CN102336431B - A kind of SnO2 flower-like structure nanomaterial and its hydrothermal preparation method - Google Patents
A kind of SnO2 flower-like structure nanomaterial and its hydrothermal preparation method Download PDFInfo
- Publication number
- CN102336431B CN102336431B CN201110177297.5A CN201110177297A CN102336431B CN 102336431 B CN102336431 B CN 102336431B CN 201110177297 A CN201110177297 A CN 201110177297A CN 102336431 B CN102336431 B CN 102336431B
- Authority
- CN
- China
- Prior art keywords
- flower
- solution
- concentration
- sncl
- sno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Catalysts (AREA)
- Colloid Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种SnO2花状结构纳米材料及其制备方法：将SnCl4·5H2O和NaOH分别溶于去离子水；将SnCl4溶液在4~25℃条件下搅拌，将NaOH溶液滴入，得到锡离子浓度为0.1mol/L~0.3mol/L，氢氧根浓度为0.9mol/L~3.3mol/L，氢氧根离子与锡离子摩尔浓度之比为9~11：1的前驱体溶液；将前驱体溶液转移到反应釜中密封，反应釜的填充度为70%，在190℃~200℃下保温8~12h；反应结束后降至室温，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直到滤液pH=7，在60℃下烘干过滤后的产物，得到花状结构SnO2纳米材料。该产物形态为三维花状纳米线簇，具体地说，花蕾是由共球心沿半径方向排列的、单晶SnO2纳米线构成，纳米线的直径为90~400nm，长度为950~1200nm，长径比为3.00~10.56。
The invention discloses a SnO 2 flower-shaped nanomaterial and a preparation method thereof: respectively dissolving SnCl 4 5H 2 O and NaOH in deionized water; stirring the SnCl 4 solution at Drop in, the tin ion concentration is 0.1mol/L~0.3mol/L, the hydroxide ion concentration is 0.9mol/L~3.3mol/L, and the molar concentration ratio of hydroxide ion to tin ion is 9~11:1 Precursor solution; transfer the precursor solution to the reactor and seal it. The filling degree of the reactor is 70%, and keep it warm at 190°C~200°C for 8~12h; Ion water and absolute ethanol were repeatedly washed and filtered until the pH of the filtrate was 7, and the filtered product was dried at 60°C to obtain a flower-like structured SnO 2 nanomaterial. The shape of the product is a three-dimensional flower-like nanowire cluster. Specifically, the flower buds are composed of single crystal SnO2 nanowires arranged along the radial direction with a common spherical center. The diameter of the nanowires is 90-400nm and the length is 950-1200nm. The aspect ratio is 3.00~10.56.
Description
技术领域 technical field
本发明属于材料制备领域，具体涉及一种SnO2花状结构纳米材料及其水热制备方法。 The invention belongs to the field of material preparation, and in particular relates to a SnO2 flower-like structure nano material and a hydrothermal preparation method thereof.
背景技术 Background technique
SnO2是一种典型的n型直接带隙宽禁带氧化物半导体材料，它具有以下几个方面的优点：(1) 室温下具有宽带隙(Eg=3.6eV)和高激子束缚能(130meV)；(2) 低成本；(3) 制备方法及产物形态结构多样。以上这些特点使得SnO2在半导体器件和功能材料领域具有其独特的优势与宽广的应用潜力，尤其是SnO2低维纳米材料已经在催化剂、锂离子电池的负极材料、电磁波吸收、太阳能电池、传感器、光电子器件等方面表现出了广阔的应用前景。同时，长径比可控的花状纳米结构SnO2高度的多功能性，使其在纳米电子器件的制造中有着不可估量的应用前景。 SnO 2 is a typical n-type direct band gap wide band gap oxide semiconductor material, which has the following advantages: (1) wide band gap (E g =3.6eV) and high exciton binding energy at room temperature (130meV); (2) Low cost; (3) Various preparation methods and product morphological structures. The above characteristics make SnO 2 have its unique advantages and broad application potential in the field of semiconductor devices and functional materials. , optoelectronic devices and other aspects have shown broad application prospects. At the same time, the high versatility of the flower-like nanostructure SnO 2 with controllable aspect ratio makes it have immeasurable application prospects in the manufacture of nanoelectronic devices.
