CN107285377A - 介孔中空球形二氧化钛及其制备方法 - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
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- APIDIPGVBRXKEJ-UHFFFAOYSA-N acetic acid titanium Chemical compound [Ti].CC(O)=O.CC(O)=O APIDIPGVBRXKEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
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Abstract
本发明提供了一种介孔中空球形二氧化钛，其中所述介孔中空球形二氧化钛粒径为1.0‑2.5μm，中空球壳壁厚为100‑150nm，比表面积大于50m2g‑1，孔径分布2‑50nm，孔体积大于0.13cm3g‑1。本发明还提供了制备介孔中空球形二氧化钛的方法。本发明的特点是：不使用模板剂(材料)，制备参数稳定且产率高，不需经过后续热处理，有望实现大规模制备。
Description
技术领域
本发明涉及一种制备二氧化钛光催化剂，特别是一种溶剂热法制备介孔中空球形二氧化钛光催化剂的方法。
背景技术
由于其较宽的带宽、环境友好、低毒、低成本等特性，二氧化钛被认为是一种最具应用前景的半导体材料之一，已被广泛用于环境催化、传感器件、光电池、储能等诸多领域。越来越多的研究表明纳米材料的应用效果和性质在很大程度上依赖于其形貌、结构、尺寸等特性。因此，针对二氧化钛的形貌结构的设计和制备能够有效提高其应用效果。
具有微米/纳米复合尺寸效应的中空球形结构具有低密度、高的表面/体积比、和空洞效应等特性，因此具有提高应用效果的能力。而目前在制备中空球形纳米颗粒时广泛采用的方法是模板法，即通常通过吸附或化学沉淀法在硬质模板(单分散聚合物微球、硅基微球、弹基微球等)或软质模板(胶束、油滴、气泡等)上形成包覆层，随即通过腐蚀、浸渍或煅烧等方法去除模板，从而生成中空球形结构。该方法的制备过程决定了其具有制备程序复杂、产物易坍塌破损等不足，而其模板剂均为消耗性材料，成本提高。因此，开发简单易行、产品稳定、且不用模板剂来制备中空球形二氧化钛的新方法对二氧化钛的发展应用具有十分重要的意义。
发明内容
本发明的目的在于提供一种制备介孔中空球形二氧化钛光催化剂的方法，该方法具有制备过程简单、技术参数稳定、不用模板剂、不需经过后续热处理等优点，避免了程序和成本的浪费，提高了产品的稳定性。
为达成上述目的，本发明提供了一种介孔中空球形二氧化钛，其中所述介孔中空球形二氧化钛粒径为1.0-2.5μm，中空球壳壁厚为100-150nm，比表面积大于50m2g-1，孔径分布2-50nm，孔体积大于0.13cm3g-1。
本发明还提供了一种利用溶剂热法制备根据本发明所述的介孔中空球形二氧化钛的方法，步骤如下：
A)前驱体制备：将无机钛盐加入到醋酸/醋酸酐混合液中生成白色悬浊液，在100-140℃下回流加热至所述悬浊液重新溶解为黄色澄清溶液后继续回流加热至生成白色沉淀，随之向反应系统中再次加入醋酸/醋酸酐混合液，继续加热至伴生酸彻底挥发，将产物过滤并淋洗彻底去除残留的醋酸/醋酸酐后在不高于100℃下减压干燥即生成白色醋酸钛前驱体；
B)介孔中空球形二氧化钛的制备：称取步骤A中制备的醋酸钛前驱体，按1/80-1/40的质量比例溶解到醇中，磁力搅拌均匀后在不高于220℃的温度下反应，冷却至室温后将产物用醇清洗数次后经60-100℃真空干燥即生成介孔中空球形二氧化钛。
根据本发明的一个实施方案，所述无机钛盐是四氯化钛。
根据本发明的一个实施方案，所述醋酸/醋酸酐混合液的体积比为3:1-4:1。
根据本发明的一个实施方案，所述伴生酸彻底挥发，经回流蒸汽检测为pH>6。
根据本发明的一个实施方案，用苯进行淋洗。
根据本发明的一个实施方案，所述醇是无水乙醇。
根据本发明的一个实施方案，所述反应在聚四氟乙烯内衬反应釜中进行。
根据本发明的一个实施方案，所述方法以前驱体溶剂热法进行一次性制备，不添加任何模板剂或材料。
根据本发明的一个实施方案，所述方法不需经过退火煅烧的后处理程序。
根据本发明制备的二氧化钛的特性为：粒径1.0-2.5μm，中空球壳壁厚约100-150nm，比表面积大于50m2g-1，孔径分布2-50nm，孔体积大于0.13cm3g-1。
