CN105948129B - 一种不同纳米晶型wo3的可控合成方法及其在废水中的应用 - Google Patents
一种不同纳米晶型wo3的可控合成方法及其在废水中的应用 Download PDFInfo
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Abstract
本发明涉及一种不同纳米晶型WO3的可控合成方法及其在废水处理中的应用,本发明首先以钨酸铵作为钨源,以十六烷基三甲基溴化铵(CTAB)作为形貌调控剂,通过硝酸酸化获得钨酸,最后在200~500摄氏度下焙烧12小时得到形似花状不同晶型的三氧化钨。本发明的优点是:1、本发明的纳米材料是首次可控合成了不同晶型的WO3;2、本发明的纳米材料具有较好的纳米吸附和光催化协同作用。3、本发明提供的制备方法简单易行、生产成本低廉、纯度高,制备的不同晶型WO3纳米材料比表面积高、吸附性能好且煅烧后可重复使用。
Description
技术领域
本发明涉及一种可控合成不同纳米晶型WO3纳米材料的方法及其在废水中的应用。
背景技术
我国对染料的使用历史主要是随着织布技术逐渐发展起来的,大约在公元前3000多年时,就已经发现有先祖开始使用天然染料;史载记录我们的先祖主要从植物中提取靛蓝、菘蓝和红花作为染料,还有从贝和螺中制取泰雅红紫染料等。过去使用的染料一般均为天然染料,即直接或间接从动物、植物乃至矿产中精炼而得到的。由于当时的科学技术落后,很少经过化学处理和加工,稳定性差,所得到的染料亦不纯,因而这些染料可以有效地被环境降解。但是这种物理处理得到的染料色牢度差、且不易着色,较为单一等一系列问题限制了染料在人们日常生活中的广泛使用。直到后来,在英国皇家化学学院霍夫曼院长的实验室里W. H. Perkin偶然获得到了马尾紫染料,随后Martius又成功地实现了偶氮染料的商品化,从此合成染料得到了迅速的发展。到目前为止,约有1万多种不同的染料被利用,而全球每年生产的染料约为百万吨。这些染料按其化学结构不同可分为偶氮染料、靛族染料、硫化染料、酞菁染料、蒽醌染料、芳甲烷染料、硝基和亚硝基染料,此外还有其他结构类型的染料,如甲川和多甲川类染料、二苯乙烯类染料以及各种杂环类染料等。近年来,我国染料产量稳居世界首位,年产量达几百万吨且逐年增加,在全球染料产量行业中所占有的份额达到了60%,然而在染料生产过程中,有很大部分的染料进入废水中,对周围水环境的污染和人类的健康造成了极大的危害,而且这种生产废水已经成为当前最主要的水体污染源之一,严重影响了人类的身体健康。
目前染料去除的方法很多,常见的有生物处理法,染料萃取法,电化学氧化法,吸附法,光催化降解法等,其中吸附、降解是染料在环境中分解、转化的重要途径之一。光催化技术基于光催化剂在太阳光照射下具有其独特的氧化还原能力,被用于净化空气和水中的污染物。
三氧化钨(WO3)是一种具有六方、立方等多种对称型结构的n型半导体材料,由于具有优异的电致变色、气致变色和光致变色等性能而备受关注。自1973年发现WO3具有光致变色现象以来,WO3在信息显示器件、高敏度光存储材料及变色玻璃等方面显示出巨大的应用前景,使其制备、结构及光致变色性能等成为国内外的研究热点之一。特别是纳米WO3因具有巨大的比表面积,其体积效应、表面效应、量子尺寸效应和宏观量子隧道效应显著,使得它的应用领域继续扩大,可作为太阳能吸收材料、隐形材料、催化剂材料。目前可控合成不同晶型的WO3的方法及其在废水处理中的协同应用尚未报道,因此探究两种晶型氧化钨的可控合成方法及其在废水中的应用是非常有意义的。
发明内容
本发明所要解决的技术问题是提供一种可控合成不同晶型的WO3的方法,并为吸附、光催化降解有机污染物提供了一种更高效的材料,本发明的纳米材料操作简单、生产成本低廉、产品纯度高,而且吸附后的材料通过煅烧处理依然可以恢复其吸附性能,是一种工艺环保制备纳米吸附、催化材料的有效方法。
本发明是这样来实现的,一种新型不同纳米晶型WO3的可控合成的方法,其特征方法步骤如下:
(1)WO3前驱体的制备:准确称取2.31克钨酸铵于100毫升的烧杯中,再加入0.05克十六烷基三甲基溴化铵(CTAB)。向上述烧杯中加入10毫升去离子水,然后用超声清洗器超声使其完全分散,置于磁力搅拌器上使之在持续搅拌中,然后向其中缓慢滴入浓硝酸,使溶液完全呈黄色,继续搅拌24小时。过滤,用去离子水洗涤2到3次,80摄氏度恒温干燥,得到黄钨酸备用;
(2)不同晶型WO3的制备:将步骤(1)中所得黄钨酸置于马弗炉中,使之分别控制在200~500摄氏度的高温下煅烧12小时,可可分别得到立方型三氧化钨(简称:c-WO3)、立方型三氧化钨和三斜型三氧化钨的混合物,以及三斜型三氧化钨(简称:m-WO3)。
本发明方法合成得到三氧化钨可应用于吸附和光催化降解污染物。
