conditions, for example, to form longer microrods, filaments or microflowers. Therefore, the present invention can greatly reduce the production cost of zinc oxide microcrystalline fiber, and is widely used in our daily life and in coloring, electronics, catalysis and the like.
  • the hydrothermal reaction described in the embodiment of the present invention can be maintained at 80-100° C. for 5 hours to 10 hours, then cooled to room temperature, and then separated, washed and dried in sequence to obtain zinc oxide microcrystalline fibers.
  • the room temperature is well known to those skilled in the art, such as 25°C.
  • the present invention has no special restrictions on the cooling method, operating parameters, etc.
  • the separation can be carried out by centrifugation, specifically at a speed of 5000 rpm, to obtain a white precipitate.
  • the white precipitate was washed several times under the action of ultrasonic waves with water and ethanol to remove unreacted chemical substances, and then centrifuged for recovery.
  • the present invention is preferably dried in the air at 60-100°C for 4-8 hours to obtain dried zinc oxide microcrystalline fibers.
  • Some embodiments of the present invention are based on Zn content, and the yield is about 10-20%.
  • the synthesis method of the zinc oxide microcrystalline fiber of the present invention is relatively simple, the synthesis process can avoid the use of autoclaves and vacuum heating systems, and does not require any complicated equipment and additional processes to separate the zinc oxide microcrystalline fiber from the template Therefore, zinc oxide microcrystalline fiber can be produced at low cost, which is beneficial to the large-scale production of zinc oxide microcrystalline fiber and its wide application in daily life.
  • the embodiment of the present invention provides a zinc oxide microcrystalline fiber having a hexagonal wurtzite crystal structure, which can be obtained by the above-mentioned synthesis method.
  • "Fiber” refers to a substance composed of continuous or discontinuous filaments, including long fibers and short fibers, and can also be classified according to different cross-sections.
  • the zinc oxide microcrystalline fiber (ZnO microcrystalline fiber) of the present invention is mainly a zinc oxide crystalline fiber with a size of micrometer ( ⁇ m), and can also be called a zinc oxide microrod.
  • the zinc oxide microcrystalline fibers may have a diameter of 0.1 ⁇ m to 5 ⁇ m and a length of 1 ⁇ m to 49 ⁇ m.
  • some zinc oxide microcrystalline fibers have a diameter of 0.1 to 0.2 ⁇ m or 0.3 to 0.5 ⁇ m, and a length of 3 to 4 ⁇ m or 5 to 10 ⁇ m, which may have various combinations.
  • the zinc oxide microcrystalline fiber has a diameter of 0.8 ⁇ m to 2.6 ⁇ m and a length of 10 ⁇ m to 40 ⁇ m.
  • the zinc oxide microcrystalline fibers described in the embodiments of the present invention can have different specific morphologies such as long microrods, filaments and microflowers. Therefore, the present invention has a wide range of applications in coloring, electronics, catalysis, etc., and can also be used in our There are more application prospects in daily life.
  • Figure 1 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 1 under 10 ⁇ m;
  • Example 2 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 1 under 20 ⁇ m;
  • Figure 3 is an XRD pattern of zinc oxide microcrystalline fibers prepared in Example 1-3;
  • Example 4 is a scanning electron microscope image of zinc oxide microcrystalline fibers prepared by using zinc acetate in Example 2 under 10 ⁇ m;
  • Figure 5 is a scanning electron microscope image of zinc oxide microcrystalline fibers prepared by zinc acetate in Example 2 under 5 ⁇ m;
  • Figure 6 is a scanning electron microscope image of zinc oxide microcrystalline fibers prepared by zinc nitrate in Example 3 under 5 ⁇ m;
  • Figure 7 is an XRD pattern of zinc oxide microcrystalline fibers prepared in Example 4-5;
  • Example 8 is an SEM image of zinc oxide microcrystalline fibers prepared by using 0.279M zinc chloride in Example 4;
  • Figure 9 is an SEM image of zinc oxide microcrystalline fibers prepared by using 0.448M zinc chloride in Example 5;
  • Figure 10 is an XRD pattern of zinc oxide microcrystalline fibers prepared in Examples 6-7;
  • Figure 11 is an SEM image of zinc oxide microcrystalline fibers prepared at a synthesis temperature of 80°C;
  • Figure 12 is an SEM image of zinc oxide microcrystalline fibers prepared at a synthesis temperature of 90°C;
  • Figure 13 is the XRD pattern of the zinc oxide microcrystalline fiber prepared in Example 8.
  • Figure 14 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 8.
  • Example 15 is an XRD pattern of the zinc oxide microcrystalline fiber prepared in Example 9;
  • Example 16 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 9.
  • Triton X-100 solution was prepared by dissolving 30 ml Triton X-100 in 900 ml deionized water. 118 mL of the prepared Zn(OH) 4 2- solution and 882 mL of Triton X-100 solution were mixed in a 1 L polypropylene container, and the resulting mixture was reacted at 100° C.
  • the resulting reaction solution was cooled to room temperature. Centrifuge the cooled reaction solution at a speed of 5000 rpm to obtain a white precipitate. Under the action of ultrasound, the white precipitate was washed several times with deionized water and ethanol to remove unreacted chemical substances, and then centrifuged to recover. Finally, the washed white precipitate was dried in the air at 60°C for 4 hours to obtain dried zinc oxide microrods.
  • the scanning electron microscope (SEM) images of the prepared zinc oxide microcrystalline fibers are shown in Figure 1 and Figure 2, which clearly shows that the obtained sample is rod-shaped.
  • the zinc oxide microcrystalline fiber has a diameter of about 0.8-2.6 ⁇ m and a length of about 10-40 ⁇ m.
  • the crystal structure of zinc oxide microcrystalline fibers was studied by X-ray diffraction (XRD), and the results are shown in Figure 3. Observed in Figure 3, the peaks are completely assigned to the hexagonal wurtzite ZnO structure (JCPDS, 36-1451), and no diffraction peaks of Zn and other impurities are found, that is, the crystal structure of the obtained zinc oxide microcrystalline fiber is hexagonal wurtzite Mine structure.
  • Example 1 According to the steps of Example 1, different zinc precursors: zinc acetate (Zn(CH 3 COO) 2 ⁇ 2H 2 O) and zinc nitrate (Zn(NO 3 ) 2 ⁇ 6H 2 O) were used to prepare zinc oxide. Microcrystalline fiber.
  • the XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 3, and its crystal structure is a hexagonal wurtzite structure.
  • the SEM images of zinc oxide microcrystalline fibers prepared with zinc acetate (II) as the zinc precursor are shown in Figures 4 and 5, and the SEM images of zinc oxide microcrystalline fibers prepared with zinc (II) nitrate as the zinc precursor are shown in Figure 6. .
  • the zinc oxide microcrystalline fiber prepared with ZnCl 2 as the zinc cation precursor chemical material has the largest length and diameter, with a diameter of about 0.8-2.6 ⁇ m and a length of about 10-40 ⁇ m.
  • the zinc oxide microcrystalline fiber prepared with Zn(CH 3 COO) 2 ⁇ 2H 2 O as the precursor chemical material of zinc cation has a diameter of 300-500nm (about 0.4 ⁇ m on average) and a length of 5-10 ⁇ m (about 10 ⁇ m on average) ); It is rod-shaped as a whole, and has a pencil-like tip.
  • the length and diameter of zinc oxide microcrystalline fiber prepared with Zn(NO 3 ) 2 ⁇ 6H 2 O as the precursor chemical raw material for zinc cations is the smallest, with a diameter of about 200-500 nm and a length of about 2-5 ⁇ m; it is in the shape of rice (a rice-like shape), part of the fibers are connected together in the form of nano-flowers.
  • Example 1 According to the steps of Example 1, using different ZnCl 2 concentrations: 0.297M and 0.448M, respectively, zinc oxide microcrystalline fibers were prepared.
  • the XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 7, and its crystal structure is a hexagonal wurtzite structure.
  • the SEM image of the zinc oxide microcrystalline fiber prepared with 0.297M ZnCl 2 concentration is shown in FIG. 8, and the SEM image of the zinc oxide microcrystalline fiber prepared with 0.448 M ZnCl 2 concentration is shown in FIG. 9.
  • the effects of different concentrations of ZnCl 2 in zinc ion solution on the morphology of zinc oxide microcrystalline fibers are as follows:
  • the resulting microcrystalline fibers are fine needles; their diameter is about 100-200 nm, and their length is about 5 ⁇ m.
