CN101508462A - Process for producing flower shaped indium hydroxide powder having high specific surface area - Google Patents
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Abstract
本发明涉及高比表面积花状氢氧化铟的制备方法，属于无机材料制备工艺技术领域。以In3+的水溶性盐为铟源，尿素为碱源，十二烷基硫酸钠为表面活性剂，采用水热法制备氢氧化铟粉体。在90－105℃低温水热条件下恒温反应12－24h，冷却至室温后过滤得到沉淀，洗涤，离心沉淀，烘干即得到由纳米片层组装而成的花状高比表面积花状氢氧化铟粉体。本发明的优点在于：本发明采用低温水热法制备花状氢氧化铟，不仅能使晶体在非受限的条件下充分生长，具有比表面积高，晶体形貌、大小可控，结晶完好等优点，而且获得的粉体的比表面积在20－40m2/g，XRD衍射表明主晶相为In(OH)3且沿[100]方向择优取向生长，杂相为InOOH且含量全部小于12％。该体系在微电子、光电、敏感器件、催化剂、碱性电池等领域拥有良好的应用前景。The invention relates to a method for preparing flower-like indium hydroxide with a high specific surface area, and belongs to the technical field of inorganic material preparation technology. Indium hydroxide powder was prepared by hydrothermal method with water-soluble salt of In 3+ as indium source, urea as alkali source, and sodium lauryl sulfate as surfactant. React at a constant temperature for 12-24 hours under low-temperature hydrothermal conditions at 90-105°C, cool to room temperature and filter to obtain a precipitate, wash, centrifuge, and dry to obtain a flower-shaped high specific surface area flower-shaped hydroxide assembled from nanosheets Indium powder. The advantage of the present invention is that: the present invention adopts the low-temperature hydrothermal method to prepare flower-shaped indium hydroxide, which not only enables the crystal to grow fully under unrestricted conditions, but also has high specific surface area, controllable crystal morphology and size, and perfect crystallization, etc. Advantages, and the specific surface area of the obtained powder is 20-40m 2 /g, XRD diffraction shows that the main crystal phase is In(OH) 3 and grows preferentially along the [100] direction, the impurity phase is InOOH and the content is all less than 12% . The system has good application prospects in the fields of microelectronics, optoelectronics, sensitive devices, catalysts, alkaline batteries and the like.
Description
技术领域 technical field
本发明属于无机材料制备工艺技术领域，特别是涉及高比表面积花状氢氧化铟的制备方法。The invention belongs to the technical field of inorganic material preparation technology, in particular to a preparation method of flower-shaped indium hydroxide with high specific surface area.
背景技术 Background technique
铟(In)是IIIA族元素，为具有四方晶体结构的低熔点金属，它易于合成例如InN、InGaN、InP和InAs的III-V族合金半导体，可用于制作发光二极管(LED)等光电器件。近年来，随着科技的发展，铟及其化合物已经被广泛地应用于各种合金的制造、半导体材料的合成、红外线检测器和震荡器的制造以及临床医学中的肿瘤放射治疗和放射性核素显影等行业。氢氧化铟作为铟的一种化合物，可以用作苯等难降解有机物的光降解催化剂以及碱性电池中的高效缓释剂，此外掺杂锡后制备的铟锡氧化物(ITO)具有高的可见光透过率以及良好的导电性而应用于以液晶显示器为主的平板显示器行业，因此铟的化合物在工业生产以及日常生活中中具有广泛的应用。Indium (In) is a group IIIA element and a low-melting metal with a tetragonal crystal structure. It is easy to synthesize III-V alloy semiconductors such as InN, InGaN, InP and InAs, and can be used to make optoelectronic devices such as light-emitting diodes (LEDs). In recent years, with the development of science and technology, indium and its compounds have been widely used in the manufacture of various alloys, the synthesis of semiconductor materials, the manufacture of infrared detectors and oscillators, and tumor radiation therapy and radionuclides in clinical medicine. Development and other industries. Indium hydroxide, as a compound of indium, can be used as a photodegradation catalyst for refractory organics such as benzene and as a high-efficiency slow-release agent in alkaline batteries. In addition, indium tin oxide (ITO) prepared after doping with tin has high Visible light transmittance and good conductivity are used in the flat panel display industry dominated by liquid crystal displays, so indium compounds are widely used in industrial production and daily life.