近年来，关于低维SnO2纳米材料的制备及应用已经得到了广泛的研究。L. Y. Jiang等人(Ling-Yan Jiang, Xing-Long Wu, Yu-Guo Guo, et al. SnO2-Based hierarchical nanomicrostructure: facile synthesis and their applications in gas sensors and lithium-ion batteries [J]. J. Phys. Chem. C, 2009,113:14213-14219)在500℃下制备了花状SnO2纳米结构，反应源物质含有多种有机成分，如：草酸、酒精等。该论文高温下制备的SnO2花蕾是由多束纳米线构成的花瓣组成。D. F. Zhang等人(Dong-Feng Zhang, Ling-Dong Sun, Gang Xu, et al. Size-controllable one-dimensinal SnO2 nanocrystals: synthesis, growth mechanism, and gas sensing property [J]. Phys. Chem. Chem. Phys., 2006, 8:4874-4880)采用微乳液辅助水热法制备了SnO2纳米线，尽管所制备的SnO2纳米线长径比有着较大的可调范围，但是反应温度仍然较高(为240℃)，制备过程也比较复杂。中国专利(申请号：200910153400.5)提出了一种水热合成花状形貌SnO2纳米结构材料的方法，该专利的材料是由SnO2薄片组成的花状团簇。在目前的研究成果中，还没有发现由共球心且沿半径方向排列的单晶纳米线构成的SnO2花状结构纳米材料的相关报道。 In recent years, the preparation and application of low-dimensional SnO 2 nanomaterials have been extensively studied. L. Y. Jiang et al. (Ling-Yan Jiang, Xing-Long Wu, Yu-Guo Guo, et al. SnO 2 -Based hierarchical nanostructure: facile synthesis and their applications in gas sensors and lithium-ion batteries [J]. J. Phys . Chem. C, 2009,113:14213-14219) prepared flower-like SnO 2 nanostructures at 500°C, and the reaction source material contained various organic components, such as: oxalic acid, alcohol, etc. The SnO 2 flower buds prepared at high temperature in this paper are composed of petals composed of bundles of nanowires. D. F. Zhang et al. (Dong-Feng Zhang, Ling-Dong Sun, Gang Xu, et al. Size-controllable one-dimensinal SnO 2 nanocrystals: synthesis, growth mechanism, and gas sensing property [J]. Phys. Chem. Chem. Phys., 2006, 8:4874-4880) prepared SnO 2 nanowires by microemulsion-assisted hydrothermal method. Although the aspect ratio of the prepared SnO 2 nanowires has a large adjustable range, the reaction temperature is still high (240°C), the preparation process is also more complicated. Chinese patent (application number: 200910153400.5) proposes a method for hydrothermally synthesizing SnO2 nanostructure materials with flower-like morphology. The material of this patent is a flower-like cluster composed of SnO2 flakes. In the current research results, there is no related report on SnO 2 flower-like structure nanomaterials composed of single crystal nanowires with a common spherical center and arranged along the radial direction.
发明内容 Contents of the invention
针对上述现有技术存在的缺陷或不足，本发明的目的在于，提供一种SnO2花状结构纳米材料及其制备方法，本发明采用水热法，通过控制反应体系中的[OH-]/[ Sn4+]、[Sn4+]、反应温度、反应时间、体系压强等因素获得了一种花状结构SnO2纳米材料。 In view of the defects or deficiencies in the above-mentioned prior art, the object of the present invention is to provide a SnO 2 flower-like structure nano-material and its preparation method. The present invention adopts a hydrothermal method, by controlling the [OH - ]/ [ Sn 4+ ], [Sn 4+ ], reaction temperature, reaction time, system pressure and other factors obtained a flower-like structure of SnO 2 nanomaterials.
为了实现上述任务，本发明采用如下技术解决方案： In order to realize above-mentioned task, the present invention adopts following technical solution:
一种SnO2花状结构纳米材料，其特征在于，该材料为三维花状纳米线簇，其花蕾由共球心沿半径方向排列的单晶SnO2纳米线构成，所述纳米线直径为90~400nm，纳米线长度为950~1200nm，纳米线长径比为3.00~10.56。 A kind of SnO flower - like structure nanomaterial, it is characterized in that, this material is three-dimensional flower-like nanowire cluster, and its flower bud is made of the single crystal SnO nanowire that co-sphere center is arranged along radial direction, and described nanowire diameter is 90 ~400nm, the length of the nanowire is 950~1200nm, and the aspect ratio of the nanowire is 3.00~10.56.