  • the diameter and length of the obtained microcrystalline fibers increased significantly to 0.8-2.6 ⁇ m and 10-40 ⁇ m.
  • the ZnCl 2 concentration is increased to 0.448M, the diameter and length of the resulting microcrystalline fibers are significantly reduced, about 200nm and 3-4 ⁇ m, respectively; some fibers are bonded together in the form of solid pieces.
  • Example 1 According to the steps of Example 1, using different synthesis temperatures: 80°C and 90°C, respectively, zinc oxide microcrystalline fibers were prepared.
  • the XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 10, and its crystal structure is a hexagonal wurtzite structure.
  • the SEM image of the zinc oxide microcrystalline fiber prepared with 80°C as the synthesis temperature is shown in FIG. 11, and the SEM image of the zinc oxide microcrystalline fiber prepared with the synthesis temperature of 90°C is shown in FIG. 12.
  • the effects of different synthesis temperatures on the morphology of zinc oxide microcrystalline fibers are as follows:
  • the results show that the diameter and length of the fiber increase with the increase of the reaction temperature.
  • the zinc oxide microcrystalline fiber prepared at a reaction temperature of 80°C has a highly branched, and forms a fan-shaped solid. As the reaction temperature increases, the branching of zinc oxide microcrystalline fibers decreases. When the reaction temperature is 100°C, the zinc oxide microcrystalline fibers have almost no branches.
  • Triton X-100 solution was prepared by dissolving 30 ml Triton X-100 in 900 ml deionized water. Mix 118 mL of the prepared Zn(OH) 4 2- solution and 882 mL of Triton X-100 solution in a 1 L polypropylene container. The resulting mixture was reacted and maintained at 100°C for 5 hours, and then the resulting reaction liquid was cooled to room temperature.
  • the cooled reaction solution was centrifuged to obtain a white precipitate.
  • the white precipitate was washed several times with deionized water and ethanol to remove unreacted chemical substances, and then centrifuged to recover. Finally, the washed white precipitate was dried in the air at 60°C for 4 hours to obtain dried zinc oxide microcrystalline fibers.
  • the XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 13, and its crystal structure is a hexagonal wurtzite structure.
  • the resulting mixture was reacted and maintained at 100°C for 5 hours, and then the resulting reaction liquid was cooled to room temperature. At a speed of 5000 rpm, the cooled reaction solution was centrifuged to obtain a white precipitate. Under the action of ultrasound, the white precipitate was washed several times with deionized water and ethanol to remove unreacted chemical substances, and then centrifuged to recover. Finally, the washed white precipitate was dried in the air at 60°C for 4 hours to obtain dried zinc oxide microrods.
  • the XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 15, and its crystal structure is a hexagonal wurtzite structure. Moreover, for the XRD spectra of all the obtained zinc oxide microcrystalline fibers, the (100) and (101) peaks are more dominant than the standard XRD spectra of ZnO (JCPDS, 36-1451). This is because the zinc oxide microcrystalline fibers have more Preferred growth direction.
  • the scanning electron microscope image of the prepared zinc oxide microcrystalline fiber is shown in Figure 16, which clearly shows that the obtained sample is rod-shaped.
  • the zinc oxide microcrystalline fiber has a diameter of about 0.1 ⁇ m and a length of 3-5 ⁇ m.
  • the synthesis of zinc oxide microcrystalline fiber in the present invention has abundant raw materials and low cost; the synthesis method is relatively simple, the synthesis process can avoid the use of autoclaves and vacuum heating systems, and does not require any complicated equipment and additional processes.
  • the zinc oxide microcrystalline fiber can be produced at low cost, which is beneficial to the large-scale production of zinc oxide microcrystalline fiber and its wide application in daily life.
  • the present invention can easily change the morphology of zinc oxide microcrystalline fibers by changing the synthesis conditions to form long microrods, filaments, microflowers and other specific forms. Therefore, the present invention has a wide range of applications in coloring, electronics, catalysis and the like.

Abstract

A zinc oxide microcrystalline fiber and a low-temperature template-free hydrothermal synthesis method therefor. The method comprises: step 1. a divalent zinc salt reacts with a strong base in water to obtain a first transparent solution containing Zn(OH)4 2-ions, the divalent zinc salt being selected from one or more of zinc chloride, zinc acetate, and zinc nitrate; and step 2. the first transparent solution reacts in a reactor having a non-sticky surface, in the presence of a surfactant and at a temperature does not exceeding 100°C to obtain a zinc oxide microcrystalline fiber, the surfactant being selected from one or more of dodecyl sulfate and polyoxyethylene octyl phenyl ether having 9 or 10 oxyethylene units. The method for synthesizing a zinc oxide microcrystalline fiber is relatively simple, can avoid the use of expensive equipment such as an autoclave, and does not require any template, thereby greatly reducing the production costs of a zinc oxide microcrystalline fiber, and facilitating the large-scale production of the zinc oxide microcrystalline fiber and wide application thereof in daily life.

Description

一种氧化锌微晶纤维及其低温无模板水热合成的方法Zinc oxide microcrystalline fiber and its low-temperature template-free hydrothermal synthesis method 技术领域Technical field
本发明属于微纳米材料合成领域，具体涉及一种氧化锌微晶纤维及其低温无模板水热合成的方法，即对微米级氧化锌微晶纤维的低温水热合成方法进行了研究。The invention belongs to the field of micro-nano material synthesis, and specifically relates to a zinc oxide microcrystalline fiber and a low-temperature template-free hydrothermal synthesis method thereof, that is, a low-temperature hydrothermal synthesis method of micron-level zinc oxide microcrystalline fiber is studied.
背景技术Background technique
氧化锌(ZnO)对当今工业和日常生活都很重要。它通常是一种白色不溶性粉末，可广泛用作纺织品、橡胶、塑料、陶瓷、玻璃、水泥、油漆和油膏等许多产品的白色颜料。同时，它是一种著名的n型半导体，宽而直接的带隙约为3.37eV，在室温下具有较大的自由激子结合能(约60meV)，这使氧化锌可作为薄膜晶体管、染料敏化太阳能电池、压电器件和葡萄糖传感器的有效半导体材料。Zinc oxide (ZnO) is very important to today's industry and daily life. It is usually a white insoluble powder and can be widely used as a white pigment in many products such as textiles, rubber, plastics, ceramics, glass, cement, paint and ointment. At the same time, it is a well-known n-type semiconductor with a wide and direct band gap of about 3.37 eV, and a large free exciton binding energy (about 60 meV) at room temperature, which makes zinc oxide useful as thin film transistors and dyes Effective semiconductor material for sensitized solar cells, piezoelectric devices and glucose sensors.
氧化锌晶体有三种结构：六边纤锌矿结构、立方闪锌矿结构，以及比较罕见的氯化钠式八面体结构，纤锌矿结构在三者中稳定性最高，因而最常见。氧化锌也有多种形态形貌，例如：氧化锌颗粒、块状氧化锌、氧化锌薄膜、氧化锌纳米线等。在各种各样的氧化锌中，一维氧化锌微晶纤维由于具有许多在现代工业中有应用前景的电子、光学和催化性能，而被称为“未来的材料”，引起了人们的广泛关注。然而，它的价格高达每克数千美元，因此很难广泛应用。它通常是通过化学气相沉积、电沉积、静电纺丝和激光辅助流动沉积来合成的，但这些方法需要复杂的设备如真空***，使得制造过程非常昂贵。Zinc oxide crystals have three structures: hexagonal wurtzite structure, cubic sphalerite structure, and relatively rare sodium chloride octahedral structure. The wurtzite structure has the highest stability among the three and is therefore the most common. Zinc oxide also has a variety of morphologies, such as: zinc oxide particles, bulk zinc oxide, zinc oxide film, zinc oxide nanowires, etc. Among the various types of zinc oxide, one-dimensional zinc oxide microcrystalline fibers have many electronic, optical and catalytic properties that are promising in modern industry, and are called "materials of the future". attention. However, its price is as high as thousands of dollars per gram, so it is difficult to be widely used. It is usually synthesized by chemical vapor deposition, electrodeposition, electrospinning, and laser-assisted flow deposition, but these methods require complicated equipment such as a vacuum system, making the manufacturing process very expensive.