目前国内外制备氧化铟及其氢氧化铟的方法很多，主要有水溶液法、热分解法、均相共沉淀法、溶胶-凝胶法、水热法等。其中采用水溶液法(卢信冲等，发明专利公开号CN1412117)的工艺特点主要是利用加入的添加剂来控制铟锡氢氧化物的长大来获得高品质的球形纳米氧化铟锡粉体，但是用水溶液法制备的样品存在严重的团聚以及粒径范围分布宽等缺点。采用热分解法(斯蒂潘·卡图希奇等，发明专利公开号CN176120)的工艺特点主要是在氧化气氛火焰中燃烧铟和锡的化合物，将其转化为铟锡复合氧化物纳米球形粉体，但这种方法的操作过程复杂，条件难以控制。另外，采用均相共沉淀法((钟兴文等，发明专利公开号CN1305957)、(宋宁等，发明专利公开号CN101214994)、(张建荣等，发明专利公开号CN1775693))的工艺特点在于将金属铟和金属锡的盐溶液分别溶解乳化，充分混合后共沉淀，洗涤，过滤，再烘干，灼烧，最后淬火磨碎，即成球形粉体，虽然工艺简单、周期短、操作方便、对设备的要求不高，但是在具体的制备过程中存在突出的团聚现象，可利用的粒子活性表面受到很大局限。采用溶胶-凝胶法((胡奇林等，发明专利公开号CN101041459)、(周慧娟等，发明专利公开号CN1225898))的工艺特点在于以金属醇盐为起始原料，利用醇盐的水解缩聚反应形成凝胶网络结构，但由于铟锡的金属醇盐价格昂贵且不易获得，不适合于大规模低成本的制备工艺要求。在这些方法中，水热法能使晶体在非受限的条件下充分生长，具有晶体形貌、大小可控，结晶完好等优点，同时反应条件也容易控制。目前已报道的利用水热法制备氢氧化铟或氧化铟的研究很少，如一种氧化铟纳米线有序集体的制备方法(占金华等，发明专利公开号CN101182031)，该发明以InCl3为原料，非极性烷烃为溶剂，十二胺、油酸作为表面活性剂，置于烘箱中于120-280℃恒温反应5-40h，产物水洗、醇洗后干燥，得到InOOH纳米线有序集聚体，InOOH在450-440℃下退火，得到In2O3纳米线有序集聚体。At present, there are many methods for preparing indium oxide and indium hydroxide at home and abroad, mainly including aqueous solution method, thermal decomposition method, homogeneous co-precipitation method, sol-gel method, hydrothermal method and so on. Wherein adopt the aqueous solution method (Lu Xinchong etc., invention patent publication number CN1412117) technological characteristic mainly is to utilize the additive that adds to control the growth of indium tin hydroxide to obtain high-quality spherical nano-indium tin oxide powder, but use The samples prepared by the aqueous solution method have serious agglomeration and wide particle size distribution. The technical characteristics of adopting the thermal decomposition method (Stepan Katusic, etc., invention patent publication number CN176120) are mainly to burn the compound of indium and tin in the oxidizing atmosphere flame, and convert it into nano-spherical powder of indium-tin composite oxide , but the operation process of this method is complicated and the conditions are difficult to control. In addition, the process characteristics of adopting the homogeneous co-precipitation method ((Zhong Xingwen, etc., patent publication number CN1305957), (Song Ning, etc., patent publication number CN101214994), (Zhang Jianrong, etc., patent publication number CN1775693)) is that metal indium Dissolve and emulsify with the salt solution of metal tin respectively, fully mix and co-precipitate, wash, filter, then dry, burn, and finally quench and grind to form a spherical powder. Although the process is simple, the cycle is short, the operation is convenient, and the equipment is The requirements of the particle are not high, but there is a prominent agglomeration phenomenon in the specific preparation process, and the available particle active surface is greatly limited. Adopt sol-gel method ((Hu Qilin etc., invention patent publication number CN101041459), (Zhou Huijuan etc., invention patent publication number CN1225898)) process characteristic is to take metal alkoxide as starting material, utilize the hydrolysis polycondensation reaction of alkoxide to form Gel network structure, but because the metal alkoxide of indium tin is expensive and not easy to obtain, it is not suitable for large-scale and low-cost preparation process requirements. Among these methods, the hydrothermal method can fully grow crystals under unrestricted conditions, and has the advantages of controllable crystal morphology, size, and perfect crystallization, and the reaction conditions are also easy to control. There are very few studies on the preparation of indium hydroxide or indium oxide by the hydrothermal method reported at present, such as a method for preparing indium oxide nanowire ordered collectives (Zhan Jinhua, etc., invention patent publication number CN101182031), this invention uses InCl3 as Raw materials, non-polar alkanes as solvents, dodecylamine and oleic acid as surfactants, placed in an oven at a constant temperature of 120-280°C for 5-40 hours, the product was washed with water and alcohol and then dried to obtain ordered aggregation of InOOH nanowires body, and InOOH was annealed at 450-440°C to obtain ordered aggregates of In 2 O 3 nanowires.
