CN102795658B - A kind of method adopting hydrogen peroxide to regulate zinc oxide crystal microstructure - Google Patents

A kind of method adopting hydrogen peroxide to regulate zinc oxide crystal microstructure Download PDF

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CN102795658B
CN102795658B CN201210265989.XA CN201210265989A CN102795658B CN 102795658 B CN102795658 B CN 102795658B CN 201210265989 A CN201210265989 A CN 201210265989A CN 102795658 B CN102795658 B CN 102795658B
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张卫华
夏培康
张博华
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Xian University of Technology
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Abstract

The invention discloses a method for regulating zinc oxide crystal microstructure by using hydrogen peroxide, and the method comprises the following steps: step 1, adding zinc oxide powder of micro-nano scale to hydrogen peroxide or the water solution of the hydrogen peroxide at room temperature, with a mol ratio of ZnO:H2H2 =1:(20-200), and stirring uniformly to obtain a mixed solution; step 2, placing the mixed solution in a closed container for reaction at constant temperature, cooling to obtain a precipitate, and after washing the precipitate by water, centrifugal separating and drying the precipitate, obtaining the zinc crystals. The method of the invention is simple in technology, high efficiency, and environment friendly; and the obtained products are a series of zinc oxide crystals with different morphologies and sizes, displaying strong nanometer size effect.

Description

一种采用双氧水调控氧化锌晶体微结构的方法A kind of method adopting hydrogen peroxide to regulate zinc oxide crystal microstructure

技术领域 technical field

本发明属于无机功能材料技术领域，涉及一种采用双氧水调控氧化锌晶体微结构的方法。The invention belongs to the technical field of inorganic functional materials, and relates to a method for regulating the microstructure of zinc oxide crystals by using hydrogen peroxide.

背景技术 Background technique

在室温下氧化锌为六方纤锌矿结构，具有较大的禁带宽度（3.37eV）和激子束缚能（60meV），是一种优异的半导体材料。纳米氧化锌由于具有表面效应、尺寸效应等纳米效应而展现出其它传统材料无法比拟的性能，在光学、电学、磁学、力学等方面表现出与宏观尺度材料大不相同的特性，其在太阳能电池、光致发光、光催化降解、紫外线屏蔽、声电器件、气敏陶瓷等领域有着重大的应用价值，成为国内外研究的热点。氧化锌的性能决定于其尺寸、形貌及制备工艺，因而其微结构的研究与控制也是纳米氧化锌研究领域的一个重要内容。Zinc oxide has a hexagonal wurtzite structure at room temperature, has a large band gap (3.37eV) and exciton binding energy (60meV), and is an excellent semiconductor material. Due to the nano-effects such as surface effect and size effect, nano-zinc oxide exhibits incomparable properties of other traditional materials. Batteries, photoluminescence, photocatalytic degradation, ultraviolet shielding, acoustoelectric devices, gas-sensitive ceramics and other fields have great application value and have become research hotspots at home and abroad. The performance of zinc oxide depends on its size, shape and preparation process, so the research and control of its microstructure is also an important content in the field of nano-zinc oxide research.

现有的纳米氧化锌的制备方法及设备，该方法采用化学气相沉积技术，先将金属锌或锌的氧化物在金属熔化室中进行感应加热，被加热物熔化后，引入燃烧火焰燃烧，收集燃烧所得氧化物冷却后即得纳米氧化锌粉体。该方法需要较昂贵的专用设备，且氧化锌的尺寸与形貌不易控制，产物不均。The existing nano-zinc oxide preparation method and equipment, the method adopts chemical vapor deposition technology, first conducts induction heating of metal zinc or zinc oxide in a metal melting chamber, after the object to be heated is melted, it is introduced into a combustion flame to burn, and collected After the oxide obtained by burning is cooled, nano zinc oxide powder is obtained. This method requires more expensive special equipment, and the size and shape of zinc oxide are not easy to control, and the product is uneven.

