CN106944042B - 一种核壳结构Ag/TiO2/ZnO纳米线及其制备方法 - Google Patents
一种核壳结构Ag/TiO2/ZnO纳米线及其制备方法 Download PDFInfo
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Abstract
本发明的核壳结构Ag/TiO2/ZnO纳米线,在Ag纳米线外层包覆有一层TiO2,并在TiO2层上诱导生长有ZnO纳米棒。其制备方法包括:将银纳米线分散于乙醇中,然后加入钛酸四丁酯及去离子水进行水热反应,得到核壳结构Ag/TiO2纳米线;将核壳结构Ag/TiO2纳米线分散于氧化锌溶胶中,均匀混合,洗涤分离,再加入到硝酸锌和六次亚甲基四胺的混合水溶液中反应,获得核壳结构Ag/TiO2/ZnO纳米线。本发明实现了一维Ag纳米线与TiO2和ZnO的三相复合,极大地提升了材料的稳定性及载流子分离效率,本发明的核壳结构Ag/TiO2/ZnO纳米线的光催化性能显著优于商业德固赛P25纳米粉,在光催化环境治理及染料敏化太阳能电池领域具有重要的应用前景。
Description
技术领域
本发明涉及一种核壳结构Ag/TiO2/ZnO纳米线及其制备方法,适用于光催化及染料敏化太阳能电池,属于环保能源领域。
背景技术
半导体材料在光催化领域以及能源领域具有广泛的应用。其中,TiO2和ZnO因为其价格低廉、制备简单、生物相容性好、无毒无害,受到了人们广泛的关注。但这两种材料都有一定的劣势,例如它们的禁带宽度较大,只能响应紫光波段,同时它们较快的光生电子-空穴对的复合速率,不利于其光催化性能。
优化纳米形貌以及引入异质结是两种有效的改性方法。一维纳米线结构可以成为光生载流子的快速通道,分支结构可以提升材料比表面积;如果同时在上述一维分支结构中引入异质结,可以更为有效地进光生电子-空穴对的分离,进而提升材料的光催化性能。就Ag、TiO2、ZnO体系而言,目前相关的技术只有在一维Ag纳米线上两相的复合,如Ag/TiO2核壳结构或者Ag/ZnO核壳结构。设计并实现一种Ag、TiO2、ZnO三相复合的一维核壳分支纳米线结构,可以更为有效地促进光生电子-空穴对的分离,同时引入贵金属的表面等离子共振效应,从而显著提升其光电性能。
文献查阅结果表明,目前还没有Ag/TiO2/ZnO一维核壳分支纳米线结构及其制备方法的报道。
发明内容
本发明的目的是提供一种核壳结构Ag/TiO2/ZnO纳米线及其制备方法。
本发明的核壳结构Ag/TiO2/ZnO纳米线,其特征是:在Ag纳米线外层包覆有一层TiO2,并在TiO2层上诱导生长有ZnO纳米棒,其中,TiO2为锐钛矿相,ZnO为六方纤锌矿结构。
上述的Ag纳米线的直径为50~100nm、长度为数十微米,包覆TiO2层后的核壳结构直径为200~300nm,ZnO纳米棒的长度为100~600nm。
核壳结构Ag/TiO2/ZnO纳米线的制备方法,包括以下步骤:
1)将银纳米线分散于乙醇溶液中,配置浓度为2.5 g/L的Ag纳米线的乙醇溶液,然后加入聚乙烯吡咯烷酮,聚乙烯吡咯烷酮与Ag纳米线的质量比为1:12.5,搅拌混合均匀后,分别逐滴加入钛酸四丁酯和去离子水,乙醇:钛酸四丁酯:去离子水的体积比=200:2:3,搅拌均匀,用去离子水洗涤分离,接着在120~200℃下水热反应8~12h,得到核壳结构Ag/TiO2纳米线;
2)分别配置浓度为2.14g/L醋酸锌的甲醇溶液和浓度为1.67g/L氢氧化钾的甲醇溶液,将醋酸锌的甲醇溶液和氢氧化钾的甲醇溶液按体积比1.9:1混合,在50℃~70℃下搅拌1h~3 h,取出冷却,得到ZnO溶胶;按每升ZnO溶胶中加入0.4~0.6g Ag/TiO2纳米线,将步骤1)制得的核壳结构Ag/TiO2纳米线分散于ZnO溶胶中,均匀混合后,洗涤分离;
3)在去离子水中加入硝酸锌和六次甲基四胺,使硝酸锌的浓度为3~15 g/L,六次甲基四胺和硝酸锌的质量比为1:2.12,将步骤3)所得产物转移到该溶液中,70~90℃下反应1~10h,得到核壳结构Ag/TiO2/ZnO纳米线。