以上有关氢氧化铟的制备方法所制备得到的球形粉体，可利用的活性表面较小且团聚而成的颗粒也为球形形貌。而目前相关文献中还没有高比表面积、形貌可控的纳米片层组装而成的花状氢氧化铟的报道。The spherical powder prepared by the above method for preparing indium hydroxide has a smaller active surface and the agglomerated particles also have a spherical shape. At present, there is no report on flower-like indium hydroxide assembled from nanosheets with high specific surface area and controllable morphology in related literature.
发明内容 Contents of the invention
本发明的目的在于提供一种步骤简单，操作方便的制备高比表面积花状氢氧化铟粉体的方法。The object of the present invention is to provide a method for preparing high specific surface area flower-shaped indium hydroxide powder with simple steps and convenient operation.
而为了得到高比表面积、形貌可控的花状氢氧化铟，本发明的技术方案为：以含In3+的水溶性无机盐水溶液为铟源，尿素(CO(NH2)2)为碱源，十二烷基硫酸钠(SDS)为表面活性剂，将以上反应物经超声震荡后，在密封反应器90-105℃低温水热反应12-24h；冷却过滤得到沉淀物经洗涤，离心沉淀，烘干后即得花状氢氧化铟。In order to obtain flower-shaped indium hydroxide with high specific surface area and controllable morphology, the technical solution of the present invention is: use a water-soluble inorganic salt solution containing In 3+ as the indium source, and urea (CO(NH 2 ) 2 ) as Alkali source, sodium dodecyl sulfate (SDS) as the surfactant, after the above reactants are ultrasonically oscillated, they are hydrothermally reacted in a sealed reactor at 90-105°C for 12-24h at low temperature; the precipitates obtained by cooling and filtering are washed, Precipitate by centrifugation and dry to obtain flower-shaped indium hydroxide.
通过本发明的方法，发明人首次制备成功高比表面积、形貌为花状氢氧化铟粉体(In(OH)3)，所述的花状是指氢氧化铟粉体表面上是由纳米片层组装而成高比表积，形貌为花状。本发明的产物结晶度高、产率高、分散性好，并且前驱体经400℃煅烧1h后获得In2O3粉体，其花状形貌保持不变。Through the method of the present invention, the inventor successfully prepared for the first time a flower-shaped indium hydroxide powder (In(OH) 3 ) with a high specific surface area. The sheets are assembled to form a high specific area, and the shape is flower-like. The product of the invention has high crystallinity, high yield and good dispersibility, and the In 2 O 3 powder is obtained after the precursor is calcined at 400° C. for 1 hour, and the flower-like shape remains unchanged.
含In3+水溶性无机盐水溶液的浓度优选为0.01-0.2mol/L。The concentration of the water-soluble inorganic salt solution containing In 3+ is preferably 0.01-0.2 mol/L.
表面活性剂十二烷基硫酸钠，其含量优选为In3+物质的量的0.5-2倍。Surfactant sodium lauryl sulfate, its content is preferably 0.5-2 times the amount of In 3+ substances.
所述的尿素的含量优选为In3+物质的量的5-7倍。The content of the urea is preferably 5-7 times the amount of In 3+ substances.
含In3+的水溶性无机盐水溶液优选为氯化铟溶液或者硝酸铟溶液。The water-soluble inorganic salt solution containing In 3+ is preferably an indium chloride solution or an indium nitrate solution.
反应器内的升温速率为5-10℃/min。The heating rate in the reactor is 5-10°C/min.