现有的纳米氧化锌的制备方法，该方法采用水热合成方法，先将脂肪醇和醋酸锌配制成混合溶液，再在80～300℃下反应2～48h，洗涤、分离后即得纳米氧化锌粉体，该方法需要甲醇、乙二醇、丙三醇等有机添加剂，对环境不利，且所得产物尺寸与形貌不均。The existing nano-zinc oxide preparation method adopts a hydrothermal synthesis method. Firstly, aliphatic alcohol and zinc acetate are prepared into a mixed solution, and then reacted at 80-300° C. for 2-48 hours. After washing and separation, nano-zinc oxide is obtained. Powder, this method requires organic additives such as methanol, ethylene glycol, glycerol, etc., which is unfavorable to the environment, and the size and shape of the obtained product are uneven.

现有的纳米氧化锌的制备方法，该方法在碳酸氢铵溶液中依次加入十二烷基硫酸钠和氯化锌，将反应后所得的白色沉淀物洗涤、分离、干燥后得到前驱体，将所得前驱体在管式炉中煅烧即得纳米氧化锌，该方法需采用有机添加剂，煅烧后会产生有害气体，对环境有害，且所得产物形貌与尺寸不均。The preparation method of existing nano-zinc oxide, this method adds sodium lauryl sulfate and zinc chloride successively in the ammonium bicarbonate solution, the white precipitate obtained after the reaction is washed, separated, dried to obtain a precursor, and the The obtained precursor is calcined in a tube furnace to obtain nano-zinc oxide. This method requires the use of organic additives, which will produce harmful gases after calcination, which is harmful to the environment, and the shape and size of the obtained product are uneven.

现有的氧化锌纳米线的制备方法，该方法先采用碳酸盐或碳酸氢盐作沉淀剂制备碱式碳酸锌，再将聚乙二醇加入碱式碳酸锌溶液中并在180～220℃下反应5～24h，洗涤、分离所得沉淀物即得氧化锌纳米线，该方法所得产物尺寸不均，且需采用聚乙二醇为添加剂，对环保不利。The existing preparation method of zinc oxide nanowires, the method first uses carbonate or bicarbonate as a precipitating agent to prepare basic zinc carbonate, then adds polyethylene glycol into the basic zinc carbonate solution and heats it at 180-220°C React for 5-24 hours, wash and separate the obtained precipitate to obtain zinc oxide nanowires. The size of the product obtained by this method is not uniform, and polyethylene glycol needs to be used as an additive, which is not conducive to environmental protection.

以上所述的方法中，棒形氧化锌的合成主要采用一步合成方法，其所得到的ZnO形貌与尺寸的一致性和均匀性不易控制，且需要有机添加剂或特殊合成方法，易造成工艺可靠性不易保证以及环境污染等问题，均不易于进行产业化技术转换。Among the above-mentioned methods, the synthesis of rod-shaped zinc oxide mainly adopts a one-step synthesis method, and the consistency and uniformity of the obtained ZnO morphology and size are not easy to control, and organic additives or special synthesis methods are required, which is easy to cause reliable process. It is not easy to carry out industrialization technology conversion due to problems such as difficult guarantee of safety and environmental pollution.

发明内容 Contents of the invention

本发明的目的是提供一种采用双氧水调控氧化锌晶体微结构的方法，解决了现有技术中的ZnO形貌与尺寸的一致性和均匀性不易控制，且需要有机添加剂或特殊合成方法，易造成工艺可靠性不易保证以及环境污染的问题。The purpose of the present invention is to provide a method for regulating the microstructure of zinc oxide crystals by using hydrogen peroxide, which solves the difficulty in controlling the consistency and uniformity of ZnO morphology and size in the prior art, and requires organic additives or special synthesis methods, which is easy Cause process reliability is difficult to guarantee and the problem of environmental pollution.