上述SnO2花状结构纳米材料的制备方法，其特征在于，具体包括如下步骤： Above - mentioned SnO The preparation method of flower-like structure nanomaterial is characterized in that, specifically comprises the following steps:
(1)将SnCl4·5H2O和NaOH分别溶于去离子水；将SnCl4溶液在4~25℃条件下搅拌，搅拌过程中将NaOH溶液滴入SnCl4溶液中，得到锡离子[Sn4+]浓度为0.1mol/L~0.3mol/L，氢氧根离子[OH-]浓度为0.9mol/L~3.3mol/L，氢氧根离子与锡离子摩尔浓度之比[OH-]/[Sn4+]=9~11：1的前驱体溶液；或者 (1) Dissolve SnCl 4 5H 2 O and NaOH in deionized water respectively; stir the SnCl 4 solution at 4~25°C, and drop the NaOH solution into the SnCl 4 solution during the stirring process to obtain tin ions [Sn 4+ ] concentration is 0.1mol/L~0.3mol/L, hydroxide ion [OH - ] concentration is 0.9mol/L~3.3mol/L, the ratio of hydroxide ion to tin ion molar concentration [OH - ] /[Sn 4+ ]=9~11:1 precursor solution; or
将SnCl4·5H2O和表面活性剂溶于去离子水得到混合溶液，所述表面活性剂为聚丙烯酰胺，该混合溶液中聚丙烯酰胺与锡离子的摩尔浓度之比[PAM] /[Sn4+]小于0.0003%；将所述混合溶液在4~25℃条件下搅拌，搅拌过程中将NaOH溶液滴入混合溶液，得到锡离子[Sn4+]浓度为0.1mol/L~0.3mol/L，氢氧根离子[OH-]浓度为0.9mol/L~3.3mol/L，氢氧根离子与锡离子摩尔浓度之比[OH-]/[Sn4+]=9~11：1的前驱体溶液； Dissolving SnCl 4 5H 2 O and a surfactant in deionized water to obtain a mixed solution, the surfactant being polyacrylamide, the ratio of the molar concentration of polyacrylamide to tin ions in the mixed solution [PAM]/[ Sn 4+ ] is less than 0.0003%; the mixed solution is stirred at 4~25°C, and NaOH solution is dropped into the mixed solution during the stirring process to obtain a tin ion [Sn 4+ ] concentration of 0.1mol/L~0.3mol /L, the concentration of hydroxide ion [OH - ] is 0.9mol/L~3.3mol/L, the ratio of hydroxide ion to tin ion molar concentration [OH - ]/[Sn 4+ ]=9~11:1 The precursor solution;
(2)将步骤(1)的前驱体溶液转移到反应釜中密封，反应釜的填充度为70%，在190℃~200℃下保温8~12h； (2) Transfer the precursor solution in step (1) to the reactor and seal it. The filling degree of the reactor is 70%, and keep it warm at 190°C~200°C for 8~12h;
(3)反应结束后降至室温，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直到滤液pH=7，在60℃下烘干过滤后的产物，得到花状结构SnO2纳米材料。 (3) After the reaction is completed, it is lowered to room temperature, and the product obtained from the reaction is repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate is 7, and the filtered product is dried at 60°C to obtain a flower-like structure SnO 2 nanomaterials.
本发明具有以下两个突出优点： The present invention has following two outstanding advantages:
(1)水热过程中无需任何有机溶剂，工艺简单，产率高，且成本低廉，适合批量生产； (1) No organic solvent is needed in the hydrothermal process, the process is simple, the yield is high, and the cost is low, which is suitable for mass production;
(2)所制备花状结构SnO2纳米线簇的形态均一，长径比Ld易于控制。 (2) The shape of the prepared flower-like structured SnO 2 nanowire clusters is uniform, and the aspect ratio L d is easy to control.
附图说明 Description of drawings
图1为实施例1-3得到产物的X射线衍射(XRD，X-ray Diffraction)图谱； Fig. 1 is that embodiment 1-3 obtains the X-ray diffraction (XRD, X-ray Diffraction) collection of products of product;
图2为实施例1得到产物的透射电子显微镜(TEM, Transmission Electron Microscopy)照片，其中图2(a)为TEM照片、图2(b)为选区电子衍射(SAED, Selected-area Electron Diffraction)照片、图2(c)为高分辨透射电子显微镜(HRTEM, High-resolution Transmission Electron Microscopy)照片。 Fig. 2 is the transmission electron microscope (TEM, Transmission Electron Microscopy) photo that embodiment 1 obtains product, wherein Fig. 2 (a) is TEM photo, Fig. 2 (b) is selected area electron diffraction (SAED, Selected-area Electron Diffraction) photo , Figure 2(c) is a high-resolution transmission electron microscope (HRTEM, High-resolution Transmission Electron Microscopy) photo.