本发明花状氢氧化铟粉体的制备方法具体的制备步骤为：The specific preparation steps of the preparation method of the flower-shaped indium hydroxide powder of the present invention are:
配制摩尔浓度为0.01-0.2mol/L的含In3+的无机盐的水溶液，在调配好的含铟的水溶性盐中加入表面活性剂十二烷基硫酸钠(其含量为In3+物质的量的0.5-2倍)，再在上述溶液中加入尿素作为碱源(尿素的含量为In3+物质的量的5-7倍)，然后超声震荡，搅拌均匀后，将混合液装入内衬为聚四氟乙烯的不锈钢反应釜内，密封后于90-105℃低温水热反应12-24h。取出后冷却至室温，将过滤得到的沉淀物，用乙醇和水的体积比为1：1的混合溶液洗涤，离心沉淀，80-90℃烘干，即得到花状氢氧化铟粉体。Prepare an aqueous solution of an inorganic salt containing In 3+ with a molar concentration of 0.01-0.2mol/L, and add a surfactant sodium lauryl sulfate (the content of which is In 3+ substance) to the prepared water-soluble salt containing indium 0.5-2 times the amount of In 3+ ), then add urea to the above solution as an alkali source (the content of urea is 5-7 times the amount of In 3+ substances), then ultrasonically vibrate, stir evenly, and put the mixed solution into In a stainless steel reaction kettle lined with polytetrafluoroethylene, after sealing, it is hydrothermally reacted at a low temperature of 90-105°C for 12-24h. Take it out and cool to room temperature, wash the precipitate obtained by filtration with a mixed solution of ethanol and water with a volume ratio of 1:1, centrifuge to precipitate, and dry at 80-90°C to obtain flower-shaped indium hydroxide powder.
本发明的优点在于：本发明采用水热法制备花状氢氧化铟，能使晶体在非受限的条件下充分生长，具有比表面积高，晶体形貌、大小可控，结晶完好等优点，并且获得的粉体的BET在20-40m2/g，XRD衍射表明主晶相为In(OH)3且沿[100]方向择优取向生长，杂相为InOOH且含量全部小于12％。该体系在微电子、光电、敏感器件、催化剂、碱性电池等领域拥有良好的应用前景。The advantage of the present invention is that: the present invention adopts the hydrothermal method to prepare flower-shaped indium hydroxide, which can make the crystal fully grow under unrestricted conditions, has the advantages of high specific surface area, controllable crystal shape and size, and perfect crystallization, etc. And the BET of the obtained powder is 20-40m 2 /g, XRD diffraction shows that the main crystal phase is In(OH) 3 and grows preferentially along the [100] direction, and the impurity phase is InOOH and its content is less than 12%. The system has good application prospects in the fields of microelectronics, optoelectronics, sensitive devices, catalysts, alkaline batteries and the like.
附图说明 Description of drawings
图1为实施例1制备的花状粉体的典型SEM照片Fig. 1 is the typical SEM photo of the flower-shaped powder prepared in embodiment 1
图2为实施例2制备的花状粉体的典型SEM照片Fig. 2 is the typical SEM photo of the flower-shaped powder prepared in embodiment 2
图3为实施例3制备的花状粉体的典型SEM照片Fig. 3 is the typical SEM photo of the flower-shaped powder prepared in embodiment 3
具体实施方式 Detailed ways
以下实施例旨在说明本发明而不是对本发明的进一步限定。The following examples are intended to illustrate the present invention without further limiting the invention.
实施例1：Example 1:
配制摩尔浓度为0.01mol/L的氯化铟无机盐的水溶液80mL，加入表面活性剂十二烷基硫酸钠0.0008mol，再加入0.004mol的尿素作为碱源。超声震荡数分钟后，将混合液装入100mL内衬为聚四氟乙烯的不锈钢反应釜内，密封后于90℃低温水热反应12h。取出，冷却至室温，将过滤得到的沉淀物，用乙醇和水的体积比为1：1的混合溶液洗涤，离心沉淀，80℃烘干，即得到花状氢氧化铟粉体。获得的粉体BET为38m2/g，XRD衍射表明主要为沿[100]方向择优取向，且含InOOH的量为8％。如图1所示。Prepare 80 mL of an aqueous solution of indium chloride inorganic salt with a molar concentration of 0.01 mol/L, add 0.0008 mol of surfactant sodium lauryl sulfate, and then add 0.004 mol of urea as an alkali source. After ultrasonic vibration for several minutes, the mixture was put into a 100mL stainless steel reaction kettle lined with polytetrafluoroethylene, sealed and then hydrothermally reacted at a low temperature of 90°C for 12h. Take it out, cool it down to room temperature, wash the precipitate obtained by filtration with a mixed solution of ethanol and water with a volume ratio of 1:1, centrifuge to precipitate, and dry at 80°C to obtain flower-shaped indium hydroxide powder. The obtained powder has a BET of 38 m 2 /g, and XRD diffraction shows that the preferred orientation is mainly along the [100] direction, and the content of InOOH is 8%. As shown in Figure 1.