本发明所采用的技术方案是，一种采用双氧水调控氧化锌晶体微结构的方法，其特征在于，按照以下步骤实施：The technical scheme adopted in the present invention is a method for regulating the microstructure of zinc oxide crystals by using hydrogen peroxide, which is characterized in that it is implemented according to the following steps:

步骤1、在室温下将微纳米尺度的氧化锌粉体加入到2～16mol/L的双氧水的水溶液中，摩尔比ZnO:H2O2=1:(20～200)，均匀搅拌30～60min，得到混合液；氧化锌粉体的直径为150～230nm，枝臂长度为800～1500nm，长径比为5～7；Step 1. Add micro-nano scale zinc oxide powder into 2-16mol/L hydrogen peroxide aqueous solution at room temperature, molar ratio ZnO:H 2 O 2 =1:(20-200), and stir evenly for 30-60min , to obtain a mixed solution; the diameter of the zinc oxide powder is 150-230nm, the arm length is 800-1500nm, and the aspect ratio is 5-7;

步骤2、将上述混合液在密闭容器内恒温150～200℃下反应6～24h，冷却后所得沉淀经水洗涤、离心分离，在40～100℃干燥12～24h后，得到氧化锌晶体，即成。Step 2. React the above mixed solution in a closed container at a constant temperature of 150-200°C for 6-24 hours. After cooling, the resulting precipitate is washed with water, centrifuged, and dried at 40-100°C for 12-24 hours to obtain zinc oxide crystals, namely become.

本发明的有益效果是，The beneficial effect of the present invention is,

1）合成路线独特，制备工艺简捷，效率高。1) The synthetic route is unique, the preparation process is simple and efficient.

2）不需要任何表面活性剂与修饰剂，对环境友好。2) It does not require any surfactants and modifiers, and is environmentally friendly.

3）所得产物为一系列不同形貌与尺寸的氧化锌晶体。调控后的尺寸可以从微米尺度连续变化到纳米尺度，棒径变化范围从10nm～1.5μm，棒长变化范围从40nm～50μm，长径比变化范围3～30。3) The obtained products are a series of zinc oxide crystals with different shapes and sizes. The adjusted size can be continuously changed from the micro scale to the nano scale, the rod diameter ranges from 10nm to 1.5 μm, the rod length ranges from 40 nm to 50 μm, and the aspect ratio ranges from 3 to 30.

4）其光催化降解染料（甲基橙水溶液）性能随ZnO纳米晶的直径减小而急剧增加，在直径尺寸小于200nm的情况下，表现出强烈的纳米尺寸效应，其光催化速率常数是微米、亚微米尺寸的ZnO晶体在相同测试条件下的2～6倍左右，如图1所示。4) Its photocatalytic degradation dye (methyl orange aqueous solution) performance increases sharply as the diameter of ZnO nanocrystals decreases. When the diameter size is less than 200nm, it shows a strong nanometer size effect, and its photocatalytic rate constant is micron , ZnO crystals with submicron size are about 2 to 6 times larger under the same test conditions, as shown in Figure 1.

5）其光致发光性能随ZnO纳米晶的直径尺寸减小而急剧增加，表现出明显的纳米尺寸效应，如图2所示。5) Its photoluminescent performance increases sharply with the decrease of the diameter of ZnO nanocrystals, showing an obvious nano-size effect, as shown in Figure 2.

附图说明 Description of drawings

图1为本发明所得产物氧化锌的光催化降解速率-棒径变化曲线；Fig. 1 is the photocatalytic degradation rate-rod diameter change curve of product zinc oxide obtained in the present invention;

图2为本发明所得产物氧化锌的特征发射峰发光强度-棒径变化曲线；Fig. 2 is the characteristic emission peak luminous intensity-rod diameter change curve of product zinc oxide obtained in the present invention;

图3为本发明所得产物氧化锌的棒径、棒长随氧化锌/双氧水的摩尔比变化曲线；Fig. 3 is the rod diameter of the present invention's gained product zinc oxide, rod length with the mol ratio change curve of zinc oxide/hydrogen peroxide;