图3(a)为实施例2得到产物的扫描电子显微镜(FEESEM, Field Emission Environment Scanning Electron Microscope)照片，图3(b)为高放大倍率FEESEM照片，图3(c)为实施例2得到产物的SAED照片。 Fig. 3 (a) is the scanning electron microscope (FEESEM, Field Emission Environment Scanning Electron Microscope) photo that embodiment 2 obtains the product, Fig. 3 (b) is the high magnification FEESEM photograph, Fig. 3 (c) obtains the product for embodiment 2 SAED photo. the
图4(a)为实施例3得到产物的TEM照片，图4(b)为实施例3得到产物的SAED照片。 Fig. 4 (a) is the TEM photo of the product obtained in Example 3, and Fig. 4 (b) is the SAED photo of the product obtained in Example 3. the
以下结合附图和具体实施方式对本发明做进一步解释说明。 The present invention will be further explained below in conjunction with the accompanying drawings and specific embodiments. the
具体实施方式 Detailed ways
本发明公开了一种SnO2花状结构纳米材料，该材料为三维花状纳米线簇，其花蕾由共球心沿半径方向排列的单晶SnO2纳米线构成，纳米线直径为90~400nm，纳米线长度为950~1200nm，纳米线长径比为3.00~10.56。 The invention discloses a SnO2 flower-like structure nanomaterial, which is a three-dimensional flower-like nanowire cluster, the flower buds of which are composed of single crystal SnO2 nanowires arranged along the radial direction with a common spherical center, and the diameter of the nanowires is 90-400nm , the length of the nanowire is 950~1200nm, and the aspect ratio of the nanowire is 3.00~10.56.
上述SnO2花状结构纳米材料的制备方法具体包括如下步骤： Above-mentioned SnO The preparation method of flower-like structure nanomaterial specifically comprises the following steps:
(1)将SnCl4·5H2O和NaOH分别溶于去离子水；将SnCl4溶液在4~25℃条件下搅拌，搅拌过程中将NaOH溶液滴入SnCl4溶液中，得到锡离子[Sn4+]浓度为0.1mol/L~0.3mol/L，氢氧根离子[OH-]浓度为0.9mol/L~3.3mol/L，氢氧根离子与锡离子摩尔浓度之比[OH-]/[Sn4+]=9~11:1的前驱体溶液；或者 (1) Dissolve SnCl 4 5H 2 O and NaOH in deionized water respectively; stir the SnCl 4 solution at 4~25°C, and drop the NaOH solution into the SnCl 4 solution during the stirring process to obtain tin ions [Sn 4+ ] concentration is 0.1mol/L~0.3mol/L, hydroxide ion [OH - ] concentration is 0.9mol/L~3.3mol/L, the ratio of hydroxide ion to tin ion molar concentration [OH - ] /[Sn 4+ ]=9~11:1 precursor solution; or
将SnCl4·5H2O和表面活性剂溶于去离子水得到混合溶液，所述表面活性剂为聚丙烯酰胺，该混合溶液中聚丙烯酰胺与锡离子的摩尔浓度之比[PAM] /[Sn4+]小于0.0003%；将所述混合溶液在4~25℃条件下搅拌，搅拌过程中将NaOH溶液滴入混合溶液，得到锡离子[Sn4+]浓度为0.1mol/L~0.3mol/L，氢氧根离子[OH-]浓度为0.9mol/L~3.3mol/L，氢氧根离子与锡离子摩尔浓度之比[OH-]/[Sn4+]=9~11：1的前驱体溶液； Dissolving SnCl 4 5H 2 O and a surfactant in deionized water to obtain a mixed solution, the surfactant being polyacrylamide, the ratio of the molar concentration of polyacrylamide to tin ions in the mixed solution [PAM]/[ Sn 4+ ] is less than 0.0003%; the mixed solution is stirred at 4~25°C, and NaOH solution is dropped into the mixed solution during the stirring process to obtain a tin ion [Sn 4+ ] concentration of 0.1mol/L~0.3mol /L, the concentration of hydroxide ion [OH - ] is 0.9mol/L~3.3mol/L, the ratio of hydroxide ion to tin ion molar concentration [OH - ]/[Sn 4+ ]=9~11:1 The precursor solution;
(2)将步骤(1)的前驱体溶液转移到反应釜中密封，反应釜的填充度为70%，在190℃~200℃下保温8~12h； (2) Transfer the precursor solution in step (1) to the reactor and seal it. The filling degree of the reactor is 70%, and keep it warm at 190°C~200°C for 8~12h;
(3)反应结束后降至室温，将反应所得产物用去离子水和无水乙醇反复洗涤并过滤，直到滤液pH=7，在60℃下烘干过滤后的产物，得到花状结构SnO2纳米材料。 (3) After the reaction is completed, it is lowered to room temperature, and the product obtained from the reaction is repeatedly washed with deionized water and absolute ethanol and filtered until the pH of the filtrate is 7, and the filtered product is dried at 60°C to obtain a flower-like structure SnO 2 nanomaterials.
