CN113856703A - 纳米花结构的硫化铟锌与钼酸铋纳米片复合光催化剂及其制备方法和应用 - Google Patents
纳米花结构的硫化铟锌与钼酸铋纳米片复合光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备方法及其应用，该复合光催化剂是以水热合成法制备出三维的Zn3In2S6纳米花结构，然后再通过二次水热的方法在Zn3In2S6纳米花结构上引入二维的Bi2MoO6纳米片，从而构建出纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂。本发明所得复合光催化剂在可见光的作用下展现了优异的光催化降解四环素性能，且其制备方法简单，易于操作，适合推广应用。
Description
技术领域
本发明属于光催化材料制备技术领域，具体涉及一种纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备方法及其应用。
背景技术
环境污染已引起全世界的广泛关注，尤其是抗生素的污染，已经严重危害到生态***以及人类的生存环境。抗生素滥用日益突出，不仅对水生生物产生慢性毒理效应，且易产生耐药性，降低人体免疫力，从而影响人类身体健康。四环素类抗生素具有价格低廉、广谱抗菌等特点，是目前使用最广泛、用量最大的抗生素种类之一，其作用原理是通过阻碍氨酰tRNA与核糖体结合位点的结合来抑制菌体蛋白合成，从而达到抑菌作用。与其它抗生素相比，四环素类抗生素在环境中更稳定，持久性强，难于降解，因而更易残留在环境中，主要是来自畜禽养殖业、医院和药厂排污等的排放。如何解决抗生素污染水体是众多科学家研究的热点之一。近几年，因半导体光催化是一种绿色、安全和无二次污染的技术，已成为解决水体污染的理想技术之一。
Bi2MoO6是钼酸铋中的γ晶型，同时也是钙钛矿层状结构的奥里维里斯(Aurivillius)化合物。Bi2MoO6与钼酸铋的α-Bi2Mo3O12、β-Bi2Mo2O9两种晶型相比具有优异的光催化性能。Bi2MoO6拥有适宜的带隙2.78 eV，其导带和价带位置为0.43 eV和3.21 eV（Chemical Engineering Journal, 2017, 316: 461-470.），以及镶嵌在[Bi2O2]2+层中的八面体片层MoO6形成的特殊结构使光生电子运动不会有阶跃势垒而能快速转移，表现出优异的光催化性能，然而，Bi2MoO6光照时产生的电子与空穴容易复合，导致在光催化过程中的量子产率很低。因此，选择一种合适的半导体与其复合提高光生载流子的分离和转移效率，从而构建一种高效的复合光催化剂。Zn3In2S6是一种三元硫族化合物，其带隙为2.81 eV，导带位置约为-0.9 eV，价带位置约为1.91 eV（ACS Applied Energy Materials, 2020, 3(11): 11275-11284），并具有良好的稳定性、环保、对可见光吸收强等优点，是一种理想的半导体敏化和复合的材料。综上所述，本发明结合半导体Bi2MoO6与Zn3In2S6材料的优势，以及合适的导带、价带位置，构建纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂，并应用于四环素的降解。
发明内容
本发明的目的在于提供一种纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备方法及其应用，其通过简单的水热合成法制备出三维的Zn3In2S6纳米花结构，然后再通过二次水热的方法在Zn3In2S6纳米花结构上引入二维的Bi2MoO6纳米片，所构建出纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂，具有优异的可见光光催化降解四环素的性能。
为实现上述目的，本发明采用如下技术方案：
一种纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备方法及其应用，其通过简单的水热合成法制备出三维的Zn3In2S6纳米花结构，然后再通过二次水热的方法在Zn3In2S6纳米花结构上引入二维的Bi2MoO6纳米片，构建出纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂。其具体包括如下步骤：
1）Zn3In2S6纳米花的制备
将2 mmol InCl3·4H2O、3 mmol ZnCl2、7 mmol CH3CSNH2加入聚四氟乙烯内衬中，向内衬中加入80 mL去离子水，然后将内衬放入超声器超声处理30 min，结束超声后持续搅拌两个小时后把反应釜放置到烘箱中，180 ℃持续反应12 h；待反应结束后先用乙醇洗涤，再用去离子水洗涤，60 ℃烘干12 h，即得三维的Zn3In2S6纳米花结构；