图4为各实例使用的初始氧化锌的扫描电镜SEM照片；Fig. 4 is the scanning electron microscope SEM photograph of the initial zinc oxide that each example uses;

图5为本发明实施例1所得产物氧化锌的扫描电镜SEM照片；Fig. 5 is the scanning electron microscope SEM photo of product zinc oxide obtained in Example 1 of the present invention;

图6为本发明实施例2所得产物氧化锌的扫描电镜SEM照片；Fig. 6 is the scanning electron microscope SEM photo of product zinc oxide obtained in Example 2 of the present invention;

图7为本发明实施例2所得产物氧化锌的光致发光3D谱；Fig. 7 is the photoluminescence 3D spectrum of the product zinc oxide obtained in Example 2 of the present invention;

图8为本发明实施例3所得产物氧化锌的扫描电镜SEM照片;Fig. 8 is the scanning electron microscope SEM photo of product zinc oxide obtained in Example 3 of the present invention;

图9本发明实施例4所得产物氧化锌的扫描电镜SEM照片。Fig. 9 is a scanning electron microscope SEM picture of the zinc oxide product obtained in Example 4 of the present invention.

具体实施方式 Detailed ways

本发明的方法是采用溶解重结晶原理，通过改变体系中的ZnO/双氧水比例来调控氧化锌晶体微结构，从而得到棒径尺寸从微米级到纳米级可控制的、高结晶度的、棒团簇花形ZnO晶体的新制备方法。The method of the present invention adopts the principle of dissolution and recrystallization, and regulates the microstructure of zinc oxide crystals by changing the ratio of ZnO/hydrogen peroxide in the system, so as to obtain rods with controllable diameters from micron to nanometers, high crystallinity, and rod clusters. A new preparation method of cluster-shaped ZnO crystals.

本发明的采用双氧水调控氧化锌晶体微结构的方法，包括以下步骤：The method of the present invention adopting hydrogen peroxide to regulate the microstructure of zinc oxide crystals comprises the following steps:

步骤1、在室温下将微纳米尺度的氧化锌粉体加入到2～16mol/L的双氧水的水溶液中，摩尔比ZnO:H2O2=1:(20～200)，均匀搅拌30～60min，使得混合充分，得到混合液；Step 1. Add micro-nano scale zinc oxide powder into 2-16mol/L hydrogen peroxide aqueous solution at room temperature, molar ratio ZnO:H 2 O 2 =1:(20-200), and stir evenly for 30-60min , so that the mixture is fully mixed to obtain a mixed solution;

步骤2、将上述混合液在密闭容器内恒温150～200℃下反应6～24h，冷却后所得沉淀经水洗涤、离心分离，在40～100℃干燥12～24h后，得到一系列不同形貌与尺寸的氧化锌晶体，即成。Step 2. React the above mixed solution in a closed container at a constant temperature of 150-200°C for 6-24 hours. After cooling, the resulting precipitate is washed with water, centrifuged, and dried at 40-100°C for 12-24 hours to obtain a series of different shapes. Serve with zinc oxide crystals of the same size.

所采用的水为去离子水、纯净水或蒸馏水。The water used is deionized water, purified water or distilled water.

所采用的双氧水为工业级、分析级或电子级商品化试剂H2O2，质量浓度为27.5%～70%。The hydrogen peroxide used is industrial-grade, analytical-grade or electronic-grade commercial reagent H 2 O 2 , with a mass concentration of 27.5% to 70%.