近年来，水热法为氧化锌微晶纤维的制备提供了一种简单、经济的方法。例如，申请公布号为CN 104831354 A的中国专利文献公开了一种ZnO晶须及基于水热技术制备ZnO晶须的方法。该方法包括以下步骤：(1)分散剂预处理二价锌盐溶液工序：将二价锌盐溶液与分散剂在室温下混合；(2)二价锌盐溶液的沉降工序：往步骤(1)得到的二价锌盐溶液中添入沉淀剂，混合均匀，调节混合溶液的pH值为8～11，得到前驱体溶液；(3)前驱体的水热反应工序：将步骤(2)生成的前驱体溶液直接转入水热反应装置中，在150℃～260℃ 水热反应5-15小时；(4)产物的洗涤及干燥工序：将步骤(3)中水热反应后得到的产物进行分离、洗涤、干燥后，得到ZnO晶须产品，该ZnO晶须长度在50-80微米。In recent years, the hydrothermal method has provided a simple and economical method for the preparation of zinc oxide microcrystalline fibers. For example, the Chinese patent document with application publication number CN 104831354 A discloses a ZnO whisker and a method for preparing ZnO whisker based on hydrothermal technology. The method includes the following steps: (1) Dispersant pretreatment process of divalent zinc salt solution: mixing the divalent zinc salt solution and dispersant at room temperature; (2) Settling process of the divalent zinc salt solution: go to step (1) ) Add a precipitant to the obtained divalent zinc salt solution, mix it evenly, adjust the pH of the mixed solution to 8-11 to obtain a precursor solution; (3) Hydrothermal reaction process of the precursor: generate step (2) The precursor solution is directly transferred to the hydrothermal reaction device and reacted hydrothermally at 150℃～260℃ for 5-15 hours; (4) The washing and drying process of the product: the product obtained after the hydrothermal reaction in step (3) After separation, washing and drying, a ZnO whisker product is obtained, and the length of the ZnO whisker is 50-80 microns.
但是，上述方法的合成温度高于100℃，因此在合成过程中需要具有不粘贴内表面的高压釜，这种用于工业用途的高压釜也比较昂贵。并且，通常水热法中氧化锌微晶纤维生长需要模板材料，因此需要额外的工艺将氧化锌微晶纤维与模板分离。这不仅增加了生产时间和成本，而且大大降低了产量，使得氧化锌微晶纤维在实际应用中难以负担。综上，现有技术采用包括水热法在内的湿化学法进行氧化锌微晶纤维的规模化生产是非常困难的。However, the synthesis temperature of the above method is higher than 100°C, so an autoclave with an inner surface not adhered is required during the synthesis process, and such an autoclave for industrial use is also relatively expensive. In addition, usually the zinc oxide microcrystalline fiber growth in the hydrothermal method requires template material, so an additional process is required to separate the zinc oxide microcrystalline fiber from the template. This not only increases the production time and cost, but also greatly reduces the output, making the zinc oxide microcrystalline fiber unaffordable in practical applications. In summary, it is very difficult for the prior art to use wet chemical methods including hydrothermal methods to produce zinc oxide microcrystalline fibers on a large scale.
发明内容Summary of the invention
有鉴于此，本发明提供一种氧化锌微晶纤维及其低温无模板水热合成的方法，本发明低温无模板湿法合成氧化锌微晶纤维的方法比较简单，能避免高压釜等昂贵设备的使用，也不需要任何模板，可以大大降低氧化锌微晶纤维的生产成本，利于规模化生产氧化锌微晶纤维及其在日常生活中的广泛应用。In view of this, the present invention provides a zinc oxide microcrystalline fiber and its low-temperature template-free hydrothermal synthesis method. The method of the present invention for low-temperature template-free wet synthesis of zinc oxide microcrystalline fiber is relatively simple and can avoid expensive equipment such as autoclaves. The use of Zinc oxide microcrystalline fiber does not require any template, which can greatly reduce the production cost of zinc oxide microcrystalline fiber, which is conducive to the large-scale production of zinc oxide microcrystalline fiber and its wide application in daily life.
本发明提供一种氧化锌微晶纤维低温无模板水热合成的方法，包括以下步骤：The invention provides a method for low-temperature template-free hydrothermal synthesis of zinc oxide microcrystalline fibers, which includes the following steps:
步骤1、将二价锌盐与强碱在水中反应，得到含Zn(OH) 4 2-离子的第一透明溶液；所述二价锌盐选自氯化锌、醋酸锌和硝酸锌中的一种或多种； Step 1. The divalent zinc salt is reacted with a strong base in water to obtain a first transparent solution containing Zn(OH) 4 2- ions; the divalent zinc salt is selected from zinc chloride, zinc acetate and zinc nitrate One or more
步骤2、将所述第一透明溶液在非粘性表面的反应器中，在表面活性剂存在且温度不超过100℃的条件下进行反应，得到氧化锌微晶纤维； Step 2. The first transparent solution is reacted in a reactor with a non-sticky surface in the presence of a surfactant and the temperature does not exceed 100°C to obtain zinc oxide microcrystalline fibers;
所述表面活性剂选自十二烷基硫酸盐和氧乙烯基单元为9～10个的聚氧乙烯辛基苯基醚中的一种或多种。The surfactant is selected from one or more of dodecyl sulfate and polyoxyethylene octyl phenyl ether with 9-10 oxyethylene units.
本发明提供的氧化锌微晶纤维的合成方法简单易行，利于工业化生产和推广应用。The method for synthesizing the zinc oxide microcrystalline fiber provided by the invention is simple and easy to implement, which is beneficial to industrialized production and popularization and application.
为降低成本等目的，本发明采用无模板水热法合成氧化锌(ZnO)微晶纤维，该方法主要以锌前体、碱和表面活性剂为原料。本发明方法中的锌前体主要是二价锌盐的形式，该含锌离子(II)的盐具体为氯化锌(II)、醋酸锌(II)和硝酸锌(II)中的一种或多种，优选为氯化锌(ZnCl 2)或醋酸锌(乙酸锌)。 此外，醋酸锌通常为Zn(CH 3COO) 2·2H 2O，硝酸锌为Zn(NO 3) 2·6H 2O。 In order to reduce costs and other purposes, the present invention adopts a template-free hydrothermal method to synthesize zinc oxide (ZnO) microcrystalline fibers, and the method mainly uses zinc precursors, alkalis and surfactants as raw materials. The zinc precursor in the method of the present invention is mainly in the form of a divalent zinc salt, and the zinc ion (II)-containing salt is specifically one of zinc chloride (II), zinc acetate (II) and zinc nitrate (II) Or more, preferably zinc chloride (ZnCl 2 ) or zinc acetate (zinc acetate). In addition, zinc acetate is usually Zn(CH 3 COO) 2 ·2H 2 O, and zinc nitrate is Zn(NO 3 ) 2 ·6H 2 O.
本发明实施例首先将所述二价锌盐溶解在水中，然后可在不断搅拌的条件下，添加强碱进行反应，得到含Zn(OH) 4 2-离子的第一透明溶液。其中，水在反应中有两个作用：第一，水起到溶剂的作用，其成本低且环保；第二，水与锌前体和碱发生反应，形成可溶的中间配合物Zn(OH) 4 2-离子。此外，实验室操作中通常采用蒸馏水、去离子水等纯水。本发明方法中的碱是强碱性或强腐蚀性的物质(简称强碱)，所述的强碱优选选自氢氧化钠和氢氧化钾中的一种或多种，更优选为氢氧化钠。 In the embodiment of the present invention, the divalent zinc salt is first dissolved in water, and then a strong base can be added to react under constant stirring to obtain a first transparent solution containing Zn(OH) 4 2- ion. Among them, water has two roles in the reaction: first, water acts as a solvent, which is low cost and environmentally friendly; second, water reacts with zinc precursors and alkali to form a soluble intermediate complex Zn(OH ) 4 2- ion. In addition, pure water such as distilled water and deionized water is usually used in laboratory operations. The alkali in the method of the present invention is a strongly alkaline or strongly corrosive substance (abbreviated as a strong alkali), and the strong alkali is preferably selected from one or more of sodium hydroxide and potassium hydroxide, more preferably hydroxide sodium.