实施例1Example 1
称取2.8331g纯度为99%的SnCl4·5H2O置于烧杯A中，称取纯度为96%3.0000g的NaOH置于烧杯B中，并分别用20ml去离子水溶解形成透明溶液，将烧杯A进行4℃的冷水浴并搅拌，搅拌过程中将烧杯B中的氢氧化钠溶液滴入烧杯A，依次用20ml、10ml和10ml的去离子水洗涤烧杯B，并将每次的洗涤液滴入烧杯A中得到前驱体溶液。此时，前驱体溶液中锡离子浓度[Sn4+]=0.1mol/L，氢氧根离子浓度[OH-]=0.9mol/L，[OH-]/[Sn4+]=9:1。用量筒依次量取两个35ml的前驱体溶液，并将量取的两个前驱体溶液分别转移到两个容积均为50ml有聚四氟乙烯内衬的高压反应釜中并密封，在190℃下反应8小时，待两个反应釜冷却到室温，将反应所得产物用去离子水和无水乙醇反复洗涤、过滤至滤液的PH=7，然后在60℃下进行干燥，最后对产物进行XRD、TEM和SEM表征。 Weigh 2.8331g of SnCl 4 5H 2 O with a purity of 99% and place it in beaker A, weigh 3.0000g of NaOH with a purity of 96% and place it in beaker B, and dissolve it with 20ml of deionized water to form a transparent solution. Beaker A was placed in a cold water bath at 4°C and stirred. During the stirring process, the sodium hydroxide solution in beaker B was dropped into beaker A, and beaker B was washed with 20ml, 10ml and 10ml of deionized water in sequence, and each washing solution Drop into beaker A to obtain the precursor solution. At this time, the tin ion concentration in the precursor solution [Sn 4+ ]=0.1mol/L, the hydroxide ion concentration [OH - ]=0.9mol/L, [OH - ]/[Sn 4+ ]=9:1 . Use a graduated cylinder to measure two 35ml precursor solutions in sequence, and transfer the measured two precursor solutions to two 50ml high-pressure reactors with Teflon linings and seal them. React at low temperature for 8 hours. After the two reactors are cooled to room temperature, the reaction product is repeatedly washed with deionized water and absolute ethanol, filtered until the pH of the filtrate is 7, and then dried at 60°C. Finally, the product is subjected to XRD , TEM and SEM characterization.
实施例2Example 2
称取2.8331g纯度为99%的SnCl4·5H2O和0.0276g纯度为85%的的聚丙烯酰胺(PAM)共同置于烧杯A中，称取3.6667g纯度为96%的NaOH置于烧杯B中，并分别用20ml去离子水溶解形成透明溶液，将烧杯A进行4℃的冷水浴并搅拌，搅拌过程中将烧杯B中的氢氧化钠溶液滴入烧杯A的混合溶液中，依次用20ml、10ml和10ml的去离子水洗涤烧杯B，并将每次的洗涤液滴入烧杯A中得到前驱体溶液。此时，前驱体溶液中锡离子浓度[Sn4+]=0.1mol/L，氢氧根离子浓度[OH-]=1.1mol/L，聚丙烯酰胺与锡离子的摩尔浓度之比PAM]/[Sn4+]=0.0001%，氢氧根离子与锡离子的摩尔浓度之比[OH-]/[Sn4+]=11:1。用量筒依次量取两个35ml的前驱体溶液，并将量取的两个前驱体溶液分别转移到两个容积均为50ml有聚四氟乙烯内衬的高压反应釜中并密封，在200℃下反应12小时，待两个反应釜冷却到室温，将反应所得产物用去离子水和无水乙醇反复洗涤、过滤至滤液的PH=7，然后在60℃下进行干燥，最后对产物进行XRD、TEM和SEM表征。 Weigh 2.8331g of SnCl 4 5H 2 O with a purity of 99% and 0.0276g of polyacrylamide (PAM) with a purity of 85% and place them in beaker A, and weigh 3.6667g of NaOH with a purity of 96% and place them in the beaker B, and dissolved with 20ml of deionized water to form a transparent solution, put beaker A in a cold water bath at 4°C and stir, during the stirring process, drop the sodium hydroxide solution in beaker B into the mixed solution in beaker A, and then use Wash beaker B with 20ml, 10ml and 10ml of deionized water, and drop each washing solution into beaker A to obtain a precursor solution. At this point, the tin ion concentration in the precursor solution [Sn 4+ ]=0.1mol/L, the hydroxide ion concentration [OH - ]=1.1mol/L, the ratio of the molar concentration of polyacrylamide to tin ion [PAM]/ [Sn 4+ ]=0.0001%, the molar concentration ratio of hydroxide ions to tin ions [OH - ]/[Sn 4+ ]=11:1. Use a graduated cylinder to measure two 35ml precursor solutions in turn, and transfer the measured two precursor solutions to two 50ml high-pressure reactors with Teflon linings and seal them. React at low temperature for 12 hours, wait for the two reactors to cool down to room temperature, wash the reaction product repeatedly with deionized water and absolute ethanol, filter until the pH of the filtrate is 7, and then dry it at 60°C, and finally carry out XRD on the product , TEM and SEM characterization.