本发明与已有的技术相比较其优点是：不使用模板剂(材料)，制备参数稳定且产率高，不需经过后续热处理，有望实现大规模制备。
附图说明
图1是根据本发明的一个实施例制备的介孔中空球形二氧化钛的扫描电镜图(a)和透射电镜图(b)。
具体实施方式
溶剂热法制备介孔中空结构二氧化钛的方法，包括以下几个步骤：
1)称取10.5g四氯化钛在搅拌下加入到75mL醋酸/醋酸酐混合液(V/V＝4:1)中生成白色悬浊液(注：本方案所有试剂均购自国药集团)；
2)将步骤1所得悬浊液在135℃下回流加热至悬浊液重新溶解为为黄色澄清溶液。
3)在步骤2基础上继续回流加热约1小时生成白色沉淀，随之向反应系统中再次加入60mL的醋酸/醋酸酐混合液(体积比为4/1)，继续加热至伴生盐酸彻底挥发；
4)将步骤3的产物过滤并用苯淋洗彻底去除残留的醋酸/醋酸酐后在80℃下减压干燥即生成白色钛前驱体；
5)称取0.5g步骤4生成的前驱体，按约1:80的质量比例溶解到50mL无水乙醇中，磁力搅拌均匀后转入聚四氟乙烯内衬反应釜中以2℃/min的升温速率加热到200℃，并保持在此温度下8小时，冷却至室温后将产物用无水乙醇清洗数次后经80℃真空干燥即生成介孔中空球形二氧化钛。
经场发射扫描电子显微镜(日本日立公司(Hitachi)，SU8000)和透射电子显微镜(日本电子(JEOL)，JEM2100)表征以该方法制备的介孔中空球形二氧化钛(参见图1)，其平均粒径为1.5μm，中空球壳壁厚约100-150nm；经比表面积和孔径分析仪(美国麦克莫瑞提克公司(Micromeritics)，ASAP2000)测试，比表面积为50m2g-1，孔径为10nm，孔体积为0.134cm3g-1。
6)在上述实施方案中，在与步骤5)相同反应条件下，减小反应时间至1小时和2小时，则分别生成粒径为3nm的纳米颗粒和粒径为70-150nm的球形大颗粒。
7)按照上述实施例，以其他无机钛盐(如四氯化钛、硫酸氧钛等)替换醋酸钛直接作为反应前驱体，不能生成中空球形二氧化钛，生成产物为不规则非晶颗粒。
以上所述为本专利的操作流程及方法，未对本专利做任何形式上的限制。任何熟悉本领域的研究及技术人员，在不脱离本专利技术方案范围的情况下，利用上述内容对本专利技术方案做出的非创新性变动和修改，均属于权利要求书保护的范围。
Claims (10)
1.一种介孔中空球形二氧化钛，其中所述介孔中空球形二氧化钛粒径为1.0-2.5μm，中空球壳壁厚为100-150nm，比表面积大于50m2g-1，孔径分布2-50nm，孔体积大于0.13cm3g-1。
2.一种利用溶剂热法制备根据权利要求1所述的介孔中空球形二氧化钛的方法，步骤如下：
A)前驱体制备：将无机钛盐加入到醋酸/醋酸酐混合液中生成白色悬浊液，在100-140℃下回流加热至所述悬浊液重新溶解为黄色澄清溶液后继续回流加热至生成白色沉淀，随之向反应系统中再次加入醋酸/醋酸酐混合液，继续加热至伴生酸彻底挥发，将产物过滤并淋洗彻底去除残留的醋酸/醋酸酐后在不高于100℃下减压干燥即生成白色醋酸钛前驱体；
B)介孔中空球形二氧化钛的制备：称取步骤A中制备的醋酸钛前驱体，按1/80-1/40的质量比例溶解到醇中，磁力搅拌均匀后在不高于220℃的温度下反应，冷却至室温后将产物用醇清洗数次后经60-100℃真空干燥即生成介孔中空球形二氧化钛。
3.根据权利要求2所述的方法，其中所述无机钛盐是四氯化钛。
4.根据权利要求2所述的方法，其中所述醋酸/醋酸酐混合液的体积比为3:1-4:1。
5.根据权利要求2所述的方法，其中所述伴生酸彻底挥发，经回流蒸汽检测为pH>6。
6.根据权利要求2所述的方法，其中用苯进行淋洗。
7.根据权利要求2所述的方法，其中所述醇是无水乙醇。
8.根据权利要求2所述的方法，其中所述反应在聚四氟乙烯内衬反应釜中进行。
9.根据权利要求2所述的方法，其中所述方法以前驱体溶剂热法进行一次性制备，不添加任何模板剂或材料。
10.根据权利要求2所述的方法，其中所述方法不需经过退火煅烧的后处理程序。
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| CN106929949A (zh) * | 2015-12-31 | 2017-07-07 | 山东大学 | 一步法合成聚醋酸氧钛前驱体、其溶胶纺丝液以及氧化钛晶体长纤维的制备方法 |
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