在本发明的具体实施例中，将0.02～0.07摩尔(mol)的二价锌盐与强碱在50～200毫升水中反应，所述二价锌盐与强碱在水中的浓度分别为0.15-1.2M和6～10M，强碱浓度优选为7M～9M；一般先将一定物质的量的二价锌盐于室温溶解在水中，然后在搅拌条件下添加强碱，直到其达到6M～10M的浓度，反应得到含Zn(OH) 4 2-离子的第一透明溶液。其中，所述二价锌盐的物质的量优选为0.035～0.055摩尔。此外，本发明对所述溶解、搅拌条件或碱添加方式等没有特殊限制，生成透明的Zn(OH) 4 2-溶液即可。 In a specific embodiment of the present invention, 0.02-0.07 moles (mol) of a divalent zinc salt and a strong base are reacted in 50-200 ml of water, and the concentrations of the divalent zinc salt and the strong base in the water are respectively 0.15- 1.2M and 6～10M, the concentration of strong base is preferably 7M～9M; generally, a certain amount of divalent zinc salt is dissolved in water at room temperature, and then the strong base is added under stirring conditions until it reaches 6M～10M. Concentration, reaction to obtain a first transparent solution containing Zn(OH) 4 2- ions. Wherein, the amount of the divalent zinc salt is preferably 0.035 to 0.055 mol. In addition, the present invention does not have special restrictions on the dissolution, stirring conditions, or alkali addition method, etc., as long as a transparent Zn(OH) 4 2- solution is generated.
得到含Zn(OH) 4 2-离子的第一透明溶液后，本发明实施例将其与表面活性剂混合在非粘性表面的反应器中，在不超过100℃的低温条件下进行反应，得到氧化锌微晶纤维。 After obtaining the first transparent solution containing Zn(OH) 4 2- ions, the embodiment of the present invention mixes it with a surfactant in a reactor with a non-stick surface, and reacts at a low temperature not exceeding 100°C to obtain Zinc oxide microcrystalline fiber.
在本发明中，所述表面活性剂选自十二烷基硫酸盐和氧乙烯基单元为9～10个的聚氧乙烯辛基苯基醚中的一种或多种；所述表面活性剂的作用是在氧化锌微晶纤维合成过程中，防止形成团聚的粒子，并且使ZnO纳米晶种持续生长成微棒，它对ZnO从纳米晶种成长为微晶纤维在形貌上有显著的影响。其中，所述十二烷基硫酸盐主要指十二烷基硫酸钠。所述氧乙烯基单元为9～10个的聚氧乙烯辛基苯基醚是一种非离子表面活性剂，具有亲水的聚氧乙烯链(平均有9.5个氧乙烯基单元)，且疏水基团为芳香烃基，具体是4-(1,1,3,3-四甲基丁基)苯基。该聚氧乙烯辛基苯基醚的英文名称为Triton X-100，分子式为C 14H 22O(C 2H 4O) n，结构式如下；本发明优选采用此结构的表面活性剂： In the present invention, the surfactant is selected from one or more of dodecyl sulfate and polyoxyethylene octyl phenyl ether with 9-10 oxyethylene units; the surfactant The role of ZnO is to prevent the formation of agglomerated particles during the synthesis of zinc oxide microcrystalline fibers, and to make ZnO nano-seeds continue to grow into micro-rods. It has a significant effect on the growth of ZnO from nano-seeds to microcrystalline fibers influences. Wherein, the dodecyl sulfate mainly refers to sodium lauryl sulfate. The polyoxyethylene octyl phenyl ether with 9-10 oxyethylene units is a nonionic surfactant, which has a hydrophilic polyoxyethylene chain (with an average of 9.5 oxyethylene units) and is hydrophobic The group is an aromatic hydrocarbon group, specifically 4-(1,1,3,3-tetramethylbutyl)phenyl. The English name of the polyoxyethylene octyl phenyl ether is Triton X-100, the molecular formula is C 14 H 22 O(C 2 H 4 O) n , and the structural formula is as follows; the present invention preferably adopts a surfactant of this structure:
Figure PCTCN2019084073-appb-000001
Figure PCTCN2019084073-appb-000001
具体地，所述表面活性剂以表面活性剂水溶液的形式加入反应器；所述表面活性剂水溶液的浓度为20～50毫升/500～2000毫升，也就是将20毫升～50毫升表面活性剂溶解在500毫升～2000毫升水中，制得该表面活性剂水溶液。所述表面活性剂体积可为25～45毫升，水的体积优选为800～1500毫升、更优选为900～1300毫升。本发明一些实施例将上述制备的Zn(OH) 4 2-溶液与制备的表面活性剂水溶液，优选以1:6～10的体积比例，混合在聚丙烯容器等非粘性表面的反应器中。例如，将100-300毫升的Zn(OH) 4 2-溶液和600-1000毫升表面活性剂溶液混合在聚丙烯容器中。 Specifically, the surfactant is added to the reactor in the form of an aqueous surfactant solution; the concentration of the aqueous surfactant solution is 20-50 ml/500-2000 ml, that is, 20-50 ml surfactant is dissolved In 500 ml to 2000 ml of water, the surfactant aqueous solution is prepared. The volume of the surfactant can be 25-45 ml, and the volume of water is preferably 800-1500 ml, more preferably 900-1300 ml. In some embodiments of the present invention, the prepared Zn(OH) 4 2- solution and the prepared surfactant aqueous solution are preferably mixed in a non-sticky surface reactor such as a polypropylene container at a volume ratio of 1:6-10. For example, 100-300 ml of Zn(OH) 4 2- solution and 600-1000 ml of surfactant solution are mixed in a polypropylene container.
本发明实施例将所述非粘性表面的反应器中的混合物于常压下，在温度不超过100℃的条件下保持，进行水热反应。在水热反应过程中，Zn(OH) 4 2-分解为氧化锌种子，且氧化锌种子在水热条件下生长，表面活性剂控制其生长过程，从而得到氧化锌微晶纤维。总体涉及的反应式如下： In the embodiment of the present invention, the mixture in the non-sticky surface reactor is maintained under normal pressure and the temperature does not exceed 100° C. to perform a hydrothermal reaction. During the hydrothermal reaction process, Zn(OH) 4 2- is decomposed into zinc oxide seeds, and the zinc oxide seeds are grown under hydrothermal conditions, and the growth process is controlled by the surfactant, thereby obtaining zinc oxide microcrystalline fibers. The overall reaction formula involved is as follows:
Zn 2++2OH -→Zn(OH) 2             (1)； Zn 2+ + 2OH - → Zn ( OH) 2 (1);
Zn(OH) 2+2H 2O→Zn(OH) 4 2-+2H +    (2)； Zn(OH) 2 +2H 2 O→Zn(OH) 4 2- +2H + (2);
Zn(OH) 4 2-→ZnO+H 2O+2OH -        (3)。 Zn (OH) 4 2- → ZnO + H 2 O + 2OH - (3).
在本发明中，所述水热过程的反应温度优选为80～100℃，例如80℃、90℃、100℃等。本发明提供了一种常压低温无模板湿法合成氧化锌微晶纤维的方法，表面无粘性、对原料无反应、具有足够的热稳定性能承受低温(～100℃)水热反应的任何容器都可以作为本发明方法中的反应器；工业上非粘性表面的反应器例如：带非粘性Teflon涂层的金属容器，或者，由聚丙烯、聚丁烯、聚甲基戊烯或Teflon(聚四氟乙烯)等制成的聚合物容器。本发明合成过程为大气压力，因此在合成过程中不需要高压釜，也不需要真空加热***等昂贵设备，利于规模化生产氧化锌微晶纤维。In the present invention, the reaction temperature of the hydrothermal process is preferably 80-100°C, such as 80°C, 90°C, 100°C and the like. The invention provides a method for synthesizing zinc oxide microcrystalline fibers by a normal-pressure low-temperature and template-free wet method, which has no stickiness on the surface, no reaction to raw materials, and sufficient thermal stability to withstand low-temperature (~100°C) hydrothermal reaction. Both can be used as the reactor in the method of the present invention; industrial reactors with non-sticky surfaces, such as metal vessels with non-stick Teflon coating, or made of polypropylene, polybutene, polymethylpentene or Teflon (poly Tetrafluoroethylene) and other polymer containers. The synthesis process of the present invention is atmospheric pressure, so there is no need for an autoclave during the synthesis process, and no need for expensive equipment such as a vacuum heating system, which is beneficial to the large-scale production of zinc oxide microcrystalline fibers.