本发明方法的工作原理是：在适当的温度和压力条件下，ZnO在不同浓度的双氧水-水环境下存在着不同程度的溶解和重结晶过程，利用这种重结晶过程，控制ZnO/H2O2摩尔比，就能够改变原有ZnO晶体的形貌、尺寸等微结构，得到高结晶度、微结构可控的ZnO晶体。在150～200℃的重结晶反应温度范围内，所得产物形貌主要为棒团簇的花形，其棒径、棒长均随着氧化锌/双氧水的摩尔比降低而减小，如图3所示。The working principle of the method of the present invention is: under appropriate temperature and pressure conditions, ZnO has different degrees of dissolution and recrystallization processes in the hydrogen peroxide-water environment of different concentrations, and this recrystallization process is used to control ZnO/H 2 The O 2 molar ratio can change the microstructure such as the morphology and size of the original ZnO crystal, and obtain a ZnO crystal with high crystallinity and controllable microstructure. In the recrystallization reaction temperature range of 150-200 °C, the morphology of the obtained product is mainly the flower shape of rod clusters, and the rod diameter and rod length decrease with the decrease of the molar ratio of zinc oxide/hydrogen peroxide, as shown in Figure 3 Show.

实施例1Example 1

在室温下将氧化锌粉体（直径为150～230nm，枝臂长度为800～1500nm，长径比为5～7，扫描电镜形貌照片如图4所示）加入到2mol/L的双氧水溶液中（摩尔比为ZnO:H2O2=1:20），搅拌30min混合均匀后在200℃下反应6h，所得沉淀经去离子水洗涤、离心分离、干燥（控制条件为65℃，20h）后即得到氧化锌晶体。经双氧水调控后重结晶析出的高结晶度的棒团簇花形ZnO晶体的扫描电镜形貌照片如图5所示，其单根棒直径为400～1500nm、长度为30～50μm、长径比为12～30。Add zinc oxide powder (diameter 150-230nm, arm length 800-1500nm, aspect ratio 5-7, scanning electron microscope photo as shown in Figure 4) into 2mol/L hydrogen peroxide solution at room temperature medium (the molar ratio is ZnO:H 2 O 2 =1:20), stirred for 30min and mixed evenly, then reacted at 200°C for 6h, and the obtained precipitate was washed with deionized water, centrifuged, and dried (control condition was 65°C, 20h) Zinc oxide crystals are then obtained. The scanning electron microscope photo of the highly crystalline rod-cluster flower-shaped ZnO crystals precipitated after recrystallization under the control of hydrogen peroxide is shown in Figure 5. The diameter of a single rod is 400-1500 nm, the length is 30-50 μm, and the aspect ratio is 12 to 30.

实施例2Example 2

在室温下将氧化锌粉体（如图4所示）加入到4mol/L的双氧水溶液中（摩尔比为ZnO:H2O2=1:60），搅拌50min混合均匀后在150℃下反应24h，所得沉淀经纯净水洗涤、离心分离、干燥（控制条件为85℃，12h）后即得到棒团簇花形氧化锌晶体，其扫描电镜形貌照片如图6所示，单根棒直径为180～330nm、长度为1～2.5μm、长径比为7～14；其光致发光PL谱如图7所示，其激发波长在300～380nm、发射波长在400～700nm的宽发射波段、特征峰位于570nm，具有宽的紫外吸收截面和优异的可见光发射特性。Add zinc oxide powder (as shown in Figure 4) into 4mol/L hydrogen peroxide solution (molar ratio ZnO:H 2 O 2 =1:60) at room temperature, stir for 50 minutes and mix well, then react at 150°C After 24 hours, the resulting precipitate was washed with pure water, centrifuged, and dried (control condition: 85°C, 12 hours) to obtain rod-cluster flower-shaped zinc oxide crystals. The scanning electron microscope morphology photo is shown in Figure 6, and the diameter of a single rod is 180-330nm, length 1-2.5μm, aspect ratio 7-14; its photoluminescence PL spectrum is shown in Figure 7, the excitation wavelength is 300-380nm, the emission wavelength is 400-700nm wide emission band, The characteristic peak is located at 570nm, and has a wide ultraviolet absorption cross section and excellent visible light emission characteristics.