2）纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备
将一定量步骤1）制得的Zn3In2S6纳米花分散到80 mL去离子水中，然后将1 mmolNa2MoO4.2H2O、2 mmol Bi(NO3)3.5H2O、0.05 g C19H42BrN加入聚四氟乙烯内衬中，持续搅拌30 min，然后把混合均匀的溶液移至反应釜中，放置在烘箱中保持100 ℃，反应24 h。待反应结束后先用乙醇洗涤，再用去离子水洗涤，60 ℃烘干12 h，即得三维的Zn3In2S6纳米花结构与Bi2MoO6纳米片复合光催化剂。
优选地，纳米花结构的Zn3In2S6占Zn3In2S6与Bi2MoO6总质量的5-20%。步骤2）中所述一定量步骤1）制得的Zn3In2S6纳米花为0.032 g、0.068 g、0.108 g和0.152 g，即质量分数为5%、10%、15%、20%。Zn3In2S6纳米花是少量的。
所述Zn3In2S6纳米花结构与Bi2MoO6纳米片复合光催化剂在可见光的激发下，可以降解浓度为10 ppm的有机污染物四环素溶液。
本发明的显著优点在于：
本发明针对现有光催化氧化技术存在的问题，特别是Bi2MoO6催化材料存在光生载流子的分离和转移效率低的问题，提供一种通过二次水热制备的Zn3In2S6纳米花结构与Bi2MoO6纳米片复合光催化剂。该复合光催化剂是一种三维的异质复合结构，可以降解浓度为10 ppm的有机污染物四环素溶液，在可见光激发下展现出优异的光催化降解性能，且其制备方法简单，易于操作，适合推广应用。
附图说明
图1（a）为实施例1制得的Zn3In2S6纳米花结构的SEM图；（b）为实施例4制得的Zn3In2S6/Bi2MoO6复合光催化剂的SEM图；
图2为实施例1-实施例6所制得样品的XRD图；
图3为实施例1-实施例6所制得不同催化剂的四环素降解率柱状图；
图4为Zn3In2S6/Bi2MoO6复合光催化剂降解四环素的反应机理。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
Zn3In2S6纳米花的制备
将2 mmol InCl3·4H2O、3 mmol ZnCl2、7 mmol CH3CSNH2加入聚四氟乙烯内衬中，向内衬中加入80 mL去离子水，然后将内衬放入超声器超声处理30 min，结束超声后持续搅拌两个小时后把反应釜放置到烘箱中，180 ℃持续反应12 h；待反应结束后先用乙醇洗涤，再用去离子水洗涤，60 ℃烘干12 h，即得三维的Zn3In2S6纳米花结构，样品编号为1。
实施例2
二维Bi2MoO6纳米片的制备
将1 mmol Na2MoO4.2H2O、2 mmol Bi(NO3)3.5H2O、0.05 g C19H42BrN加入聚四氟乙烯内衬中，向内衬中加入80 mL 去离子水，持续搅拌30 min，然后把混合均匀的溶液移至反应釜中，放置在烘箱中保持100 ℃，反应24 h。待反应结束后先用乙醇洗涤，再用去离子水洗涤，60 ℃烘干12 h，即得二维Bi2MoO6纳米片，样品编号为2。
实施例3
1）Zn3In2S6纳米花的制备
将2 mmol InCl3·4H2O、3 mmol ZnCl2、7 mmol CH3CSNH2加入聚四氟乙烯内衬中，向内衬中加入80 mL去离子水，然后将内衬放入超声器超声处理30 min，结束超声后持续搅拌两个小时后把反应釜放置到烘箱中，180 ℃持续反应12 h；待反应结束后先用乙醇洗涤，再用去离子水洗涤，60 ℃烘干12 h，即得三维的Zn3In2S6纳米花结构；
2）纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备
将0.032g步骤1）制得的Zn3In2S6纳米花分散到80 mL去离子水中，然后将1 mmolNa2MoO4.2H2O、2 mmol Bi(NO3)3.5H2O、0.05 g C19H42BrN加入聚四氟乙烯内衬中，持续搅拌30 min，然后把混合均匀的溶液移至反应釜中，放置在烘箱中保持100 ℃，反应24 h。待反应结束后先用乙醇洗涤，再用去离子水洗涤，60 ℃烘干12 h，即得Zn3In2S6/Bi2MoO6复合光催化剂，样品编号为3。
实施例4
将实施例3步骤3）中Zn3In2S6纳米花加入的质量由0.032 g改为0.068 g，其余步骤同实施例2，所得Zn3In2S6/Bi2MoO6复合光催化剂的样品编号为4。
实施例5
将实施例3步骤3）中Zn3In2S6纳米花加入的质量由0.032 g改为0.108 g，其余步骤同实施例2，所得Zn3In2S6/Bi2MoO6复合光催化剂的样品编号为5。
实施例6
将实施例3步骤3）中Zn3In2S6纳米花加入的质量由0.032 g改为0.152 g，其余步骤同实施例2，所得Zn3In2S6/Bi2MoO6复合光催化剂的样品编号为6。