同时，本发明锌前体、表面活性剂、碱等原料来源丰富，成本低廉；在合成过程中不需要任何模板材料，也不需要额外的工艺将氧化锌微晶纤维与模板 分离。此外，本发明通过改变合成条件，可以很容易地改变氧化锌微晶纤维的具体形貌，例如形成较长的微棒、细丝或微花。因此，本发明可以大大降低氧化锌微晶纤维的生产成本，在我们的日常生活中以及在着色、电子、催化等方面得到广泛的应用。At the same time, the zinc precursor, surfactant, alkali and other raw materials of the present invention have abundant sources and low cost; no template material is required in the synthesis process, and no additional process is required to separate the zinc oxide microcrystalline fiber from the template. In addition, the present invention can easily change the specific morphology of the zinc oxide microcrystalline fiber by changing the synthesis conditions, for example, to form longer microrods, filaments or microflowers. Therefore, the present invention can greatly reduce the production cost of zinc oxide microcrystalline fiber, and is widely used in our daily life and in coloring, electronics, catalysis and the like.
本发明实施例所述的水热反应可在80～100℃保持5小时～10小时，然后冷却至室温，再依次经分离、洗涤和干燥，得到氧化锌微晶纤维。The hydrothermal reaction described in the embodiment of the present invention can be maintained at 80-100° C. for 5 hours to 10 hours, then cooled to room temperature, and then separated, washed and dried in sequence to obtain zinc oxide microcrystalline fibers.
其中，所述室温为本领域技术人员所熟知的，例如25℃。并且，本发明对所述冷却的方式、操作参数等没有特殊限制。所述分离可采用离心的方式，具体以5000转/分的速度离心，分离得到白色沉淀。本发明一些实施例用水和乙醇在超声波作用下清洗该白色沉淀数次，去除未反应的化学物质，然后离心回收。最后，本发明优选在60～100℃空气中干燥，时间可为4～8小时，获得干燥的氧化锌微晶纤维。本发明一些实施例以Zn含量为基准，产率约为10-20％。Wherein, the room temperature is well known to those skilled in the art, such as 25°C. In addition, the present invention has no special restrictions on the cooling method, operating parameters, etc. The separation can be carried out by centrifugation, specifically at a speed of 5000 rpm, to obtain a white precipitate. In some embodiments of the present invention, the white precipitate was washed several times under the action of ultrasonic waves with water and ethanol to remove unreacted chemical substances, and then centrifuged for recovery. Finally, the present invention is preferably dried in the air at 60-100°C for 4-8 hours to obtain dried zinc oxide microcrystalline fibers. Some embodiments of the present invention are based on Zn content, and the yield is about 10-20%.
本发明所述氧化锌微晶纤维的合成方法比较简单，合成过程能避免高压釜和真空加热***的使用，也不需要任何复杂的设备和额外的工艺来将氧化锌微晶纤维从模板中分离出来，从而可以低成本生产氧化锌微晶纤维，利于氧化锌微晶纤维规模化生产及其在日常生活中的广泛应用。The synthesis method of the zinc oxide microcrystalline fiber of the present invention is relatively simple, the synthesis process can avoid the use of autoclaves and vacuum heating systems, and does not require any complicated equipment and additional processes to separate the zinc oxide microcrystalline fiber from the template Therefore, zinc oxide microcrystalline fiber can be produced at low cost, which is beneficial to the large-scale production of zinc oxide microcrystalline fiber and its wide application in daily life.
本发明实施例提供一种氧化锌微晶纤维，具有六方纤锌矿晶体结构，可由上文所述的合成方法获得。“纤维”是指由连续或不连续的细丝组成的物质，有长纤维、短纤维，也可按照不同的横截面分类。本发明所述的氧化锌微晶纤维(ZnO microcrystalline fiber)主要是尺寸为微米(μm)级别的氧化锌晶体纤维，也可称为氧化锌微棒(zinc oxide microrod)。The embodiment of the present invention provides a zinc oxide microcrystalline fiber having a hexagonal wurtzite crystal structure, which can be obtained by the above-mentioned synthesis method. "Fiber" refers to a substance composed of continuous or discontinuous filaments, including long fibers and short fibers, and can also be classified according to different cross-sections. The zinc oxide microcrystalline fiber (ZnO microcrystalline fiber) of the present invention is mainly a zinc oxide crystalline fiber with a size of micrometer (μm), and can also be called a zinc oxide microrod.
在本发明的一些实施例中，所述氧化锌微晶纤维的直径可为0.1μm～5μm，长度为1μm～49μm。例如，一些氧化锌微晶纤维的直径为0.1～0.2μm或0.3～0.5μm，长度为3～4μm或5～10μm，可具有多种组合。作为优选，所述氧化锌微晶纤维的直径为0.8μm～2.6μm，长度为10μm～40μm。In some embodiments of the present invention, the zinc oxide microcrystalline fibers may have a diameter of 0.1 μm to 5 μm and a length of 1 μm to 49 μm. For example, some zinc oxide microcrystalline fibers have a diameter of 0.1 to 0.2 μm or 0.3 to 0.5 μm, and a length of 3 to 4 μm or 5 to 10 μm, which may have various combinations. Preferably, the zinc oxide microcrystalline fiber has a diameter of 0.8 μm to 2.6 μm and a length of 10 μm to 40 μm.
本发明实施例所述氧化锌微晶纤维可为长的微棒、细丝和微花等不同的具体形貌，因此本发明在着色、电子、催化等方面具有广泛的应用，也可在我们日常生活中有更多的应用前景。The zinc oxide microcrystalline fibers described in the embodiments of the present invention can have different specific morphologies such as long microrods, filaments and microflowers. Therefore, the present invention has a wide range of applications in coloring, electronics, catalysis, etc., and can also be used in our There are more application prospects in daily life.
附图说明Description of the drawings
图1为实施例1制备的氧化锌微晶纤维10μm下的扫描电镜图像；Figure 1 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 1 under 10 μm;
图2为实施例1制备的氧化锌微晶纤维20μm下的扫描电镜图像；2 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 1 under 20 μm;
图3为实施例1-3制备的氧化锌微晶纤维的XRD图谱；Figure 3 is an XRD pattern of zinc oxide microcrystalline fibers prepared in Example 1-3;
图4为实施例2采用醋酸锌制备的氧化锌微晶纤维10μm下的扫描电镜图像；4 is a scanning electron microscope image of zinc oxide microcrystalline fibers prepared by using zinc acetate in Example 2 under 10 μm;
图5为实施例2采用醋酸锌制备的氧化锌微晶纤维5μm下的扫描电镜图像；Figure 5 is a scanning electron microscope image of zinc oxide microcrystalline fibers prepared by zinc acetate in Example 2 under 5 μm;
图6为实施例3采用硝酸锌制备的氧化锌微晶纤维5μm下的扫描电镜图像；Figure 6 is a scanning electron microscope image of zinc oxide microcrystalline fibers prepared by zinc nitrate in Example 3 under 5 μm;
图7为实施例4-5制备的氧化锌微晶纤维的XRD图谱；Figure 7 is an XRD pattern of zinc oxide microcrystalline fibers prepared in Example 4-5;
图8为实施例4采用0.279M氯化锌制备的氧化锌微晶纤维的SEM图像；8 is an SEM image of zinc oxide microcrystalline fibers prepared by using 0.279M zinc chloride in Example 4;
图9为实施例5采用0.448M氯化锌制备的氧化锌微晶纤维的SEM图像；Figure 9 is an SEM image of zinc oxide microcrystalline fibers prepared by using 0.448M zinc chloride in Example 5;
图10为实施例6-7制备的氧化锌微晶纤维的XRD图谱；Figure 10 is an XRD pattern of zinc oxide microcrystalline fibers prepared in Examples 6-7;
图11为采用80℃合成温度制备的氧化锌微晶纤维的SEM图像；Figure 11 is an SEM image of zinc oxide microcrystalline fibers prepared at a synthesis temperature of 80°C;
图12为采用90℃合成温度制备的氧化锌微晶纤维的SEM图像；Figure 12 is an SEM image of zinc oxide microcrystalline fibers prepared at a synthesis temperature of 90°C;
图13为实施例8制备的氧化锌微晶纤维的XRD图谱；Figure 13 is the XRD pattern of the zinc oxide microcrystalline fiber prepared in Example 8;
图14为实施例8制备的氧化锌微晶纤维的扫描电镜图像；Figure 14 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 8;
图15为实施例9制备的氧化锌微晶纤维的XRD图谱；15 is an XRD pattern of the zinc oxide microcrystalline fiber prepared in Example 9;
图16为实施例9制备的氧化锌微晶纤维的扫描电镜图像。16 is a scanning electron microscope image of the zinc oxide microcrystalline fiber prepared in Example 9.