本发明中,所述的Ag纳米线可以根据Yang [C. Yang, et al., Adv. Mater.,2011, 23, 3052-3056.] 报道的方法获得。
本发明的有益效果:
本发明的核壳结构Ag/TiO2/ZnO纳米线实现了一维Ag纳米线与TiO2和ZnO的三相复合,极大地提升了材料的稳定性及载流子分离效率,所得Ag/TiO2/ZnO一维核壳分支纳米线的光催化性能显著优于商业德固赛P25纳米粉,在光催化环境治理及染料敏化太阳能电池领域有重要的应用前景。
附图说明
图1为实施例1制备的Ag纳米线的场发射扫描电子显微镜照片;
图2为实施例1制备的Ag/TiO2一维纳米线结构的场发射扫描电子显微镜照片;
图3为实施例1制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的场发射扫描电子显微镜照片;
图4为实施例1制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的透射电子显微镜照片;
图5为实施例1制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的X射线衍射图谱;
图6为实施例2制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的场发射扫描电子显微镜照片;
图7为实施例3制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的场发射扫描电子显微镜照片;
图8为实施例4制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的场发射扫描电子显微镜照片;
图9为实施例5制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的场发射扫描电子显微镜照片;
图10为实施例1制备的Ag/TiO2/ZnO一维核壳分支纳米线结构的光催化降解苯酚曲线。
具体实施方式
以下结合实例进一步阐述本发明,但本发明不仅仅局限于下述实施例。
实施例1
1)Ag纳米线制备:将2.93g聚乙烯吡咯烷酮加入到95mL丙三醇中,90℃下搅拌1.5h,然后停止加热,使其降温到50℃,加入0.79g 硝酸银;配制29.5mg氯化钠、0.25mL 去离子水、 5mL 丙三醇的混合溶液,然后将混合溶液加入容器中,再升温到210℃,总计反应40min,停止加热,取出洗涤分离得到直径50~100nm、长度数十微米的银纳米线。
2)将100mg 银纳米线分散于40mL乙醇溶液中,然后加入8mg 聚乙烯吡咯烷酮,磁力搅拌10min,然后逐滴加入0.4 mL 钛酸四丁酯及0.6mL 去离子水,继续搅拌30min,用去离子水洗涤,分散到10mL的去离子水中,在160℃下水热反应12h,得到核壳结构Ag/TiO2纳米线。
3)将68.5mg醋酸锌加入到32mL甲醇中,在60℃下搅拌40min,然后加入16.5mL的含有27.5mg氢氧化钾的甲醇溶液,60℃下搅拌2h,取出冷却,得到ZnO溶胶。将25mg核壳结构Ag/TiO2纳米线分散于ZnO溶胶中,搅拌2h,然后洗涤分离。
4)将步骤3)所得产物转移到30mL含有0.178g硝酸锌,0.084g六次甲基四胺的水溶液中,80℃下搅拌反应4 h,得到核壳结构Ag/TiO2/ZnO纳米线。
图1的场发射扫描电子显微镜照片显示了步骤1)制备的Ag纳米线,其直径50~100nm、长度数十微米;经步骤2)处理后,Ag纳米线外层包覆一层TiO2纳米颗粒,包覆后的核壳结构直径约为200~300nm(见图2);经步骤3)、4)后,在TiO2层上诱导生长直径20~40nm、长度为300~400nm的ZnO纳米棒(见图3)。图4的透射电子显微照片清楚显示了Ag/TiO2/ZnO一维核壳分支纳米线结构。图5的X射线衍射图谱表明,TiO2为纯锐钛矿相,ZnO为六方纤锌矿结构。
实施例2
1)同实施例1步骤(1)。
2)将100mg 银纳米线分散于40mL乙醇溶液中,然后加入8mg 聚乙烯吡咯烷酮,磁力搅拌10min,然后逐滴加入0.4mL 钛酸四丁酯及0.6mL 去离子水,继续搅拌30min,用去离子水洗涤,分散到10mL的去离子水中,在120℃下水热反应12h,得到核壳结构Ag/TiO2纳米线。