本发明的优点是:1、本发明的纳米材料是首次可控合成了不同晶型的WO3;2、本发明的纳米材料具有较好的纳米吸附和光催化协同作用。3、本发明提供的制备方法简单易行、生产成本低廉、纯度高,制备的不同晶型WO3纳米材料比表面积高、吸附性能好且易回收重复利用。4、本发明所制备出来的WO3纳米材料是一种比表面积高、热稳定性好、光学性能优良的吸附剂和光催化剂,在环境功能材料、污水处理、光催化等领域具有潜在的应用前景。
附图说明
图1为本发明的不同晶型WO3纳米材料在不同温度下的X射线粉末衍射对比图。
图2为本发明的c-WO3和m-WO3纳米材料的扫描电镜图。
图3为本发明的c-WO3和m-WO3纳米材料比表面积对比图。
图4为本发明的c-WO3和m-WO3纳米材料对亚甲基蓝吸附去除的对比图。
图5为本发明的m-WO3纳米材料对亚甲基蓝的光催化降解趋势图。
图6为本发明的c-WO3纳米材料对亚甲基蓝吸附去除的动力学数据图。
图7为本发明的c-WO3和m-WO3的纳米材料的紫外漫反射和肖特基曲线图。
图8为本发明的c-WO3和m-WO3纳米材料的能带图。
具体实施方式
以下结合附图说明对本发明的实施例作进一步详细描述,但本实施例并不用于限制本发明,凡是采用本发明的相似结构及其相似变化,均应列入本发明的保护范围。
本发明的纳米材料的合成:
(1)WO3前驱体的制备:准确称取2.31克钨酸铵于100毫升的烧杯中,再加入0.05克十六烷基三甲基溴化铵(CTAB)。向上述烧杯中加入10毫升去离子水,然后用超声清洗器超声使其完全分散,置于磁力搅拌器上使之在持续搅拌中,然后向其中缓慢滴入浓硝酸,使溶液完全呈黄色,继续搅拌24小时。过滤,用去离子水洗涤2到3次,80摄氏度恒温干燥,得到黄钨酸备用;
(2)不同晶型WO3的制备:将步骤(1)中所得黄钨酸置于马弗炉中,使之分别控制在200、250、300、350、400、450和500摄氏度的高温下煅烧12小时,控制在200摄氏度时可得到c-WO3,控制在500摄氏度时可得到m-WO3,而控制在250、300、350、400和450的时候均得到c-WO3和m-WO3的混合物。
如图1所示,本发明的不同晶型WO3纳米材料在不同温度下的X射线粉末衍射图随着温度的改变,立方晶型三氧化钨(c-WO3)逐渐转化为三斜晶型的三氧化钨(m-WO3),且c-WO3和m-WO3的标准卡片(JCPDS NO. 00-041-0905和JCPDS NO.01-072-1465)一一对应,说明本发明成功制备出了纯相的c-WO3和m-WO3纳米材料。
如图2所示,本发明的c-WO3和m-WO3纳米材料的扫描电镜图,可以看出,纳米材料为层状材料,层与层之间的堆列形似花状的纳米结构,说明本发明制备出的WO3纳米材料具有较大的比表面积,其比表面积图详见图3。
如图4所示,本发明的c-WO3和m-WO3纳米材料对亚甲基蓝吸附去除的热力学数据表明,c-WO3对亚甲基蓝具有很好的吸附性能,而m-WO3 几乎无吸附性能,但从图5可知,在紫外可见光下,200毫克的m-WO3可将10毫克的亚甲基蓝降解完全,说明m-WO3有着很好的光催化性能。
图6为本发明的c-WO3纳米材料对亚甲基蓝吸附去除的动力学研究,数据表明,在40毫克每升的亚甲基蓝溶液中,c-WO3不但具有很好的吸附效果,而且吸附速率非常快。另外,吸附饱和后回收c-WO3,然后进行低温煅烧(200~300摄氏度),煅烧后的c-WO3仍然具有和新合成的c-WO3的吸附效果。这说明本发明合成的c-WO3可以重复多次使用,可用于实际有机废水处理中。
图7为本发明的c-WO3和m-WO3的纳米材料的紫外漫反射和肖特基曲线图。通过紫外可见漫反射和肖特基曲线可以计算出c-WO3和m-WO3的导带底和价带顶的位置,进而可以绘制如图8所示的光催化能带图,且为异质结构,这种异质结可以有效的阻碍了光生电子和空穴的复合,从而提高了催化剂的光催化性能。
Claims (2)
1.一种不同晶型WO3的可控合成的方法,其特征步骤如下:
(1)WO3前驱体的制备:准确称取2~3克钨酸铵于100毫升的烧杯中,再加入0.02~0.09克十六烷基三甲基溴化铵;向上述烧杯中加入10毫升去离子水,然后用超声清洗器超声使其完全分散,置于磁力搅拌器上使之在持续搅拌中,然后向其中缓慢滴入浓硝酸,使溶液完全呈黄色,继续搅拌24小时;过滤,用去离子水洗涤2到3次,80摄氏度恒温干燥,得到黄钨酸备用;
(2)不同晶型WO3的制备:将步骤(1)中所得黄钨酸置于马弗炉中,使之分别控制在200~500摄氏度的高温下煅烧12小时,200℃下煅烧得到立方型三氧化钨、500℃下煅烧得到三斜型三氧化钨、200-500℃之间煅烧得到立方型三氧化钨和三斜型三氧化钨的混合物。
2.如权利要求1所述的一种不同晶型WO3的可控合成的方法,其特征在于:合成得到三氧化钨可应用于吸附和光催化降解污染物。
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