具体实施方式Detailed ways
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following describes the technical solutions in the embodiments of the present invention clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
为了进一步理解本申请，下面结合实施例对本发明提供的一种氧化锌微晶纤维及其低温无模板水热合成的方法进行具体地描述。以下实施例所用试剂为市售产品。In order to further understand the present application, a detailed description of a zinc oxide microcrystalline fiber and its low-temperature template-free hydrothermal synthesis method provided by the present invention will be given below in conjunction with examples. The reagents used in the following examples are commercially available products.
实施例1Example 1
在典型的合成中，将0.037摩尔氯化锌(II)溶解在100毫升去离子水中，浓度为0.371M，然后在不断搅拌下添加氢氧化钠(NaOH)，直到达到8M的浓度，生成透明的Zn(OH) 4 2-溶液。Triton X-100溶液是通过将30毫升Triton X-100溶解在900毫升去离子水中制备的。将118mL制备的Zn(OH) 4 2-溶液和882mL Triton X-100溶液混合在1L聚丙烯容器中，将所得混合物在100℃下反应保持5小时，然后所得反应液冷却至室温。以5000转/分的速度，将冷却的反应液离心，得到白色沉淀。在超声波作用下，用去离子水和乙醇清洗该白色沉淀数次，去除未反应的化学物质，然后离心回收。最后，将洗涤后的白色沉淀在60℃的空气中干燥4小时，获得干燥的氧化锌微棒。 In a typical synthesis, 0.037 mol of zinc (II) chloride is dissolved in 100 ml of deionized water with a concentration of 0.371M, and then sodium hydroxide (NaOH) is added under constant stirring until it reaches a concentration of 8M, resulting in a transparent Zn(OH) 4 2- solution. The Triton X-100 solution was prepared by dissolving 30 ml Triton X-100 in 900 ml deionized water. 118 mL of the prepared Zn(OH) 4 2- solution and 882 mL of Triton X-100 solution were mixed in a 1 L polypropylene container, and the resulting mixture was reacted at 100° C. for 5 hours, and then the resulting reaction solution was cooled to room temperature. Centrifuge the cooled reaction solution at a speed of 5000 rpm to obtain a white precipitate. Under the action of ultrasound, the white precipitate was washed several times with deionized water and ethanol to remove unreacted chemical substances, and then centrifuged to recover. Finally, the washed white precipitate was dried in the air at 60°C for 4 hours to obtain dried zinc oxide microrods.
制备的氧化锌微晶纤维的扫描电镜(SEM)图像如图1、图2所示，它清楚地表明所得的样品是棒状的。所述氧化锌微晶纤维的直径约为0.8-2.6μm，长度约为10-40μm。The scanning electron microscope (SEM) images of the prepared zinc oxide microcrystalline fibers are shown in Figure 1 and Figure 2, which clearly shows that the obtained sample is rod-shaped. The zinc oxide microcrystalline fiber has a diameter of about 0.8-2.6 μm and a length of about 10-40 μm.
用X射线衍射(XRD)研究了氧化锌微晶纤维的晶体结构，结果如图3所示。图3中观察得到，峰完全分配给六方纤锌矿ZnO结构(JCPDS，36-1451)，未发现Zn和其它杂质的衍射峰，即所得到的氧化锌微晶纤维的晶体结构为六方纤锌矿结构。The crystal structure of zinc oxide microcrystalline fibers was studied by X-ray diffraction (XRD), and the results are shown in Figure 3. Observed in Figure 3, the peaks are completely assigned to the hexagonal wurtzite ZnO structure (JCPDS, 36-1451), and no diffraction peaks of Zn and other impurities are found, that is, the crystal structure of the obtained zinc oxide microcrystalline fiber is hexagonal wurtzite Mine structure.
实施例2-3Example 2-3
按照实施例1的步骤，采用不同的锌前体：醋酸锌(Zn(CH 3COO) 2·2H 2O)、硝酸锌(Zn(NO 3) 2·6H 2O)，分别制备得到氧化锌微晶纤维。 According to the steps of Example 1, different zinc precursors: zinc acetate (Zn(CH 3 COO) 2 ·2H 2 O) and zinc nitrate (Zn(NO 3 ) 2 ·6H 2 O) were used to prepare zinc oxide. Microcrystalline fiber.
所得氧化锌微晶纤维的XRD谱如图3所示，其晶体结构为六方纤锌矿结构。The XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 3, and its crystal structure is a hexagonal wurtzite structure.
以醋酸锌(II)为锌前体制备的氧化锌微晶纤维的SEM图像参见图4、图5，以硝酸锌(II)为锌前体制备的氧化锌微晶纤维的SEM图像参见图6。与这两种锌阳离子前驱体相比，以ZnCl 2为锌阳离子前驱体化学材料制备的氧化锌微晶纤维的长度和直径最大，直径约0.8～2.6μm，长度约10-40μm。 The SEM images of zinc oxide microcrystalline fibers prepared with zinc acetate (II) as the zinc precursor are shown in Figures 4 and 5, and the SEM images of zinc oxide microcrystalline fibers prepared with zinc (II) nitrate as the zinc precursor are shown in Figure 6. . Compared with the two zinc cation precursors, the zinc oxide microcrystalline fiber prepared with ZnCl 2 as the zinc cation precursor chemical material has the largest length and diameter, with a diameter of about 0.8-2.6 μm and a length of about 10-40 μm.
同时，图2等图像还清楚地显示出横截面和铅笔状的尖端(a pencil-like tip)。以Zn(CH 3COO) 2·2H 2O为锌阳离子前驱体化学材料制备的氧化锌微晶纤维的直径为300～500nm(平均约为0.4μm)，长度为5～10μm(平均约为10μm)；它整体是棒状的，也有一个类似铅笔的尖端。以Zn(NO 3) 2·6H 2O为锌阳离子前 驱体化学原料制备的氧化锌微晶纤维的长度和直径最小，其直径约为200～500nm，长度约为2～5μm；它呈大米形状(a rice-like shape)，部分纤维以纳米花(nano-flower)的形式连接在一起。 At the same time, images such as Figure 2 clearly show the cross-section and a pencil-like tip. The zinc oxide microcrystalline fiber prepared with Zn(CH 3 COO) 2 ·2H 2 O as the precursor chemical material of zinc cation has a diameter of 300-500nm (about 0.4μm on average) and a length of 5-10μm (about 10μm on average) ); It is rod-shaped as a whole, and has a pencil-like tip. The length and diameter of zinc oxide microcrystalline fiber prepared with Zn(NO 3 ) 2 ·6H 2 O as the precursor chemical raw material for zinc cations is the smallest, with a diameter of about 200-500 nm and a length of about 2-5 μm; it is in the shape of rice (a rice-like shape), part of the fibers are connected together in the form of nano-flowers.
实施例4-5Example 4-5
按照实施例1的步骤，采用不同的ZnCl 2浓度：0.297M、0.448M，分别制备得到氧化锌微晶纤维。 According to the steps of Example 1, using different ZnCl 2 concentrations: 0.297M and 0.448M, respectively, zinc oxide microcrystalline fibers were prepared.
所得氧化锌微晶纤维的XRD谱如图7所示，其晶体结构为六方纤锌矿结构。The XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 7, and its crystal structure is a hexagonal wurtzite structure.
采用0.297M ZnCl 2浓度制备的氧化锌微晶纤维的SEM图像参见图8，采用0.448M ZnCl 2浓度制备的氧化锌微晶纤维的SEM图像参见图9。ZnCl 2在锌离子溶液中不同浓度对氧化锌微晶纤维形态的影响如下： The SEM image of the zinc oxide microcrystalline fiber prepared with 0.297M ZnCl 2 concentration is shown in FIG. 8, and the SEM image of the zinc oxide microcrystalline fiber prepared with 0.448 M ZnCl 2 concentration is shown in FIG. 9. The effects of different concentrations of ZnCl 2 in zinc ion solution on the morphology of zinc oxide microcrystalline fibers are as follows:
当ZnCl 2浓度为0.297M时，得到的微晶纤维为细针(fine needles)；其直径为约100-200nm，而其长度约为5μm。当ZnCl 2浓度增加到0.371M时，得到的微晶纤维的直径和长度显著增加到0.8-2.6μm和10-40μm。另一方面，当ZnCl 2浓度增加到0.448M时，所得微晶纤维的直径和长度显著减小，分别约为200nm和3～4μm；一些纤维以固体(solid pieces)的形式粘合在一起。 When the ZnCl 2 concentration is 0.297M, the resulting microcrystalline fibers are fine needles; their diameter is about 100-200 nm, and their length is about 5 μm. When the ZnCl 2 concentration increased to 0.371M, the diameter and length of the obtained microcrystalline fibers increased significantly to 0.8-2.6μm and 10-40μm. On the other hand, when the ZnCl 2 concentration is increased to 0.448M, the diameter and length of the resulting microcrystalline fibers are significantly reduced, about 200nm and 3-4μm, respectively; some fibers are bonded together in the form of solid pieces.
