CN1237654A - 单晶二氧化钛纳米丝的制备方法 - Google Patents
单晶二氧化钛纳米丝的制备方法 Download PDFInfo
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- CN1237654A CN1237654A CN98111329.XA CN98111329A CN1237654A CN 1237654 A CN1237654 A CN 1237654A CN 98111329 A CN98111329 A CN 98111329A CN 1237654 A CN1237654 A CN 1237654A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000004408 titanium dioxide Substances 0.000 title description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 41
- 239000011780 sodium chloride Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000013021 overheating Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910011011 Ti(OH)4 Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002159 nanocrystal Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- MQGIBEAIDUOVOH-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCOCCCC MQGIBEAIDUOVOH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Abstract
一种获得微米量级的TiO2纳米丝，尤其是单晶TiO2纳米丝的方法，制备NaCl溶液的微乳和TiO2前驱物Ti(OH) 4微乳，将NaCl溶液与Ti(OH) 4两种微乳均匀混合并在一定温度下作热处理，经过热处理，再经过分离、烘干，即得单晶TiO2纳米丝。所用原料是普通的化学药品，制备过程简单，无特殊要求。所得纳米棒尺寸均匀，通过改变成分配比，可以方便地改变纳米晶丝尺寸。重复性好。
Description
本发明涉及纳米丝状材料的制备，尤其涉及单晶二氧化钛纳米丝的制备方法。
现有碳弧法、激光烧融、膜模法，气液固(vls)等方法分别制备出纳米碳管、纳米硅(Si)和锗(Ge)棒、GaN棒(纳米级)等长度是微米而直径为几至几十纳米的丝、棒或管。至今还未曾见过获得微米量级的TiO2纳米丝，尤其是单晶TiO2纳米丝的制备方法。
本发明的目的是提出一种获得微米量级的TiO2纳米丝、尤其是单晶TiO2纳米丝的方法。
本发明的目的是这样实现的：一种获得微米量级的TiO2纳米丝，尤其是单晶TiO2纳米丝的方法，其特征是制备NaCl溶液的微乳和TiO2前驱物Ti(OH)4微乳将NaCl溶液与Ti(OH)4两种微乳均匀混合并在一定温度下作热处理，经过热处理0。5-4小时，再经过分离、烘干，即得单晶TiO2纳米丝。
其技术关键是实现Ti(OH)4和NaCl两种微乳的充分均匀混合和控制温度制备过程简单、易重复实现。
本发明的特点是：能获得微米量级的TiO2纳米丝，尤其是单晶TiO2纳米丝，这种材料是微电子、光电器件中具有广泛的应用前景。所用原料是普通的化学药品，易买到。制备过程简单，无特殊要求。所得纳米棒尺寸均匀，通过改变成分配比，可以方便地改变纳米晶丝尺寸。重复性好。
以下结合附图和通过实施例对本发明作进一步说明：
图1为单晶TiO2纳米丝的形貌
图2为单晶TiO2纳米丝的高分辨率像，直径25nm，丝内无缺陷。
微乳法制备TiO2前驱物Ti(OH)4
实验所用微乳体系中，油相为环己烷；表面活性剂是壬基酚聚氧乙烯五醚和九醚分别NP5、NP9，亦可以为其它表面活性剂，其重量比为NP5∶NP9=1∶1的NP5/NP9混合物；水相分别是TiCl4溶液，氨水和NaCl溶液。
本方法主要包括两步，第一步实现NaCl微乳和TiO2的前驱物Ti(OH)4微乳的充分混合；第二步将上述混合物在一定的温度下热处理分离、烘干后即得到制品。具体过程如下：
1：制备TiO2前驱物Ti(OH)4微乳
实验所用微乳体系中，油相为C6-8的芳、烃族溶剂，如环己烷；表面活性剂是重量比NP5∶NP9=1∶1的NP5/NP9混合物；水相分别是TiCl4溶液，氨水和NaCl溶液。
将适量环己烷，NP5/NP9,0.5M TiCl4溶液在烧杯中混合制成TiCl4溶液的微乳；将适量环己烷，NP5/NP9,2M NH4OH溶液混合制成NH4OH溶液的微乳；再将适量上述两种微乳充分混合，反应得到Ti(OH)4的微乳。所有操作在10-25℃下进行。
2:NaCl溶液微乳的制备：
将适量环己烷，NP5/NP9,2M NaCl溶液在10-25℃下混合制成NaCl溶液的微乳。
3．Ti(OH)4和NaCl的充分均匀混合：
将适量Ti(OH)4微乳和NaCl微乳在10-25℃下充分混合，混合微乳中Ti和Na的原子比记作NT.NT一般取值20-2000。将混合微乳倒入足量丙酮中，沉淀生成。沉淀离心分离后，用丙酮清洗两遍，烘干后得到白色NaCl和Ti(OH)4混合粉末。
4热处理；
将上述粉末在适当温度热处理一段时间。产物用水溶解，除去其中NaCl。沉淀离心分离，用水再洗两遍，烘干。即制成具有金红石晶体结构的TiO2纳米晶丝。
表1给出了三组成分配比及所得TiO2纳米晶丝的尺寸。热处理为在750℃保温2小时。其中，环己烷，丙酮，NaCl和氨水为分析纯，TiCl4为化学纯，表面活性剂是直接从化工厂购买的工业原料，水是一次蒸馏水，热处理炉为管式定碳炉。表中TiCl4微乳成分是：0.2ml 0.5M TiCl4溶液+6.6ml环己烷+3.4mlNP5/NP9；NH4OH微乳的成分为0.2ml 2M氨水+6.6ml环己烷+3.4mlNP5/NP9；NaCl微乳的成分是0.2ml 2M NaCl溶液+6.6ml环己烷+3.4mlNP5/NP9。从表中可以看出，纳米TiO2晶丝的尺寸随NT的值变化，NT越大，品丝越细长。NT的值取20-2000。
本发明方法的关键是在微乳体系中实现Ti(OH)4和NaCl的充分均匀混合。对比实验表明，若二者混合不均匀，则棒较粗，粗细不均匀。
表1微乳体系的成分和TiO2纳米晶丝的尺寸
| 123 | TiCl4微乳4ml2mllml | NH4OH微乳4ml2mllml | NaCl微乳12ml24ml30ml | NT1004001000 | 晶须平均尺寸(长度直径)2μm、75nm2μm、30nm4μm、22nm |
Claims (5)
1．一种获得微米量级的TiO2纳米丝，尤其是单晶TiO2纳米丝的方法，其特征是制备NaCl溶液的微乳和TiO2前驱物Ti(OH)4微乳将NaCl溶液与Ti(OH)4两种微乳均匀混合并在一定温度下作热处理，经过热处理，再经过分离、烘干，即得单晶TiO2纳米丝。
2．由权利要求1所述的制备微米量级的TiO2纳米丝的方法，其特征是微乳体系中，油相为C6nC8-的芳、烃族溶液，如环己烷；水相分别是TiCl4溶液，氨水和NaCl溶液，再加上表面活性剂使微乳充分均匀。
3．由权利要求1、2所述的制备微米量级的TiO2纳米丝的方法，其特征是表面活性剂为NP5/NP9，以0.5M TiCl4溶液混合制成TiCl4溶液的微乳；将适量环己烷，NP5/NP9,2M NH4OH溶液混合制成NH4OH溶液的微乳；再将适量上述两种微乳充分混合，反应得到Ti(OH)4的微乳，所有操作在10-25℃下进行。
4．由权利要求1、2所述的制备微米量级的TiO2纳米丝的方法，其特征是过热处理时间为0。5-4小时。
5由权利要求1、2所述的制备微米量级的TiO2纳米丝的方法，其特征是混合微乳中Ti和Na的原子比取值20-2000。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332909C (zh) * | 2004-12-07 | 2007-08-22 | 清华大学 | LiFePO4/Li－Ti－O纳米纤维复合材料制备方法 |
| CN100415952C (zh) * | 2006-12-28 | 2008-09-03 | 上海交通大学 | 热蒸发法合成小直径单晶SiC纳米丝有序阵列的方法 |
| CN100441751C (zh) * | 2005-12-20 | 2008-12-10 | 中国科学院兰州化学物理研究所 | 油溶性二氧化钛纳米棒的制备方法 |
| CN101994154A (zh) * | 2010-11-26 | 2011-03-30 | 浙江大学 | 一种腰鼓形单晶锐钛矿二氧化钛及其聚集微球的制备方法 |
| CN102995120A (zh) * | 2012-12-12 | 2013-03-27 | 国家纳米科学中心 | 一种纳米TiO2单晶材料、其制备方法及用途 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19639835A1 (de) * | 1996-09-27 | 1998-04-09 | Rwe Ges Fuer Forschung Und Ent | Verfahren zur Herstellung feinstkristalliner Metalloxidschichten und -pulver |
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1998
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332909C (zh) * | 2004-12-07 | 2007-08-22 | 清华大学 | LiFePO4/Li－Ti－O纳米纤维复合材料制备方法 |
| CN100441751C (zh) * | 2005-12-20 | 2008-12-10 | 中国科学院兰州化学物理研究所 | 油溶性二氧化钛纳米棒的制备方法 |
| CN100415952C (zh) * | 2006-12-28 | 2008-09-03 | 上海交通大学 | 热蒸发法合成小直径单晶SiC纳米丝有序阵列的方法 |
| CN101994154A (zh) * | 2010-11-26 | 2011-03-30 | 浙江大学 | 一种腰鼓形单晶锐钛矿二氧化钛及其聚集微球的制备方法 |
| CN101994154B (zh) * | 2010-11-26 | 2012-06-06 | 浙江大学 | 一种腰鼓形单晶锐钛矿二氧化钛及其聚集微球的制备方法 |
| CN102995120A (zh) * | 2012-12-12 | 2013-03-27 | 国家纳米科学中心 | 一种纳米TiO2单晶材料、其制备方法及用途 |
| CN102995120B (zh) * | 2012-12-12 | 2015-05-20 | 国家纳米科学中心 | 一种纳米TiO2单晶材料、其制备方法及用途 |
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