CN106348340B - 一种TiO2单晶空心四方纳米锥材料、制备方法及其应用 - Google Patents
一种TiO2单晶空心四方纳米锥材料、制备方法及其应用 Download PDFInfo
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Abstract
本发明提供了一种TiO2单晶空心四方纳米锥材料、制备方法及其应用。将1,6‑己二胺与环己烷混合后，加入Ti(OC4H9)4；然后加入去离子水搅拌混合，获得悬浊液；将所得悬浊液密封加热反应，冷却、离心，沉淀洗涤、干燥，得到TiO2单晶空心四方纳米锥材料。与现有技术相比，本发明制备的锐钛矿TiO2单晶空心四方纳米锥，具有大量暴露的{101}面和大的比表面积；对有机染料罗丹明B、甲基橙和无色有机小分子苯酚展现出卓越的光催化活性，而且降解效率高、稳定性好以及环境友好、工艺简单、成本低的优点。
Description
技术领域
本发明属于纳米材料制备方法及环境化学和光电化学交叉应用领域，具体涉及一种TiO2单晶空心四方纳米锥材料、制备方法及其应用。
背景技术
二氧化钛(TiO2)是一种无毒、低成本、光活性和稳定性好的宽带隙半导体金属氧化物材料，在光催化可再生能源创造和环境整治上获得广泛研究。近十几年来.随着社会的发展和人们对环境保护的觉醒，纳米级TiO2半导体光催化材料的研究引起了国内外物理、化学、材料和环境等领域科学家的广泛关注，成为最活跃的研究领域之一。其中，TiO2光催化技术在环保领域的应用研究.引起了污水治理方面的技术革命。
通常，TiO2的性能取决于晶相、结晶性、形貌和比表面积等。在四种天然存在的锐钛矿、金红石、板钛矿和TiO2(B)中，锐钛矿TiO2被公认为是在环境应用中活性最强的相。TiO2晶体的晶面取向决定其光催化活性，当TiO2光催化剂拥有大的活性面时可以实现高的光催化活性。
人们对锐钛矿TiO2高比例的高能{001}面和小尺寸粒径的研究越来越多。另一方面，根据计算结果，锐钛矿TiO2三个面的相对光氧化和光还原活性次序是：{010}＞{101}＞{001}。而且，通过实验比较{001}、{101}和{010}三个不同优势晶面的光催化产氢、羟基自由 基产生和光还原反应得出锐钛矿TiO2低指数晶面的光活性顺序是{001}<{101}<{010}。所以实现低能{101}面占主导地位的TiO2晶体更值得关注。
与获得上述活性面同样重要的是，促进表面电荷载体的分离与转移，降低严重的块材载体复合以提高光催化活性。使用最广的策略是通过减小粒子尺寸特别是到纳米尺度来缩短块材载体的扩散长度。然而纳米尺寸的粒子很容易团聚，不仅减小了比表面积还增加了晶体界面的电子空穴复合率。
发明内容
本发明的目的在于提供一种TiO2单晶空心四方纳米锥材料及其制备方法，利用液相界面合成法，制备锐钛矿TiO2单晶空心四方纳米锥，具有大量暴露的{101}面和大的比表面积，工艺简单、成本低。
本发明还提供了一种TiO2单晶空心四方纳米锥材料的应用，作为光催化剂，催化降解有机染料罗丹明B、甲基橙和无色有机小分子苯酚。
本发明提供的一种TiO2单晶空心四方纳米锥材料的制备方法，包括以下步骤：
(1)将1,6-己二胺与环己烷混合后，加入Ti(OC4H9)4；然后加入去离子水搅拌混合，获得悬浊液；
(2)将步骤(1)所得悬浊液密封加热反应，冷却、离心，沉淀洗涤、干燥，得到TiO2单晶空心四方纳米锥材料。
进一步的，步骤(1)中1,6-己二胺、环己烷、Ti(OC4H9)4和去离 子水的体积比为3-8:15-40:0.5-2:0.5-3；搅拌混合时间为8-15min。
进一步的，步骤(2)中加热反应条件为：160-200℃下反应8-24h；所述加热反应在聚四氟乙烯内衬的不锈钢反应釜中进行；所述洗涤为：先用去离子水洗涤3-5次，再用无水乙醇洗涤3-5次；所述干燥为55-60℃真空干燥箱中干燥6-12h。