实施例3Example 3
称取8.4993g纯度为99%的SnCl4·5H2O和0.0276g纯度为85%的聚丙烯酰胺(PAM)共同置于烧杯A中，称取11.0001g纯度为96%的NaOH置于烧杯B中，并分别用20ml去离子水溶解形成透明溶液，将烧杯A进行25℃的冷水浴并搅拌，搅拌过程中将烧杯B中的氢氧化钠溶液滴入烧杯A的混合溶液中，依次用20ml、10ml和10ml的去离子水洗涤烧杯B，并将每次的洗涤液滴入烧杯A中得到前驱体溶液。此时，前驱体溶液中锡离子浓度[Sn4+]=0.3mol/L，氢氧根离子浓度[OH-]=3.3mol/L，聚丙烯酰胺与锡离子的摩尔浓度之比[PAM]/[Sn4+]=0.0003%，氢氧根离子与锡离子的摩尔浓度之比[OH-]/[Sn4+]=11:1。用量筒依次量取两个35ml的前驱体溶液，并将量取的两个前驱体溶液分别转移到两个容积均为50ml有聚四氟乙烯内衬的高压反应釜中并密封，在200℃下反应12小时，待两个反应釜冷却到室温，将反应所得产物用去离子水和无水乙醇反复洗涤、过滤至滤液的PH=7，然后在60℃下进行干燥，最后对产物进行XRD、TEM和SEM表征。 Weigh 8.4993g of SnCl 4 5H 2 O with a purity of 99% and 0.0276g of polyacrylamide (PAM) with a purity of 85% in beaker A, and weigh 11.0001g of NaOH with a purity of 96% in beaker B , and dissolved with 20ml of deionized water to form a transparent solution, place beaker A in a cold water bath at 25°C and stir, during the stirring process, drop the sodium hydroxide solution in beaker B into the mixed solution in beaker A, and then use 20ml , 10ml and 10ml of deionized water to wash beaker B, and drop each washing solution into beaker A to obtain a precursor solution. At this time, the concentration of tin ions in the precursor solution [Sn 4+ ]=0.3mol/L, the concentration of hydroxide ions [OH - ]=3.3mol/L, the ratio of the molar concentration of polyacrylamide to tin ions [PAM] /[Sn 4+ ]=0.0003%, the ratio of the molar concentration of hydroxide ions to tin ions [OH - ]/[Sn 4+ ]=11:1. Use a graduated cylinder to measure two 35ml precursor solutions in turn, and transfer the measured two precursor solutions to two 50ml high-pressure reactors with Teflon linings and seal them. React at low temperature for 12 hours, wait for the two reactors to cool down to room temperature, wash the reaction product repeatedly with deionized water and absolute ethanol, filter until the pH of the filtrate is 7, and then dry it at 60°C, and finally carry out XRD on the product , TEM and SEM characterization.
[0017]图1为实施例1-3产物的X射线衍射(XRD，X-ray Diffraction)图谱，从图中可以看出，实施例1-3所得产物均为四方晶系金红石结构的SnO2； Fig. 1 is the X-ray diffraction (XRD, X-ray Diffraction) collection of illustrative plates of embodiment 1-3 product, as can be seen from the figure, embodiment 1-3 gained product is the SnO of tetragonal system rutile structure ;
图2为实施例1产物的透射电子显微镜(TEM, Transmission Electron Microscopy)照片，其中图2(a)为TEM照片、图2(b)为选区电子衍射(SAED, Selected-area Electron Diffraction)照片、图2(c)为高分辨透射电子显微镜(HRTEM, High-resolution Transmission Electron Microscopy)照片，从图中可以看出所制备的SnO2为花状结构，单根纳米线为金红石结构的单晶，且沿[001]方向取向生长。 Fig. 2 is the transmission electron microscope (TEM, Transmission Electron Microscopy) photo of embodiment 1 product, wherein Fig. 2 (a) is TEM photo, Fig. 2 (b) is selected area electron diffraction (SAED, Selected-area Electron Diffraction) photo, Figure 2(c) is a high-resolution transmission electron microscope (HRTEM, High-resolution Transmission Electron Microscopy) photo. It can be seen from the figure that the prepared SnO 2 has a flower-like structure, and a single nanowire is a single crystal of rutile structure, and Oriented growth along the [001] direction.