实施例6-7Example 6-7
按照实施例1的步骤，采用不同的合成温度：80℃、90℃，分别制备得到氧化锌微晶纤维。According to the steps of Example 1, using different synthesis temperatures: 80°C and 90°C, respectively, zinc oxide microcrystalline fibers were prepared.
所得氧化锌微晶纤维的XRD谱如图10所示，其晶体结构为六方纤锌矿结构。The XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 10, and its crystal structure is a hexagonal wurtzite structure.
以80℃为合成温度制备的氧化锌微晶纤维的SEM图像参见图11，以90℃为合成温度制备的氧化锌微晶纤维的SEM图像参见图12。不同合成温度对氧化锌微晶纤维形貌的影响如下：The SEM image of the zinc oxide microcrystalline fiber prepared with 80°C as the synthesis temperature is shown in FIG. 11, and the SEM image of the zinc oxide microcrystalline fiber prepared with the synthesis temperature of 90°C is shown in FIG. 12. The effects of different synthesis temperatures on the morphology of zinc oxide microcrystalline fibers are as follows:
结果表明，纤维的直径和长度随反应温度的升高而增大。同时，反应温度为80℃制备的氧化锌微晶纤维具有高度分枝(highly branched)，且形成扇形固体(a fan-shaped solid)。随着反应温度的升高，氧化锌微晶纤维的分枝减少。当反应温度为100℃时，氧化锌微晶纤维几乎没有分枝。The results show that the diameter and length of the fiber increase with the increase of the reaction temperature. At the same time, the zinc oxide microcrystalline fiber prepared at a reaction temperature of 80°C has a highly branched, and forms a fan-shaped solid. As the reaction temperature increases, the branching of zinc oxide microcrystalline fibers decreases. When the reaction temperature is 100°C, the zinc oxide microcrystalline fibers have almost no branches.
实施例8Example 8
按照实施例1的步骤，采用不同的强碱：KOH，制备得到氧化锌微晶纤维。 具体如下：According to the steps of Example 1, using different strong bases: KOH, the zinc oxide microcrystalline fibers were prepared. details as follows:
在典型的合成中，将0.037摩尔氯化锌(II)溶解在100毫升去离子水中，然后在不断搅拌下添加氢氧化钾(KOH)，直到达到8M的浓度，生成透明的Zn(OH) 4 2-溶液。Triton X-100溶液是通过将30毫升Triton X-100溶解在900毫升去离子水中制备的。将118mL制备的Zn(OH) 4 2-溶液和882mL Triton X-100溶液混合在1L聚丙烯容器中。将所得混合物在100℃下反应保持5小时，然后所得反应液冷却至室温。以5000转/分的速度，将冷却的反应液通过离心分离，得到白色沉淀。在超声波作用下，用去离子水和乙醇清洗该白色沉淀数次，去除未反应的化学物质，然后离心回收。最后，将洗涤后的白色沉淀在60℃的空气中干燥4小时，获得干燥的氧化锌微晶纤维。 In a typical synthesis, 0.037 mol of zinc (II) chloride is dissolved in 100 ml of deionized water, and then potassium hydroxide (KOH) is added under constant stirring until it reaches a concentration of 8M, resulting in a transparent Zn(OH) 4 2- Solution. The Triton X-100 solution was prepared by dissolving 30 ml Triton X-100 in 900 ml deionized water. Mix 118 mL of the prepared Zn(OH) 4 2- solution and 882 mL of Triton X-100 solution in a 1 L polypropylene container. The resulting mixture was reacted and maintained at 100°C for 5 hours, and then the resulting reaction liquid was cooled to room temperature. At a speed of 5000 rpm, the cooled reaction solution was centrifuged to obtain a white precipitate. Under the action of ultrasound, the white precipitate was washed several times with deionized water and ethanol to remove unreacted chemical substances, and then centrifuged to recover. Finally, the washed white precipitate was dried in the air at 60°C for 4 hours to obtain dried zinc oxide microcrystalline fibers.
所得氧化锌微晶纤维的XRD谱如图13所示，其晶体结构为六方纤锌矿结构。The XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 13, and its crystal structure is a hexagonal wurtzite structure.
制备的氧化锌微晶纤维的扫描电镜图像如图14所示，它清楚地表明，氧化锌微晶纤维结合在一起，形成直径为2-6μm的微花形状(micro-flower)。与氢氧化钾相比，氢氧化钠具有更好的碱性，因为它提供了大量的氧化锌微晶纤维。The scanning electron microscope image of the prepared zinc oxide microcrystalline fibers is shown in Figure 14, which clearly shows that the zinc oxide microcrystalline fibers are bonded together to form a micro-flower with a diameter of 2-6 μm. Compared with potassium hydroxide, sodium hydroxide has better alkalinity because it provides a large amount of zinc oxide microcrystalline fibers.
实施例9Example 9
按照实施例1的步骤，采用不同的表面活性剂：十二烷基硫酸钠，制备得到氧化锌微晶纤维。具体如下：According to the steps of Example 1, different surfactants: sodium lauryl sulfate were used to prepare zinc oxide microcrystalline fibers. details as follows:
在典型的合成中，将0.037摩尔氯化锌(II)溶解在100毫升去离子水中，然后在不断搅拌下添加氢氧化钠，直到达到8M的浓度，生成透明的Zn(OH) 4 2-溶液。十二烷基硫酸钠溶液是将30毫升十二烷基硫酸钠溶解在900毫升去离子水中制备的。将118毫升制备的Zn(OH) 4 2-溶液和882毫升十二烷基硫酸钠溶液混合在1升聚丙烯容器中。将所得混合物在100℃下反应保持5小时，然后所得反应液冷却至室温。以5000转/分的速度，将冷却的反应液通过离心分离，得到白色沉淀。在超声波作用下，用去离子水和乙醇清洗该白色沉淀数次，去除未反应的化学物质，然后离心回收。最后，将洗涤后的白色沉淀在60℃的空气中干燥4小时，获得干燥的氧化锌微棒。 In a typical synthesis, 0.037 mol of zinc (II) chloride is dissolved in 100 ml of deionized water, and then sodium hydroxide is added with constant stirring until it reaches a concentration of 8M, resulting in a transparent Zn(OH) 4 2- solution . The sodium lauryl sulfate solution was prepared by dissolving 30 ml of sodium lauryl sulfate in 900 ml of deionized water. Mix 118 ml of the prepared Zn(OH) 4 2- solution and 882 ml of sodium lauryl sulfate solution in a 1-liter polypropylene container. The resulting mixture was reacted and maintained at 100°C for 5 hours, and then the resulting reaction liquid was cooled to room temperature. At a speed of 5000 rpm, the cooled reaction solution was centrifuged to obtain a white precipitate. Under the action of ultrasound, the white precipitate was washed several times with deionized water and ethanol to remove unreacted chemical substances, and then centrifuged to recover. Finally, the washed white precipitate was dried in the air at 60°C for 4 hours to obtain dried zinc oxide microrods.
所得氧化锌微晶纤维的XRD谱如图15所示，其晶体结构为六方纤锌矿结构。并且，对于所有得到的氧化锌微晶纤维的XRD谱，(100)和(101)峰比 ZnO(JCPDS，36-1451)的标准XRD谱更占优势，这是因为氧化锌微晶纤维具有更优选的生长方向。The XRD spectrum of the obtained zinc oxide microcrystalline fiber is shown in Figure 15, and its crystal structure is a hexagonal wurtzite structure. Moreover, for the XRD spectra of all the obtained zinc oxide microcrystalline fibers, the (100) and (101) peaks are more dominant than the standard XRD spectra of ZnO (JCPDS, 36-1451). This is because the zinc oxide microcrystalline fibers have more Preferred growth direction.