光催化降解性能的评价
将40毫克催化剂加入到80毫升10 ppm的四环素溶液中，持续搅拌和暗吸附60分钟，以保证催化剂的吸附/脱附平衡。待暗吸附完毕后，开氙灯光照，每隔一定的时间后，取4毫升反应液离心，然后取上清液在紫外可见分光光度计上测试，实验结果见图3。
图1（a）为实施例1制得的Zn3In2S6纳米花结构的SEM图；（b）为实施例4制得的Zn3In2S6/Bi2MoO6复合光催化剂的SEM图。图1（a）展示了纯Zn3In2S6的纳米花状结构，通过二次水热后，在Zn3In2S6花状结构表面引入Bi2MoO6纳米片，构建了Zn3In2S6纳米花结构与Bi2MoO6纳米片复合光催化剂，如图1（b）所示。
图2为实施例1-实施例6所制得样品的XRD图。图中清楚地展示了纯相Bi2MoO6光催化剂在10.54°处的衍射峰对应(020)晶面、28.44°的衍射峰对应(131)晶面、32.72°处的衍射峰对应(200)晶面等特征衍射峰，结果表面制备的纯相Bi2MoO6是正交晶型。另外，引入Zn3In2S6后，构建的Zn3In2S6/Bi2MoO6复合光催化剂同时出现Zn3In2S6和Bi2MoO6的特征衍射峰，说明本发明成功地制备出Zn3In2S6/Bi2MoO6复合光催化剂。
图3为实施例1-实施例6所制得不同催化剂的四环素降解率柱状图。通过该图可知，当Zn3In2S6含量为15%时，其光催化活性最高，经过36 min的可见光激发，其降解率可达77.6%，说明我们制备Zn3In2S6/Bi2MoO6复合光催化剂是一种高效的光催化剂。当Zn3In2S6含量超过20%时，可能是由于过多的Zn3In2S6，覆盖了多数Bi2MoO6纳米片，降低了Zn3In2S6/Bi2MoO6复合光催化剂的吸收效率，导致其光催化降解率降低。
图4为Zn3In2S6/Bi2MoO6复合光催化剂降解四环素可能的反应机理。基于Zn3In2S6和Bi2MoO6的研究报告，Bi2MoO6的导带和价带位置为0.43 eV和3.21 eV，Zn3In2S6的导带和价带位置为-0.9 eV和1.91 eV，该反应的途径可能为Zn3In2S6和Bi2MoO6同时被可见光激发，Zn3In2S6产生的电子还原O2产生超氧自由基（•O2 -），同时Bi2MoO6价带的空穴直接氧化部分的四环素。另外，Bi2MoO6导带电子转移到Zn3In2S6价带，构建成固态的Z型机制，提高光生载流子的转移和分离效率，从而提高其光催化反应效率。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (4)
1.一种纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备方法，其特征在于：采用水热合成法制备出三维的Zn3In2S6纳米花结构，然后再通过水热的方法引入Bi2MoO6纳米片，构建出具有纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂。
2.根据权利要求1所述的纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备方法，其特征在于：包括如下步骤：
1）Zn3In2S6纳米花的制备
将InCl3·4H2O、ZnCl2、CH3CSNH2加入聚四氟乙烯内衬中，向内衬中加入去离子水，然后将内衬放入超声器超声处理30 min，结束超声后持续搅拌两个小时后把反应釜放置到烘箱中，180℃持续反应12 h；待反应结束后先用乙醇洗涤，再用去离子水洗涤，60℃烘干12 h，即得三维的Zn3In2S6纳米花结构；
2）纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的制备
将步骤1）制得的Zn3In2S6纳米片分散到去离子水中并加入聚四氟乙烯内衬中，然后加入Na2MoO4.2H2O、Bi(NO3)3.5H2O、C19H42BrN，持续搅拌30 min，在100℃下反应24h，待反应结束后先用乙醇洗涤，再用去离子水洗涤，60℃烘干12 h，即得纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂。
3.一种如权利要求1-2任一项所述的制备方法制得的纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂其特征在于：纳米花结构的Zn3In2S6占Zn3In2S6与Bi2MoO6总质量的5-20%。
4.一种如权利要求3所述的纳米花结构的Zn3In2S6与Bi2MoO6纳米片复合光催化剂的应用，其特征在于：所述的纳米花结构Zn3In2S6与Bi2MoO6纳米片复合光催化剂应用于可见光降解有机污染物四环素。
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