CN100482591C - 纳米氧化锡颗粒的制备方法 - Google Patents
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000008187 granular material Substances 0.000 title claims description 8
- 238000000034 method Methods 0.000 title abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- -1 polyoxyethylene Polymers 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 14
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
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Abstract
本发明公开了一种纳米氧化锡颗粒的制备方法，该方法是以金属锡盐、柠檬酸、聚乙二醇为原料，将之混合溶解于去离子水中，而后通过微波加热制得凝胶前驱体，经马弗炉焙烧后可以得到分散性好、团聚少、平均晶粒尺寸为17.0nm左右的纳米氧化锡颗粒，本方法具有工艺简单、生产周期短、成本低等特点。
Description
技术领域
本发明属于纳米材料领域，本发明具体涉及一种纳米氧化锡颗粒的制备方法，该材料可以用于制备气敏元件、导电材料、催化剂、催化剂载体等。
背景技术
纳米氧化锡是一种重要的无机功能材料。氧化锡具有熔点高、高温下不易分解、化学性质稳定、不易与强酸强碱反应，响应速度快等特点，广泛应用于气敏材料。作为n型半导体，氧化锡具有优良的光电子特性，可以用于导电材料。氧化锡也是一种很好的催化剂和催化剂载体，不仅具有较强的完全氧化能力，也有较好的选择氧化活性和水热稳定性，可用于烃类氧化、脱氢环化、不饱和醛、酮或者羧酸的选择加氢、NOx的还原等，此外在有机催化、光催化和电催化中都广泛应用。
氧化锡的性能与比表面有很强的依赖性，要得到优异性能氧化锡材料，必须制备超细氧化锡粉体。目前报道的方法有溶胶-凝胶法(Shek C.H.Nanostruct.Mater.1999，11：887—893)、化学沉淀法(李来风等.材料研究学报，2000，14(1)：37-41)、水热合成法(Wang Chengyuan Nanostruct.Mater.1996，7：421—427)、醇盐水解法(Sophie de Monredon，J.Mater.Chem.2002，12：2396—2400)、柠檬酸燃烧法(Fraigi L.B.Mater.Lett.2001，47：262—266)、微乳液法(潘庆谊等，无机材料学报，1999，14：83—88)、气体凝聚法(Suh S.Thin Solid Films 1999，345：240—249)等。目前相关的中国专利有94117467.0采用均匀沉淀—超临界干燥方法制备用于低温气敏元件的氧化锡；专利97114210.6采用溶胶凝胶以及水解法制备SnO2用于常温气敏元件；专利200310108633.6采用溶胶凝胶法制备用于气敏元件的氧化锡粉体；专利200310107905.0采用水热法以及专利03118150.3采用固相法制备纳米SnO2等。
传统的柠檬酸溶胶法制备纳米SnO2，需要水浴或者其他热源缓慢蒸干水分，成胶时间长。而柠檬酸燃烧法需要金属的硝酸盐作强氧化剂，制备锡的硝酸盐过程较繁琐，耗费时间。微波辐射加热具有快速、均匀的特点，较之传统加热方式有独特的优势。在材料制备方面，利用微波辐射加热，可以加快陶瓷材料的合成和烧结、提高分子筛的晶化以及改善催化剂的催化性能等。本发明把柠檬酸盐法和微波加热的优点相结合制备氧化锡纳米粒子。
发明内容
本发明提供一种工艺简单、成本低廉、晶粒尺寸小的氧化锡纳米颗粒的制备方法。
本发明采用金属锡盐、柠檬酸、聚乙二醇为原料，将之混合溶解于去离子水中，而后通过微波加热方式制得凝胶前驱体，对该前驱体进行焙烧即可得到氧化锡颗粒。配置的锡盐溶液的浓度在0.1～4.0mol·L-1，锡盐与柠檬酸的摩尔比在1∶2～1∶4之间，加入的聚乙二醇的量为0.1～0.3g，溶液配制温度为常温或者加热。使用微波加热形成凝胶，微波加热的时间在5～15min，微波加热功率为200～700W。凝胶前驱体焙烧的时间为2～6h，焙烧温度为450～600℃。
本发明采用四氯化锡、柠檬酸、聚乙二醇400或者600为原料，将之混合溶解于去离子水中，而后同过微波加热制得凝胶前驱体，而后在马弗炉中焙烧凝胶前驱体即得到纳米颗粒。
工艺条件：SnCl4的摩尔浓度为0.1～4.0mol·L-1，锡盐与柠檬酸的摩尔比在1：2～1：4之间，加入的聚乙二醇的量为0.1～0.3g，溶液配制温度为常温或者加热，微波加热的时间在5～15min，微波加热功率为200～700W，凝胶前驱体焙烧的时间为2～6h，焙烧温度为450～600℃。
纳米颗粒特征：颗粒粒径小，晶粒约为17.0nm，大小分布较均匀，采用微波加热的方式，成胶时间由原来的1～3d缩短到10min左右，且成胶质量好，节省了时间和能源，提高了效率，简化了操作，拓展了微波在材料制备方面的应用和纳米粒子的制备方法
附图说明
图1：不同焙烧温度的样品的XRD图；
图2：450℃焙烧样品的TEM图；
图3：500℃焙烧样品的TEM图；
图4：600℃焙烧样品的TEM图；
具体实施方式
实例：
1、取SnCl4·5H2O约7.0188g、柠檬酸8.4065g、聚乙二醇(400)0.3g加入10ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热9min后600℃下在马弗炉焙烧3h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为17.4nm。