制备的氧化锌微晶纤维的扫描电镜图像如图16所示，它清楚地表明所得的样品是棒状的。所述氧化锌微晶纤维的直径约为0.1μm，长度为3-5μm。The scanning electron microscope image of the prepared zinc oxide microcrystalline fiber is shown in Figure 16, which clearly shows that the obtained sample is rod-shaped. The zinc oxide microcrystalline fiber has a diameter of about 0.1 μm and a length of 3-5 μm.
由以上实施例可知，本发明合成氧化锌微晶纤维的原料丰富，成本低廉；合成方法比较简单，合成过程能避免高压釜和真空加热***的使用，也不需要任何复杂的设备和额外的工艺来将氧化锌微晶纤维从模板中分离出来，从而可以低成本生产氧化锌微晶纤维，利于氧化锌微晶纤维规模化生产及其在日常生活中的广泛应用。并且，本发明通过改变合成条件，可以容易地改变氧化锌微晶纤维的形貌，形成长的微棒、细丝和微花等具体形态。因此，本发明在着色、电子、催化等方面具有广泛的应用。It can be seen from the above examples that the synthesis of zinc oxide microcrystalline fiber in the present invention has abundant raw materials and low cost; the synthesis method is relatively simple, the synthesis process can avoid the use of autoclaves and vacuum heating systems, and does not require any complicated equipment and additional processes. To separate the zinc oxide microcrystalline fiber from the template, the zinc oxide microcrystalline fiber can be produced at low cost, which is beneficial to the large-scale production of zinc oxide microcrystalline fiber and its wide application in daily life. In addition, the present invention can easily change the morphology of zinc oxide microcrystalline fibers by changing the synthesis conditions to form long microrods, filaments, microflowers and other specific forms. Therefore, the present invention has a wide range of applications in coloring, electronics, catalysis and the like.
以上所述仅是本发明的优选实施方式，应当指出，对于使本技术领域的专业技术人员，在不脱离本发明技术原理的前提下，是能够实现对这些实施例的多种修改的，而这些修改也应视为本发明应该保护的范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the technical principles of the present invention, various modifications to these embodiments can be implemented. These modifications should also be regarded as the scope of the present invention.

Claims (10)

  1. 氧化锌微晶纤维低温无模板水热合成的方法，其特征在于，包括以下步骤：The method for low-temperature template-free hydrothermal synthesis of zinc oxide microcrystalline fibers is characterized in that it comprises the following steps:
    步骤1、将二价锌盐与强碱在水中反应，得到含Zn(OH) 4 2-离子的第一透明溶液；所述二价锌盐选自氯化锌、醋酸锌和硝酸锌中的一种或多种； Step 1. The divalent zinc salt is reacted with a strong base in water to obtain a first transparent solution containing Zn(OH) 4 2- ions; the divalent zinc salt is selected from zinc chloride, zinc acetate and zinc nitrate One or more
    步骤2、将所述第一透明溶液在非粘性表面的反应器中，在表面活性剂存在且温度不超过100℃的条件下进行反应，得到氧化锌微晶纤维；Step 2. The first transparent solution is reacted in a reactor with a non-sticky surface in the presence of a surfactant and the temperature does not exceed 100°C to obtain zinc oxide microcrystalline fibers;
    所述表面活性剂选自十二烷基硫酸盐和氧乙烯基单元为9～10个的聚氧乙烯辛基苯基醚中的一种或多种。The surfactant is selected from one or more of dodecyl sulfate and polyoxyethylene octyl phenyl ether with 9-10 oxyethylene units.
  2. 根据权利要求1所述的方法，其特征在于，步骤1中，所述强碱选自氢氧化钠和氢氧化钾中的一种或多种。The method according to claim 1, wherein in step 1, the strong base is selected from one or more of sodium hydroxide and potassium hydroxide.
  3. 根据权利要求1所述的方法，其特征在于，步骤1具体为：将0.02～0.07摩尔的二价锌盐与强碱在50～200毫升水中反应，所述强碱在水中的浓度为6～10M，得到含Zn(OH) 4 2-离子的第一透明溶液。 The method according to claim 1, wherein step 1 specifically includes: reacting 0.02-0.07 moles of divalent zinc salt with a strong base in 50-200 ml of water, and the concentration of the strong base in the water is 6- 10M, a first transparent solution containing Zn(OH) 4 2- ions was obtained.
  4. 根据权利要求3所述的方法，其特征在于，步骤2中，所述表面活性剂以表面活性剂水溶液的形式加入反应器，所述表面活性剂水溶液的浓度为20～50毫升/500～2000毫升，所述第一透明溶液与表面活性剂水溶液的体积比为1:6～10。The method according to claim 3, wherein in step 2, the surfactant is added to the reactor in the form of an aqueous solution of surfactant, and the concentration of the aqueous solution of surfactant is 20-50 ml/500-2000 Milliliter, the volume ratio of the first transparent solution to the aqueous surfactant solution is 1:6-10.
  5. 根据权利要求1～4中任一项所述的方法，其特征在于，步骤2中，所述反应的温度为80～100℃。The method according to any one of claims 1 to 4, wherein in step 2, the reaction temperature is 80-100°C.
  6. 根据权利要求5所述的方法，其特征在于，步骤2中，所述反应保持5～10小时，然后冷却至室温，再依次经分离、洗涤和干燥，得到氧化锌微晶纤维。The method according to claim 5, characterized in that, in step 2, the reaction is maintained for 5-10 hours, and then cooled to room temperature, and then separated, washed and dried in order to obtain zinc oxide microcrystalline fibers.
  7. 根据权利要求6所述的方法，其特征在于，步骤2中，所述干燥的温度为60～100℃，时间为4～8小时。The method according to claim 6, wherein in step 2, the drying temperature is 60-100°C, and the time is 4-8 hours.
  8. 一种氧化锌微晶纤维，具有六方纤锌矿结构，其特征在于，由权利要求1～7中任一项所述的方法获得。A zinc oxide microcrystalline fiber having a hexagonal wurtzite structure, characterized in that it is obtained by the method according to any one of claims 1-7.
  9. 根据权利要求8所述的氧化锌微晶纤维，其特征在于，所述氧化锌微 晶纤维的直径为0.1～5μm，长度为1～49μm。The zinc oxide microcrystalline fiber according to claim 8, wherein the zinc oxide microcrystalline fiber has a diameter of 0.1 to 5 m and a length of 1 to 49 m.
  10. 根据权利要求9所述的氧化锌微晶纤维，其特征在于，所述氧化锌微晶纤维的直径为0.8～2.6μm，长度为10～40μm。The zinc oxide microcrystalline fiber of claim 9, wherein the zinc oxide microcrystalline fiber has a diameter of 0.8-2.6 μm and a length of 10-40 μm.
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Publication number Priority date Publication date Assignee Title
JPS5467596A (en) * 1977-11-09 1979-05-31 Matsushita Electric Ind Co Ltd Preparation of hexagonal plate zinc oxide crystal powder
CN1887720A (en) * 2006-07-26 2007-01-03 中国科学院上海硅酸盐研究所 Prepn process of nanometer Zinc oxide powder
CN101066776A (en) * 2007-06-05 2007-11-07 武汉理工大学 Zinc oxide synthesizing process
CN102234129A (en) * 2010-05-07 2011-11-09 广西民族大学 Preparation method of one-dimensional nano-ZnO
CN106379930A (en) * 2016-11-09 2017-02-08 上海天地涂料有限公司 Interface microwave preparation method of zinc oxide nanometer material
CN109627048A (en) * 2018-12-28 2019-04-16 株洲电力机车广缘科技有限责任公司 A kind of method and silicon carbide fibre in silicon carbide fibre growing zinc oxide crystal whisker on surface

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5467596A (en) * 1977-11-09 1979-05-31 Matsushita Electric Ind Co Ltd Preparation of hexagonal plate zinc oxide crystal powder
CN1887720A (en) * 2006-07-26 2007-01-03 中国科学院上海硅酸盐研究所 Prepn process of nanometer Zinc oxide powder
CN101066776A (en) * 2007-06-05 2007-11-07 武汉理工大学 Zinc oxide synthesizing process
CN102234129A (en) * 2010-05-07 2011-11-09 广西民族大学 Preparation method of one-dimensional nano-ZnO
CN106379930A (en) * 2016-11-09 2017-02-08 上海天地涂料有限公司 Interface microwave preparation method of zinc oxide nanometer material
CN109627048A (en) * 2018-12-28 2019-04-16 株洲电力机车广缘科技有限责任公司 A kind of method and silicon carbide fibre in silicon carbide fibre growing zinc oxide crystal whisker on surface

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