实施例2：Example 2:
配制摩尔浓度为0.1mol/L的氯化铟水溶液80mL，加入0.008mol十二烷基硫酸钠及0.048mol尿素。反应温度为95℃，反应时间为18h，可以得到BET为31m2/g，含InOOH量为10％的花状氢氧化铟粉体。其余同实施例1。如图2所示。Prepare 80 mL of indium chloride aqueous solution with a molar concentration of 0.1 mol/L, add 0.008 mol of sodium lauryl sulfate and 0.048 mol of urea. The reaction temperature is 95°C, the reaction time is 18 hours, and the flower-shaped indium hydroxide powder with a BET of 31 m 2 /g and an InOOH content of 10% can be obtained. All the other are with embodiment 1. as shown in picture 2.
实施例3：Example 3:
配制摩尔浓度为0.2mol/L的硝酸铟水溶液80mL，加入0.032mol十二烷基硫酸钠及0.112mol尿素。反应温度为105℃，反应时间为24h，可以得到BET为23m2/g，含InOOH量为11％的花状氢氧化铟粉体。其余同实施例1。如图3所示。Prepare 80 mL of indium nitrate aqueous solution with a molar concentration of 0.2 mol/L, add 0.032 mol of sodium lauryl sulfate and 0.112 mol of urea. The reaction temperature is 105°C, the reaction time is 24 hours, and the flower-shaped indium hydroxide powder with a BET of 23 m 2 /g and an InOOH content of 11% can be obtained. All the other are with embodiment 1. As shown in Figure 3.
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| CN101857263A (en) * | 2010-06-23 | 2010-10-13 | 东华大学 | A method for preparing nano-indium oxide with controllable morphology by hydrothermal method |
| CN102134092A (en) * | 2011-02-17 | 2011-07-27 | 四川大学 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
| CN102826593A (en) * | 2012-09-11 | 2012-12-19 | 电子科技大学 | Preparation method for indium oxide nanometer material |
| CN103241767A (en) * | 2012-10-26 | 2013-08-14 | 河南圣玛斯光电科技有限公司 | Microemulsion-solvothermal technique of orthorhombic InOOH |
| CN105664973A (en) * | 2016-02-26 | 2016-06-15 | 大连理工大学 | A three-dimensional flower-like In2S3/In2O3 composite microsphere photocatalytic material and its preparation method |
| CN107827148A (en) * | 2017-11-21 | 2018-03-23 | 临沂大学 | A kind of chiasma type indium oxide nanometer material preparation method |
| CN110436514A (en) * | 2018-05-05 | 2019-11-12 | 北京化工大学 | The preparation method and application of transition metal element doped flower-shaped indium oxide gas sensitive |
| CN113877556A (en) * | 2021-10-18 | 2022-01-04 | 常州大学 | Indium oxyhydroxide/modified attapulgite photocatalytic composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857263A (en) * | 2010-06-23 | 2010-10-13 | 东华大学 | A method for preparing nano-indium oxide with controllable morphology by hydrothermal method |
| CN102134092A (en) * | 2011-02-17 | 2011-07-27 | 四川大学 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
| CN102134092B (en) * | 2011-02-17 | 2013-03-27 | 四川大学 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
| CN102826593A (en) * | 2012-09-11 | 2012-12-19 | 电子科技大学 | Preparation method for indium oxide nanometer material |
| CN103241767A (en) * | 2012-10-26 | 2013-08-14 | 河南圣玛斯光电科技有限公司 | Microemulsion-solvothermal technique of orthorhombic InOOH |
| CN103241767B (en) * | 2012-10-26 | 2014-12-24 | 河南圣玛斯光电科技有限公司 | Microemulsion-solvothermal technique of orthorhombic InOOH |
| CN105664973A (en) * | 2016-02-26 | 2016-06-15 | 大连理工大学 | A three-dimensional flower-like In2S3/In2O3 composite microsphere photocatalytic material and its preparation method |
| CN107827148A (en) * | 2017-11-21 | 2018-03-23 | 临沂大学 | A kind of chiasma type indium oxide nanometer material preparation method |
| CN107827148B (en) * | 2017-11-21 | 2019-11-15 | 临沂大学 | A kind of cross type indium oxide nano material preparation method |
| CN110436514A (en) * | 2018-05-05 | 2019-11-12 | 北京化工大学 | The preparation method and application of transition metal element doped flower-shaped indium oxide gas sensitive |
| CN113877556A (en) * | 2021-10-18 | 2022-01-04 | 常州大学 | Indium oxyhydroxide/modified attapulgite photocatalytic composite material and preparation method and application thereof |
| CN113877556B (en) * | 2021-10-18 | 2023-01-17 | 常州大学 | Indium oxyhydroxide/modified attapulgite photocatalytic composite material and its preparation method and application |
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