3)同实施例1步骤(3)。
4)将步骤3)所得产物转移到30mL含有0.178g硝酸锌,0.084g六次甲基四胺的水溶液中,80℃下搅拌反应1 h,得到核壳结构Ag/TiO2/ZnO纳米线。
图6的场发射扫描电子显微镜照片显示成功获得了Ag/TiO2/ZnO一维核壳分支纳米线结构。
实施例3
1)同实施例1步骤(1)。
2)将100mg 银纳米线分散于40mL乙醇溶液中,然后加入8mg 聚乙烯吡咯烷酮磁力搅拌10min,然后逐滴加入0.4mL 钛酸四丁酯及0.6mL 去离子水,继续搅拌30min,用去离子水洗涤,分散到10mL的去离子水中,在200℃下水热反应8h,得到核壳结构Ag/TiO2纳米线。
3)同实施例1步骤(3)。
4)将步骤3)所得产物转移到30mL含有0.178g硝酸锌,0.084g六次甲基四胺的水溶液中,90℃下搅拌反应2h,得到核壳结构Ag/TiO2/ZnO纳米线。
图7的场发射扫描电子显微镜照片显示成功获得了Ag/TiO2/ZnO一维核壳分支纳米线结构。
实施例4
1)同实施例1步骤(1)。
2)同实施例1步骤(2)。
3)同实施例1步骤(3)。
4)将步骤3)所得产物转移到30mL含有0.178g硝酸锌,0.084g六次甲基四胺的水溶液中,80℃下搅拌反应10 h,得到核壳结构Ag/TiO2/ZnO纳米线。
图8的场发射扫描电子显微镜照片显示成功获得了Ag/TiO2/ZnO一维核壳分支纳米线结构。
实施例5
1)同实施例1步骤(1)。
2)同实施例1步骤(2)。
3)同实施例1步骤(3)。
4)将步骤3)所得产物转移到30mL含有0.178g硝酸锌,0.084g六次甲基四胺的水溶液中,70℃下搅拌反应4 h,得到核壳结构Ag/TiO2/ZnO纳米线。
图9的场发射扫描电子显微镜照片显示成功获得了Ag/TiO2/ZnO一维核壳分支纳米线结构。
光催化降解苯酚性能测试
测试条件:采用18W紫外灯,紫外光光强为:5.0 mW/cm2,降解物为50mL 初始浓度为10ppm 苯酚,催化剂用量为10mg。
测试结果:实施例1制备的Ag/TiO2/ZnO一维核壳分支纳米线光催化降解水中苯酚的性能显著优于德固赛公司的商用P25二氧化钛纳米粉体(图10)。本发明获得的优异的光催化活性来源于本发明的核壳纳米结构设计,即Ag/TiO2/ZnO一维核壳分支纳米线兼具TiO2/ZnO异质结和半导体-贵金属接触,合理的能带结构使得两者具有协同作用,充分提升了光生电子-空穴对的分离效率。
Claims (1)
1.一种核壳结构Ag/TiO2/ZnO纳米线的制备方法,其特征在于,在Ag纳米线外层包覆有一层TiO2,并在TiO2层上诱导生长有ZnO纳米棒,其中,TiO2为纯锐钛矿相,ZnO为六方纤锌矿结构,主要包括以下步骤:
1)将银纳米线分散于乙醇溶液中,配置2.5g/L的Ag纳米线的乙醇溶液,然后加入聚乙烯吡咯烷酮,聚乙烯吡咯烷酮与Ag纳米线的质量比为1:12.5,搅拌混合均匀后,分别逐滴加入钛酸四丁酯和去离子水,乙醇:钛酸四丁酯:去离子水的体积比=200:2:3,搅拌均匀,用去离子水洗涤分离,接着在120~200℃下水热反应8~12h,得到核壳结构Ag/TiO2纳米线;
2)分别配置浓度为2.14g/L醋酸锌的甲醇溶液和浓度为1.67g/L氢氧化钾的甲醇溶液,将醋酸锌的甲醇溶液和氢氧化钾的甲醇溶液按体积比1.9:1混合,在50℃~70℃下搅拌1h~3h,取出冷却,得到ZnO溶胶;按每升ZnO溶胶中加入0.4~0.6gAg/TiO2纳米线,将步骤1)制得的核壳结构Ag/TiO2纳米线分散于ZnO溶胶中,均匀混合后,洗涤分离;
3)在去离子水中加入硝酸锌和六次甲基四胺,使硝酸锌的浓度为3~15g/L,六次甲基四胺和硝酸锌的质量比为1:2.12,将步骤3)所得产物转移到该溶液中,70~90℃下反应1~10h,得到核壳结构Ag/TiO2/ZnO纳米线。
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