本发明提供的一种TiO2单晶空心四方纳米锥材料，采用以上方法制备，为锥长平均为200nm，锥口直径平均为100nm的空心四方锥。
本发明提供的一种TiO2单晶空心四方纳米锥材料的应用，作为光催化剂的应用，具体的，光催化降解有机染料罗丹明B、甲基橙和无色有机小分子苯酚的应用。
具体光催化降解方法为：将制备的TiO2单晶空心四方纳米锥材料加入到有机染料罗丹明B溶液、甲基橙溶液或无色有机小分子苯酚溶液中，超声后，黑暗处搅拌，然后300W氙灯光照催化处理，实现催化降解。
所述TiO2单晶空心四方纳米锥材料与有机染料罗丹明B溶液、甲基橙溶液或无色有机小分子苯酚溶液的用量比为1:10mg/mL；所述有机染料罗丹明B溶液、甲基橙溶液或无色有机小分子苯酚溶液的浓度为0.01mmol/L。
降解过程中每隔5min用离心管取3mL试样，离心后，取上清液，使用紫外-可见分光光度计(Shimadzu UV-2550)测定溶液的吸收光谱。分别通过554nm、463nm和270nm处的特征吸收峰来确定 RhB、MO和苯酚的浓度。
与现有技术相比，本发明通过液相界面化学合成法，在非极性溶剂环己烷和微量的水以及1,6-己二胺混合液中，利用Ti(OC4H9)4缓慢水解获得TiO2单晶空心四方纳米锥结构。先将1,6-己二胺、环己烷混合后再加Ti(OC4H9)4，之后再加去离子水，否则Ti(OC4H9)4快速水解，无法获得特定的形貌。Ti(OC4H9)在少量水和大量环己烷形成的界面上缓慢水解，1,6-己二胺在TiO2{101}晶面族上优先配位，形成大量(101)面暴露的TiO2单晶空心四方纳米锥结构。然后密封加热反应，在特定温度压力下，调控物理化学反应，生成目标产物。制备的锐钛矿TiO2单晶空心四方纳米锥，具有大量暴露的{101}面和大的比表面积；对有机染料罗丹明B、甲基橙和无色有机小分子苯酚展现出卓越的光催化活性，而且降解效率高、稳定性好以及环境友好、工艺简单、成本低的优点。
附图说明
图1为实施例1制备的TiO2单晶空心四方纳米锥的X-射线粉末衍射(XRD)图；
图2为实施例1制备的TiO2单晶空心四方纳米锥的扫描电子显微镜(SEM)图；
图3为实施例1制备的TiO2单晶空心四方纳米锥的透射电子显微镜(TEM)图；
图4为实施例1制备的TiO2单晶空心四方纳米锥的高分辨透射电子显微镜(HRTEM)图；
图5为实施例1制备的TiO2单晶空心四方纳米锥的氮气吸附-脱附等温线图；
图6为实施例2TiO2单晶空心四方纳米锥光催化降解罗丹明B的浓度随时间变化图；
图7为实施例2TiO2单晶空心四方纳米锥光催化降解甲基橙的浓度随时间变化图；
图8为实施例2TiO2单晶空心四方纳米锥光催化降解苯酚的浓度随时间变化图。
具体实施方式
实施例1
一种TiO2单晶空心四方纳米锥材料的制备方法，包括以下步骤：
(1)将5mL1,6-己二胺加入25mL环己烷中，随后加入1mL Ti(OC4H9)4，再加入1mL去离子水，持续搅拌10min，获得白色悬浊液；
(2)然后上述白色悬浊液转移到50mL聚四氟乙烯内衬的不锈钢反应釜中，将高压釜密封在180℃下反应12h，反应结束后，自然冷却至室温，白色的沉淀物离心收集并用去离子水洗涤3-5次，再用无水乙醇洗涤3-5次，置于60℃真空干燥箱中干燥6-12h，得TiO2单晶空心四方纳米锥材料。
产物的结构和形貌表征