图3(a)为实施例2产物的扫描电子显微镜(FEESEM, Field Emission Environment Scanning Electron Microscope)照片，图3(b)为高放大倍率FEESEM照片，从图中可以看出所制备样品为形态均一的花状纳米线蔟，花状结构的花蕾是由共球心且沿半径方向排列的纳米线构成，纳米线的平均长度约为950nm，平均直径约为90nm，长径比约为10.56；图3(c)为实施例2产物的SAED照片，从图中可以看出组成花状结构的纳米线是单晶，且单根纳米线沿[001]方向生长。 Fig. 3 (a) is the scanning electron microscope (FEESEM, Field Emission Environment Scanning Electron Microscope) photo of embodiment 2 products, and Fig. 3 (b) is the FEESEM photo of high magnification, it can be seen from the figure that the prepared sample is uniform in shape The flower-like nanowire cluster, the flower bud of the flower-like structure is composed of nanowires with a common spherical center and arranged along the radial direction. The average length of the nanowires is about 950nm, the average diameter is about 90nm, and the aspect ratio is about 10.56; Figure 3 (c) is the SAED photo of the product of Example 2. It can be seen from the figure that the nanowires forming the flower-like structure are single crystals, and a single nanowire grows along the [001] direction. the
图4(a)为实施例3产物的TEM照片，图4(b)为实施例3产物的SAED照片。 Figure 4(a) is a TEM photo of the product of Example 3, and Figure 4(b) is a SAED photo of the product of Example 3. the
从图4可以看到，实施例3产物具有三维花状结构，具体地说，花蕾是由共球心且沿半径方向排列的单晶SnO2纳米线构成，纳米线的平均长度约为750nm，平均直径约为75nm，长径比约为10。 As can be seen from Figure 4, the product of Example 3 has a three-dimensional flower-like structure. Specifically, the flower bud is composed of single-crystal SnO nanowires arranged at the center of the sphere and arranged along the radial direction, and the average length of the nanowires is about 750nm. The average diameter is about 75nm, and the aspect ratio is about 10.
可以看出，采用表面活性剂与SnCl4·5H2O混合后制备的溶液作为反应原料，比单独采用SnCl4·5H2O制备的溶液作为反应原料所制备的纳米线的长度要长，直径要短。 It can be seen that the length of nanowires prepared by using the solution prepared by mixing surfactant and SnCl 4 ·5H 2 O as the reaction raw material is longer than that of the solution prepared by using SnCl 4 ·5H 2 O alone as the reaction raw material. to be short.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110177297.5A CN102336431B (en) | 2011-06-28 | 2011-06-28 | A kind of SnO2 flower-like structure nanomaterial and its hydrothermal preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110177297.5A CN102336431B (en) | 2011-06-28 | 2011-06-28 | A kind of SnO2 flower-like structure nanomaterial and its hydrothermal preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102336431A CN102336431A (en) | 2012-02-01 |
| CN102336431B true CN102336431B (en) | 2014-03-26 |
Family
ID=45512439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110177297.5A Expired - Fee Related CN102336431B (en) | 2011-06-28 | 2011-06-28 | A kind of SnO2 flower-like structure nanomaterial and its hydrothermal preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102336431B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102213688B (en) * | 2011-04-11 | 2013-06-05 | 大连理工大学 | Method of electrochemically measuring permanganate index by virtue of stannic oxide nanometer electrode |
| CN103043710B (en) * | 2011-10-17 | 2015-09-16 | 中国科学院福建物质结构研究所 | A kind of at α-Fe 2o 3nanocrystal surface Heteroepitaxy nano SnO 2method |
| CN102942215A (en) * | 2012-09-10 | 2013-02-27 | 重庆大学 | A kind of three-dimensional SnO2 nano-flower material grown on metal titanium substrate and its preparation method |
| CN104803411B (en) * | 2015-05-12 | 2016-08-24 | 中国科学院新疆理化技术研究所 | A kind of preparation method of hypersensitive nitrogen dioxide sensing material |
| CN104865296B (en) * | 2015-06-02 | 2017-05-10 | 中国科学院新疆理化技术研究所 | A method for controlling nitrogen dioxide sensitivity by regulating the surface defect concentration of tin dioxide |
| CN104974752B (en) * | 2015-08-07 | 2017-03-22 | 京东方科技集团股份有限公司 | White-light fluorescent material as well as preparation method and application thereof |
| CN105198004B (en) * | 2015-08-18 | 2017-03-29 | 西北大学 | A kind of Fe3O4-SnO2 nanocomposite material and preparation method thereof |