2、取SnCl4·5H2O约7.0188g、柠檬酸8.4056g、聚乙二醇(400)0.3g加入10ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热13min后500℃下在马弗炉焙烧4h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为18.3nm
3、取SnCl4·5H2O约7.0188g、柠檬酸16.8112g、聚乙二醇(600)0.3g加入15ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热11min后500℃下在马弗炉焙烧4h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为16.8nm。
4、取SnCl4·5H2O约7.0188g、柠檬酸12.6084g、聚乙二醇(600)0.3g加入12ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热9min后600℃下在马弗炉焙烧2h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为18.1nm。
5、取SnCl4·5H2O约7.0188g、柠檬酸8.4065g、聚乙二醇(400)0.3g加入10ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热9min后450℃下在马弗炉焙烧4h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为14.1nm。
6、取SnCl4·5H2O约7.0188g、柠檬酸8.4065g、聚乙二醇(400)0.3g加入10ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热7min后500℃下在马弗炉焙烧4h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为14.5nm。
7、取SnCl4·5H2O约3.5094g、柠檬酸4.2033g、聚乙二醇(400)0.1g加入10ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热9min后500℃下在马弗炉焙烧4h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为14.7nm。
8、取SnCl4·5H2O约7.0188g、柠檬酸8.4065g、聚乙二醇(400)0.25g加入10ml去离子水中混合，搅拌均匀，然后放入微波炉中采用中等微波功率加热9min后500℃下在马弗炉焙烧6h。根据XRD的结果，由Scherrer方程求得纳米颗粒晶粒大小为17.2nm。
Claims (3)
1、一种纳米氧化锡颗粒的制备方法，其特征在于：采用四氯化锡、柠檬酸、聚乙二醇为原料，将之混合溶解于去离子水中，而后通过微波加热方式制得凝胶前驱体，微波加热的时间为5～15min，微波加热功率为200～700W，对该前驱体进行焙烧即可得到氧化锡颗粒。
2、按权利要求1所述的一种纳米氧化锡颗粒的制备方法，其特征在于：配置的四氯化锡溶液的浓度在0.1～4.0mol·L-1，四氯化锡与柠檬酸的摩尔比在1:2～1:4之间，加入的聚乙二醇的量为0.1～0.3g，溶液配制温度为常温或者加热。
3、按权利要求1或2所述的一种纳米氧化锡颗粒的制备方法，其特征在于：凝胶前驱体焙烧的时间为2～6h，焙烧温度为450～600℃。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19828692A1 (de) * | 1997-06-27 | 1999-01-07 | Ami Doduco Gmbh | Verfahren zum Granulieren von Zinnoxidpulver und damit hergestellte Kontaktwerkstoffe auf der Basis von Silber-Zinnoxid |
| CN1544334A (zh) * | 2003-11-14 | 2004-11-10 | 中国科学院上海硅酸盐研究所 | 一种氧化锡粉体的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19828692A1 (de) * | 1997-06-27 | 1999-01-07 | Ami Doduco Gmbh | Verfahren zum Granulieren von Zinnoxidpulver und damit hergestellte Kontaktwerkstoffe auf der Basis von Silber-Zinnoxid |
| CN1544334A (zh) * | 2003-11-14 | 2004-11-10 | 中国科学院上海硅酸盐研究所 | 一种氧化锡粉体的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| SnO2纳米晶的制备及性能研究. 韩巧凤等.上海化工，第18期. 2002 |
| SnO2纳米晶的制备及性能研究. 韩巧凤等.上海化工，第18期. 2002 * |
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