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CN106830085B - 一种稳定氢钨青铜纳米片的制备方法 - Google Patents

一种稳定氢钨青铜纳米片的制备方法 Download PDF

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CN106830085B
CN106830085B CN201710052389.8A CN201710052389A CN106830085B CN 106830085 B CN106830085 B CN 106830085B CN 201710052389 A CN201710052389 A CN 201710052389A CN 106830085 B CN106830085 B CN 106830085B
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陈伟凡
方晓辰
尧牡丹
郭兰玉
卓明鹏
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Abstract

一种稳定氢钨青铜纳米片的制备方法，包括以下步骤：（1）根据H0.33WO3的化学计量比及制备量，称取WO3‑x（0.05≤x≤1），配制成WO3‑x与分散剂质量比为1/10~1/2的分散液，并加入适量的表面活性剂；（2）球磨步骤（1）得到的分散液0.5～12小时；（3）洗涤和过滤步骤（2）得到的产物；（4）配制好水和乙醇的混合液，将步骤（3）的产物按照质量比为1～15%加入其中，紫外线辐照1～12小时；（5）步骤（4）的产物经洗涤、过滤和干燥后，即得氢钨青铜纳米片。本发明以还原态氧化钨为原料，经球磨超细化和紫外光辐照处制备钨氢青铜纳米片，具有原料易得、工艺简单、成本低廉和绿色环保的特点。

Description

一种稳定氢钨青铜纳米片的制备方法
技术领域
本发明属于纳米材料制备技术领域，涉及氢钨青铜纳米片的制备方法。
背景技术
WO3以其特殊的性能在光催化、传感器、光致变色等领域有着广泛的应用，通过向其晶体结构中所特有的隧道结构中掺入碱金属离子、铵离子和氢离子所制得的钨青铜，是稳定性较高的具有深蓝色金属光泽的阳离子掺杂金属氧化物，一般用MxWO3表示它的通式，呈现出金属导体或者半导体的性质，其颜色与性能随着M与x的不同也会产生相应的差异。目前，钨青铜纳米盐因其对紫外与近红外具有较高的吸收率而在光催化以及节能红外吸收透明隔热涂层中有着广泛的应用。
目前制备纳米钨青铜的方法有一些，如专利CN103496744 A公开了一种还原态铵钨青铜的合成方法，使用WCl6作为钨源，加入油酸作为溶剂，W：NH4 +的摩尔比为1：（0.2～0.3），在150～350 ℃的高温条件下晶化反应0.5～48 h，最终获得还原态铵钨青铜纳米粉体。这种方法合成时间很长，产率很低，成本很高，红外吸收性能较差。专利CN 104528829 A报道了使用钨酸盐溶液通过阳离子交换得到钨酸溶胶，再加入还原剂与铯源得到相应的前驱体，将前驱体加入到反应釜中进行水热反应后可制得铯钨青铜纳米盐。该方法在制备前躯体的过程中使用了阳离子交换法，因此单次合成的量有限，且水热合成法耗时较长，反应过程中需要高温高压条件，能耗较大，对设备的要求较高，因此纳米钨青铜特别是氢钨青铜的有工业化应用前景的合成方法成为制约其广泛应用的瓶颈。
发明内容
本发明提出了一种稳定氢钨青铜纳米片的制备方法，以还原态氧化钨为原料，有机溶剂作为分散剂，并加入少量的表面活性剂，经机械球磨超细化处理得到前驱体，然后将其分散在乙醇的水溶液中，在持续搅拌下用紫外光辐照便可以获得大小均匀，分散性好的氢青铜纳米粉体，该法原料易得、工艺简单、成本低廉、绿色环保。
本发明是通过以下技术方案实现的。
本发明所述的一种氢钨青铜纳米片的制备方法，包括以下步骤。
（1）根据氢钨青铜化学组成式H0.33WO3的化学计量比及其制备量，称取适量的WO3-x（0.05≤x≤1）粉体，制备WO3-x与分散剂的质量比为1/8~1/2的分散液，并加入分散液质量0.01～1%的表面活性剂。
（2）将步骤（1）得到的分散液放入球磨机中，球磨0.5～12 小时。
（3）将步骤（2）得到的产物取出，洗涤和过滤。
（4）配制水和乙醇的体积比为20～70%的混合液，将步骤（3）中所得产物按照质量比为1～15%加入混合液中，在持续搅拌下用波长200～400 nm的紫外光线辐照1～12小时。
（5）将步骤（4）中样品取出，经洗涤、过滤和干燥后，即得氢钨青铜纳米片。
本发明步骤（1）中所述的分散剂为水、乙醇、乙二醇或丙酮中的一种或两种以上；表面活性剂为月桂酸二乙醇酰胺、聚丙烯酰胺、辛基酚聚氧乙烯醚、十二烷基硫酸钠或烷基苯磺酸钠中的一种或两种以上。
本发明步骤（2）中所述的球磨机为行星式球磨机、搅拌磨、砂磨或振动磨。
本发明步骤（4）中所述的紫外光线为汞灯或氙灯所提供。
本发明的主要特点是：（1）产物氢钨青铜为大小均匀的纳米片，分散性好、性能稳定；（2）原料易得、工艺简单、成本低廉、绿色环保。
附图说明
图1为实施例1所用原料还原氧化钨的X射线衍射图谱，该图谱与JCPDS卡片号(84-1516) WO2.72的图谱吻合。
图2为实例1产物的X射线衍射图谱，该图谱与JCPDS卡片号（06-0706）H0.33WO3的图谱吻合。
图3为实例1产物的透射电镜照片，如图所示，产物为纳米片状结构，分散性好。
图4为实例1产物的高倍透射电镜照片以及局部的高分辨透射电镜照片(HRTEM)，如图所示，产物片径大小约为20～40 nm，由HRTEM可以看清晰的晶格条纹，显示其结晶性较好，分析表明该晶面间距为0.380 nm。
图5为实例2产物的透射电镜照片，如图所示，产物为纳米片状结构，径大小约为20～40 nm，分散性好。
图6为实例3产物的透射电镜照片，如图所示，产物为纳米片状结构，径大小约为20～40 nm，分散性好。
图7为实例4产物的透射电镜照片，如图所示，产物为纳米片状结构，径大小约为20～40 nm，分散性好。
具体实施方式
本发明将通过以下实施例作进一步说明。
实施例1。
称取5 g WO2.72，分散在45 ml水中，再加入0.044 g烷基苯磺酸钠，放入行星式球磨机中，球磨3小时，然后取出产物，洗涤和过滤，即得前驱体，将前驱体分散在150 ml乙醇与水的体积比为1:1的混合液中，在持续搅拌下用紫外灯辐照8小时，经乙醇洗涤，过滤和干燥后，可得氢钨青铜纳米片。
实施例2。
称取5 g WO2.72，分散在45 ml乙醇中，再加入0.044 g聚丙烯酰胺，放入行星式球磨机中，球磨5小时，然后取出产物，洗涤和过滤，即得前驱体，将前驱体分散在150 ml乙醇与水的体积比为1:1的混合液中，在持续搅拌下用紫外灯辐照8小时，经乙醇洗涤，过滤和干燥后，可得氢钨青铜纳米片。
实施例3。
称取5 g WO2.72，分散在45 ml乙醇中，再加入0.044 g辛基酚聚氧乙烯醚，放入行星式球磨机中，球磨6 小时，然后取出产物，洗涤和过滤，即得前驱体，将前驱体分散在150ml乙醇与水的体积比为1:1的混合液中，在紫外灯下辐照12小时，经乙醇洗涤，过滤和干燥后，可得氢钨青铜纳米片。
实施例4。
称取5 g WO2.72，分散在45 ml乙醇中，再加入0.044 g月桂酸二乙醇酰胺，放入行星式球磨机中，球磨5小时，然后取出产物，洗涤和过滤，即得前驱体，将前驱体分散在150ml乙醇与水的体积比为1:1的混合液中，在紫外灯下辐照6小时，经乙醇洗涤，过滤和干燥后，可得氢钨青铜纳米片。