| CN105600818B (en) * | 2016-01-12 | 2017-06-23 | 济南大学 | The method and products obtained therefrom of a kind of stannic oxide nanometer powder prepared rich in Lacking oxygen |
| CN106830057B (en) * | 2017-01-13 | 2018-01-12 | 西北大学 | A kind of stannous oxide material and preparation method thereof |
| CN111116232A (en) * | 2019-12-13 | 2020-05-08 | 苏州麦茂思传感技术有限公司 | Synthesis method of formaldehyde gas sensor sensitive material |
| CN114122375A (en) * | 2021-11-12 | 2022-03-01 | 天津市捷威动力工业有限公司 | A kind of preparation method of nano-sheet SnO2/PPy solid-state battery anode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005062785A2 (en) * | 2003-12-17 | 2005-07-14 | The University Of North Carolina At Chapel Hill | Solution-phase synthesis of metal oxide nanostructures |
| CN101941734A (en) * | 2010-10-08 | 2011-01-12 | 北京化工大学 | Tin oxide nanomaterial and preparation method thereof |
-
2011
- 2011-06-28 CN CN201110177297.5A patent/CN102336431B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005062785A2 (en) * | 2003-12-17 | 2005-07-14 | The University Of North Carolina At Chapel Hill | Solution-phase synthesis of metal oxide nanostructures |
| CN101941734A (en) * | 2010-10-08 | 2011-01-12 | 北京化工大学 | Tin oxide nanomaterial and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102336431A (en) | 2012-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102336431B (en) | A kind of SnO2 flower-like structure nanomaterial and its hydrothermal preparation method | |
| CN101948130B (en) | Zinc oxide hollow microspheres and preparation method thereof | |
| Shi et al. | Growth of flower-like ZnO via surfactant-free hydrothermal synthesis on ITO substrate at low temperature | |
| CN101723436B (en) | Self-assembly zinc oxide hollow sphere and preparation method thereof | |
| CN102275981B (en) | A method for preparing self-substrate SnO2 nanorod arrays | |
| CN104528810A (en) | Preparation method for preparing stannic oxide nanorod cluster by using one-step hydrothermal method | |
| CN102134092B (en) | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application | |
| CN104324715A (en) | Three-dimensional MoS2/SnO2 heterogeneous semiconductor nanomaterial and its preparation method | |
| CN102502783A (en) | Method for preparing alkali zinc chloride nano-powder in hexagonal flake structures | |
| CN105152202A (en) | Preparation method for antimony-doped flower-ball-shaped tin dioxide gas-sensing material | |
| CN102826593A (en) | Preparation method for indium oxide nanometer material | |
| CN101311376A (en) | Method for preparing strontium titanate nanometer powder of one-dimensional structure | |
| CN107459065A (en) | A kind of Bi2Fe4O9The preparation method of nanometer rods or nanometer pie material | |
| CN103754837A (en) | Method for preparation of bismuth-containing nano-hollow ball by using porous bismuth oxide as template | |
| CN101613121A (en) | A kind of preparation method of ellipsoidal zinc oxide | |
| CN103043630B (en) | Preparation method of spherical nickel diselenide powder | |
| CN104192908A (en) | MoS2 micron hollow sphere structure semiconductor material surrounded by nanospheres and preparation method thereof | |
| CN103771490B (en) | A kind of simple and easy stirring at room temperature prepares the method for micro-/ nano zinc oxide | |
| Zhang et al. | Synthesis of SnO2 single-layered hollow microspheres and flowerlike nanospheres through a facile template-free hydrothermal method | |
| CN103466703B (en) | Bismuth titanate nanoneedle and preparation method thereof | |
| CN102718255B (en) | Preparation method of titanium dioxide hollow nano structure | |
| CN104402065A (en) | Preparation method of spheroidic CoS2 nanometer powder | |
| Hu et al. | Novel synthesis of CuO nanofiber balls and films and their UV–visible light filteration property | |
| CN101941677A (en) | Method for preparing manganese oxide surface modified zinc oxide nano rod | |
| CN101880067B (en) | A kind of preparation method of rod-shaped NiTiO3 nanocrystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140326 Termination date: 20180628 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |