CN108295836A - 一种核壳结构ato/二氧化硅/二氧化钛复合材料的制备方法 - Google Patents
一种核壳结构ato/二氧化硅/二氧化钛复合材料的制备方法 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010703 silicon Substances 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 31
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 31
- 239000002114 nanocomposite Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 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
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
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- 230000008859 change Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 8
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 239000012774 insulation material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
本发明公开了一种核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法。采用化学共沉淀法制备纳米锑掺杂二氧化锡(ATO)颗粒，并通过在纳米ATO颗粒表面进一步包覆SiO2及TiO2层，获得新型核壳结构ATO/SiO2/TiO2纳米复合材料。该核壳结构纳米复合材料制备工艺简单，核壳比可以控制，利用SiO2作为桥梁可以一体化实现纳米ATO及纳米TiO2的功能，将其应用于涂料中制备出纳米复合涂料，可以解决“透明与隔热”这一矛盾性问题,具有极高的应用价值。
Description
技术领域
本发明涉及纳米材料领域，特别涉及一种核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法。
背景技术
核壳异质纳米结构材料具有不同于任何单一物质的性质，在材料化学和纳米技术领域引起了广泛的关注。核壳异质纳米结构材料可由不同组成功能的材料构成，通过材料复合、互补和优化可以构建更优质的复合功能材料与器件，满足发展的需求。在颗粒表面包覆壳层物质形成核壳结构材料，可以很好地控制粒子之间的相互作用，通过改变包覆物的尺寸、结构以及粒子的组成能够赋予颗粒特殊的功能特性，从而使其得到更加广泛的潜在应用。
纳米锑掺杂二氧化锡(Antimony doped Tin Oxide，ATO)是一种优异的透明隔热填料，而纳米TiO2是一种具备较高亲水性能和光催化性能的隔热填料。若采用适当方式将两者复合形成一种新型隔热材料，采用核壳结构可以一体化实现纳米ATO及纳米TiO2的功能，将其应用于涂料中制备出纳米复合涂料，可以解决“透明与隔热”这一矛盾性问题,具有极高的应用价值。
发明内容
本发明的目的在于克服现有技术中存在的缺点，提供一种核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法。通过引入一层薄的SiO2隔离层作为桥梁将纳米ATO和纳米TiO2两种纳米粒子共组装，制备核-壳异质纳米结构的ATO/SiO2/TiO2纳米复合材料，该方法既保持两种材料的特性，又使各组分间协同作用，制作工艺简单，成本低，易于大规模生产。
本发明的目的通过下述技术方案实现：
一种核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法，是采过化学共沉淀法制备纳米ATO前驱物；然后通过氨水催化水解正硅酸乙酯在纳米ATO前驱物表面包覆SiO2，通过洗涤、烘干、煅烧，获得核壳结构ATO/SiO2粉体；配制TiO2溶胶，再通过溶胶浸渍法获得核壳结构ATO/SiO2/TiO2纳米复合材料。
具体包括下述步骤：
(1)采用化学共沉淀法制备纳米ATO前驱物：按锑掺杂摩尔浓度为2～10％称取SnCl4·5H2O和SbCl3溶于盐酸溶液中，加入体积浓度为5～30％的氨水至pH＝3～4；将溶液50～80℃恒温水热15～120min，生成浅黄色沉淀；抽滤，用乙醇和去离子水清洗，获得纳米ATO前驱物；
(2)将纳米ATO前驱物加入无水乙醇，超声分散15～60min；加入体积浓度为5～25％的氨水，搅拌15～60min；滴加正硅酸乙酯反应3～4h；抽滤，用乙醇和去离子水清洗，烘干，450～700℃煅烧2～6h，自然冷却，获得核壳结构ATO/SiO2粉体；
(3)配制TiO2溶胶：在无水乙醇中加入二乙醇胺，滴加钛酸四丁酯，常温下封口搅拌0.5～3h；再缓慢滴加去离子水，搅拌0.5～3h，静置老化12～24h，获得TiO2溶胶；
(4)将ATO/SiO2粉体加入到TiO2溶胶中，超声分散15～30min；密封静置12～36h；乙醇洗涤，抽滤，烘干；450～700℃煅烧2～6h，得到核壳结构ATO/SiO2/TiO2纳米复合材料。
步骤(1)中，所述SnCl4·5H2O和SbCl3质量配比为(30～40):2；所述盐酸溶液浓度为2～3mol/L。
步骤(2)中，所述纳米ATO前驱物、无水乙醇、氨水、正硅酸乙酯的配比为1:(80～120):(5～30):(10～50)，其中纳米ATO前驱物以质量单位g计算，无水乙醇、氨水、正硅酸乙酯以体积单位ml计算。步骤(3)中，所述无水乙醇、二乙醇胺、钛酸四丁酯、去离子水按体积配比为(100～300):(5～30):5:(1～10)。
步骤(4)中，ATO/SiO2粉体与TiO2溶胶的配比为1:30～60，ATO/SiO2粉体以质量单位g计算，TiO2溶胶以体积单位ml计算。
所述核壳结构ATO/二氧化硅/二氧化钛复合材料，是以纳米ATO为内核，外面依次包覆SiO2和TiO2层的核壳结构。
本发明与现有技术相比具有如下优点和效果：
(1)本发明通过在纳米ATO颗粒表面包覆SiO2层及TiO2层，制备新型核壳结构ATO/SiO2/TiO2纳米复合材料，实验设备及工艺方法简单，经济成本低。
(2)通过SiO2隔离层作为桥梁将纳米ATO和纳米TiO2两种纳米粒子共组装，可一体化实现纳米ATO及纳米TiO2的功能，发挥其协同作用，在隔热涂料、光催化、光电等领域具有潜在的应用前景。
附图说明
图1是核壳结构ATO/SiO2/TiO2纳米复合材料的SEM图。
图2是核壳结构ATO/SiO2/TiO2纳米复合材料的TEM图。
图3是核壳结构ATO/SiO2/TiO2纳米复合材料的EDS图谱。
图4是核壳结构ATO/SiO2/TiO2纳米复合材料的XRD图谱。
具体实施方式
下面结合实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。
实施例1
称量33g SnCl4·5H2O及2g SbCl3溶于2mol/L盐酸溶液中，加入体积浓度为10％的氨水至pH＝3；将溶液60℃恒温水热30min，至生成浅黄色沉淀；抽滤，用乙醇和去离子水清洗10次，得到黄色沉淀的纳米ATO前驱物。
将1g纳米ATO前驱物加入100mL无水乙醇，超声分散30min；加入体积浓度为10％的10mL氨水，搅拌30min；滴加正硅酸乙酯20mL，反应3h；抽滤，用乙醇和去离子水清洗，80℃烘干12h，取出放入马弗炉650℃煅烧2h，自然冷却，获得ATO/SiO2粉体。
在75mL无水乙醇中加入5mL二乙醇胺，滴加2.5mL钛酸四丁酯，常温下封口搅拌1h；再缓慢滴加1mL去离子水，搅拌1h，静置老化24h，获得TiO2溶胶。
将2gATO/SiO2粉体加入到上述50mlTiO2溶胶中，超声分散30min；密封静置24h；乙醇洗涤3次，抽滤，80℃烘干12h，取出放入马弗炉500℃煅烧2h，得到目标产物：核壳结构ATO/SiO2/TiO2纳米复合材料。
图1为制得的核壳结构ATO/SiO2/TiO2纳米复合材料的SEM图。由图1可见，呈较均匀球型结构，粒径约为100nm～150nm。
图2为制得的核壳结构ATO/SiO2/TiO2纳米复合材料样品的TEM图。由图2可见，在单个微球的中央部分和边缘部分，具有明显不同的吸收衍射衬度，微球形成了核壳结构，核为纳米ATO，由于SiO2为无定性结构且包覆层较薄，因此SiO2层边界不明显，晶状的TiO2纳米粒子包覆在ATO/SiO2表面形成一层粗糙的包覆层，厚度约为20nm。
图3为制得的核壳结构ATO/SiO2/TiO2纳米复合材料的EDS图谱。从图3中，可以清楚看出Sn、Sb、Si、O和Ti元素存在，进一步证明了ATO、SiO2及TiO2层的存在。
图4为制得的核壳结构ATO/SiO2/TiO2纳米复合材料的XRD图谱。如图4所示，出现了SnO2的(110)，(101)，(200)，(211)，(220)，(310)，(301)等晶面的多重衍射峰，其衍射数据与JCPDS(21～1250)标准卡片相符，为金红石结构的SnO2。未见氧化锑的衍射峰出现，表明锑已完全掺杂进入到SnO2晶格中。在ATO/SiO2/TiO2样品中，由于复合材料中纳米TiO2粒子较细，仅在2θ≈26.5°处出现金红石TiO2(101)晶面特征衍射峰，与SnO2的(110)晶面的特征衍射峰叠加。
Claims (6)
1.一种核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法，其特征在于：是采过化学共沉淀法制备纳米ATO前驱物；然后通过氨水催化水解正硅酸乙酯在纳米ATO前驱物表面包覆SiO2，通过洗涤、烘干、煅烧，获得核壳结构ATO/SiO2粉体；配制TiO2溶胶，再通过溶胶浸渍法获得核壳结构ATO/SiO2/TiO2纳米复合材料。
2.根据权利要求1所述的核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法，其特征在于：包括下述步骤：
(1)采用化学共沉淀法制备纳米ATO前驱物：按锑掺杂摩尔浓度为2～10％称取SnCl4·5H2O和SbCl3溶于盐酸溶液中，加入体积浓度为5～30％的氨水至pH＝3～4；将溶液50～80℃恒温水热15～120min，生成浅黄色沉淀；抽滤，用乙醇和去离子水清洗，获得纳米ATO前驱物；
(2)将纳米ATO前驱物加入无水乙醇，超声分散15～60min；加入体积浓度为5～25％的氨水，搅拌15～60min；滴加正硅酸乙酯反应3～4h；抽滤，用乙醇和去离子水清洗，烘干，450～700℃煅烧2～6h，自然冷却，获得核壳结构ATO/SiO2粉体；
(3)配制TiO2溶胶：在无水乙醇中加入二乙醇胺，滴加钛酸四丁酯，常温下封口搅拌0.5～3h；再缓慢滴加去离子水，搅拌0.5～3h，静置老化12～24h，获得TiO2溶胶；
(4)将ATO/SiO2粉体加入到TiO2溶胶中，超声分散15～30min；密封静置12～36h；乙醇洗涤，抽滤，烘干；450～700℃煅烧2～6h，得到核壳结构ATO/SiO2/TiO2纳米复合材料。
3.根据权利要求2所述的核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法，其特征在于：步骤(1)中，所述SnCl4·5H2O和SbCl3质量配比为(30～40):2；所述盐酸溶液浓度为2～3mol/L。
4.根据权利要求2所述的核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法，其特征在于：步骤(2)中，所述纳米ATO前驱物、无水乙醇、氨水、正硅酸乙酯的配比为1:(80～120):(5～30):(10～50)，其中纳米ATO前驱物以质量单位g计算，无水乙醇、氨水、正硅酸乙酯以体积单位ml计算。
5.根据权利要求2所述的核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法，其特征在于：步骤(3)中，所述无水乙醇、二乙醇胺、钛酸四丁酯、去离子水的体积配比为(100～300):(5～30):5:(1～10)。
6.根据权利要求2所述的核壳结构ATO/二氧化硅/二氧化钛复合材料的制备方法，其特征在于：步骤(4)中，ATO/SiO2粉体与TiO2溶胶的配比为1:30～60，ATO/SiO2粉体以质量单位g计算，TiO2溶胶以体积单位ml计算。
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