用Rigaku TTRIII X-射线粉末衍射仪对实施例1所得产物进行物相鉴定，如图1所示。所有的衍射峰与四方相锐钛矿TiO2完全吻合 (JCPDS标准卡片号：71-1166)，无其它杂质峰出现，表明制得的产物是四方相锐钛矿TiO2，且具有高度的结晶性。用扫描电子显微镜对TiO2单晶空心四方纳米锥进行形貌分析，结果如图2所示。表明所制备的样品为锥长平均为200nm，锥口直径平均为100nm的空心四方纳米锥。用透射电子显微镜进一步对实施例1所得产物进行了形貌分析，结果如图3所示。进一步表明样品为空心四方纳米锥结构。图3中的插图为选区电子衍射图，表明四方纳米锥是单晶结构，具有低能{101}暴露面。用高分辨透射电子显微镜进一步对实施例1所得产物进行了分析，结果如图4所示。图中晶格条纹清晰，展现出很好的结晶性，0.35nm的晶面间距对应四方相TiO2的(101)晶面，0.48nm的晶面间距对应四方相TiO2的(002)晶面，晶面夹角68.3o。用氮气吸附-脱附实验进一步对实施例1所得产物进行了分析，结果如图5所示。表明TiO2单晶空心四方纳米锥的比表面积是331.3m2g-1，具有很大的比表面积。
实施例2
一种TiO2单晶空心四方纳米锥材料光催化降解有机染料罗丹明B(RhB)、甲基橙(MO)和无色有机小分子苯酚的应用。
将上述制备的TiO2单晶空心四方纳米锥称取3份各10mg，分别加入100mL浓度为0.01mmol/L RhB、MO溶液和苯酚溶液中，超声1-2min后，置于黑暗处搅拌1h，使催化剂表面达到吸附-解吸附平衡。之后，分别使用300W氙灯照射。每隔5min用离心管取3mL试样，离心后(10000rpm,2min)，取上清液，使用紫外-可见分光光度计 (Shimadzu UV-2550)测定溶液的吸收光谱。分别通过554nm、463nm和270nm处的特征吸收峰来确定RhB、MO和苯酚的浓度。降解过程浓度随时间的变化曲线分别如图6、图7和图8所示(同时给出P25(商业TiO2)光催化结果以作比较)。氙灯光照30min后，溶液中的RhB、MO或苯酚降解率分别达到95.0％、90.7％和90.5％。显然，具有大量(101)暴露面和高比表面积的TiO2单晶空心四方纳米锥结构极大地促进了表面电荷载体分离/转移，减小了光生电子空穴复合速率。而且，大量(101)暴露面的单晶空心纳米锥结构能够通过捕获电子显著增强O2分子表面键合，具有良好的产生·O2 -活性物种的能力。因此，TiO2单晶空心四方纳米锥的光催化活性远远优于商业P25。
Claims (7)
1.一种TiO2单晶空心四方纳米锥材料的制备方法，其特征在于，所述制备方法包括以下步骤：
（1）将1,6-己二胺与环己烷混合后，加入Ti(OC4H9)4；然后加入去离子水搅拌混合，获得悬浊液；
（2）将步骤（1）所得悬浊液密封加热反应，冷却、离心，沉淀洗涤、干燥，得到TiO2单晶空心四方纳米锥材料；
步骤（1）中1,6-己二胺、环己烷、Ti(OC4H9)4和去离子水的体积比为3-8 : 5-40 : 0.5-2 : 0.5-3；
步骤（2）中加热反应条件为：160-200℃下反应8-24h；
所述TiO2单晶空心四方纳米锥材料为锥长平均为200nm，锥口直径平均为100nm的空心四方锥。
2.根据权利要求1所述的TiO2单晶空心四方纳米锥材料的制备方法，其特征在于，搅拌混合时间为8-15min。
3.根据权利要求1所述的TiO2单晶空心四方纳米锥材料的制备方法，所述干燥为55-60℃真空干燥箱中干燥6-12 h。
4.一种如权利要求1所述的制备方法制备得到的TiO2单晶空心四方纳米锥材料的应用，其特征在于，作为光催化剂的应用。
5.根据权利要求4所述的应用，其特征在于，催化降解染料罗丹明B、甲基橙和无色有机小分子苯酚的应用。
6.根据权利要求5所述的应用，其特征在于，具体催化降解方法为：将制备的TiO2单晶空心四方纳米锥材料加入有机染料罗丹明B溶液、甲基橙溶液或无色有机小分子苯酚溶液中，超声后，黑暗处搅拌，然后光照催化处理，实现光催化降解。
7.根据权利要求6所述的应用，其特征在于，所述TiO2单晶空心四方纳米锥材料与有机染料罗丹明B溶液、甲基橙溶液或无色有机小分子苯酚溶液的用量比为1:10mg/mL；所述有机染料罗丹明B溶液、甲基橙溶液或无色有机小分子苯酚溶液的浓度为0.01mmol/L。
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