实施例3Example 3

在室温下将氧化锌粉体（如图4所示）加入到8mol/L的双氧水溶液中（摩尔比为ZnO:H2O2=1:100），搅拌60min混合均匀后在170℃下反应15h，所得沉淀经去离子水洗涤、离心分离、负压干燥（控制条件为40℃，24h）后即得到花簇状纳米氧化锌晶体（直径为30～250nm、600nm～1.5μm、长径比为10～20），其SEM扫描电镜形貌照片如图8所示。另外还包括有部分ZnO纳米晶须（其直径为10～20nm，长度为2～4μm）。Add zinc oxide powder (as shown in Figure 4) into 8mol/L hydrogen peroxide solution (molar ratio ZnO:H 2 O 2 =1:100) at room temperature, stir for 60 minutes and mix well, then react at 170°C After 15 hours, the resulting precipitate was washed with deionized water, centrifuged, and dried under negative pressure (control condition: 40°C, 24 hours) to obtain flower cluster nano-zinc oxide crystals (diameter 30-250nm, 600nm-1.5μm, aspect ratio 10-20), and its SEM scanning electron micrograph is shown in Fig. 8. In addition, some ZnO nano-whiskers (with a diameter of 10-20 nm and a length of 2-4 μm) are also included.

实施例4Example 4

在室温下将氧化锌粉体（如图4所示）加入到16mol/L的双氧水溶液中（摩尔比为ZnO:H2O2=1:200），搅拌30min混合均匀后在180℃下反应10h，所得沉淀经蒸馏水洗涤、离心分离、干燥（控制条件为100℃，15h）后即得到短棒形纳米氧化锌晶体（直径为10～30nm、棒长为40～200nm、长径比为3～10）。其棒团簇花形ZnO晶体的SEM扫描电镜形貌照片如图9所示。Add zinc oxide powder (as shown in Figure 4) into 16mol/L hydrogen peroxide solution (molar ratio ZnO:H 2 O 2 =1:200) at room temperature, stir for 30 minutes and mix well, then react at 180°C After 10 hours, the resulting precipitate was washed with distilled water, centrifuged, and dried (control condition: 100°C, 15 hours) to obtain short rod-shaped nano-zinc oxide crystals (diameter 10-30nm, rod length 40-200nm, aspect ratio 3 ~10). The SEM scanning electron microscope topography photo of its rod-cluster flower-shaped ZnO crystal is shown in Fig. 9 .

Claims (2)

1.一种采用双氧水调控氧化锌晶体微结构的方法，其特征在于，按照以下步骤实施：1. a method adopting hydrogen peroxide to regulate and control the microstructure of zinc oxide crystals is characterized in that, it is implemented according to the following steps: 步骤1、在室温下将微纳米尺度的氧化锌粉体加入到2～16mol/L的双氧水的水溶液中，摩尔比ZnO:H2O2=1:(20～200)，均匀搅拌30～60min，得到混合液；Step 1. Add micro-nano scale zinc oxide powder into 2-16mol/L hydrogen peroxide aqueous solution at room temperature, molar ratio ZnO:H 2 O 2 =1:(20-200), and stir evenly for 30-60min , to obtain a mixture; 所述的双氧水为工业级、分析级或电子级商品化试剂H2O2，质量浓度为27.5%～70%；The hydrogen peroxide is industrial-grade, analytical-grade or electronic-grade commercial reagent H 2 O 2 , with a mass concentration of 27.5% to 70%; 步骤2、将上述混合液在密闭容器内恒温150～200℃下反应6～24h，冷却后所得沉淀经水洗涤、离心分离，在40～100℃干燥12～24h后，得到氧化锌晶体，即成。Step 2. React the above mixed solution in a closed container at a constant temperature of 150-200°C for 6-24 hours. After cooling, the resulting precipitate is washed with water, centrifuged, and dried at 40-100°C for 12-24 hours to obtain zinc oxide crystals, namely become. 2.根据权利要求1所述的采用双氧水调控氧化锌晶体微结构的方法，其特征在于：所述的水为去离子水、纯净水或蒸馏水。2. The method for regulating the microstructure of zinc oxide crystals using hydrogen peroxide according to claim 1, wherein the water is deionized water, pure water or distilled water.
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