Claims (3)

1.一种稳定氢钨青铜纳米片的制备方法，其特征是包括以下步骤：
（1）根据氢钨青铜化学组成式H0.33WO3的化学计量比及其制备量，称取适量的WO3-x，0.05≤x≤1粉体，配制成WO3-x与分散剂的质量比为1/10~1/2的分散液，并加入分散液质量0.01～1%的表面活性剂；
（2）将步骤（1）得到的分散液放入球磨机中，球磨0.5～12 小时；
（3）将步骤（2）得到的产物取出，洗涤和过滤；
（4）配制水和乙醇的体积比为20～70%的混合液，将步骤（3）中所得产物按照质量比为1～15%加入混合液中，在持续搅拌下用波长200～400 nm的紫外线辐照1～12小时；
（5）将步骤（4）得到的产物取出，经乙醇洗涤、过滤和干燥后，即得氢钨青铜纳米片；
步骤（1）中所述的分散剂为水、乙醇、乙二醇或丙酮中的一种或两种以上；表面活性剂为月桂酸二乙醇酰胺、聚丙烯酰胺、辛基酚聚氧乙烯醚、十二烷基硫酸钠或烷基苯磺酸钠中的一种或两种以上。
2.根据权利要求1所述的制备方法，其特征是步骤（2）中所述的球磨机为行星式球磨机、搅拌磨、砂磨机或振动磨。
3.根据权利要求1所述的制备方法，其特征是步骤（4）中所述的紫外线为汞灯或氙灯所提供。
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* Cited by examiner, † Cited by third party
Title
钨青铜化合物MxWO3的研究现状;苏铭汉 等;《哈尔滨工业大学学报》;20060228;第38卷(第2期);238-242，323 *

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