CN103406147B - 一种纳米管状溴化亚铜光催化材料的制备方法及其应用 - Google Patents
一种纳米管状溴化亚铜光催化材料的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种纳米管状溴化亚铜光催化材料的制备方法及其应用，将CuBr2和三乙烯二胺的混合物溶于甲醇和水体积比为4∶2的甲醇溶液中并用磁力搅拌器搅拌，CuBr2和三乙烯二胺摩尔比为5∶3；搅拌过程中滴加高氯酸调节溶液的pH值；30分钟后将混合液转移到带有聚四氟乙烯衬底的反应釜中，置于100℃烘箱内加热保持96小时；再以每小时5℃的速度冷却到室温，过滤并水洗即得。该发明只需一步反应，即可得到其纳米颗粒，避免了高温烧结的晶粒粗化与团聚，并且原料廉价易得，制备工艺操作简单、条件温和；反应过程中的参数可调，易于控制产物的结晶度与物相组成。
Description
技术领域
本发明涉及一种纳米管状溴化亚铜光催化材料的制备方法及其应用，属于功能材料技术领域。
背景技术
自1972年Fujishima和Honda发现在TiO2电极材料表面光响应产氢现象以来(Fujishima，A.Honda，K.，Nature238，37-38)，光催化作为解决环境污染和能源危机一种潜在技术引起全世界的关注。在半导体光催化过程中，光照射激发价带中的电子跃迁至导带，在导带上形成光生电子和价带上形成光生空穴；载流子迁移到粉末颗粒表面后，充分与周围的环境作用，发生复杂的氧化、还原反应。
目前国内外光催化剂的研究多数停留在TiO2及相关修饰，如材料的纳米化及高比表面化、掺杂、半导体复合、贵金属及氧化物负载等。尽管这些工作卓有成效，但其量子产率不高，而且难以用于光催化裂解水产氢的用途，因此，寻找新型高效光催化剂已成为当前此领域最重要的课题之一。根据已发现的光催化材料，其体系可分为氧化物、硫化物、氧硫化物、氮化物以及氧氮化物，其中氧化物往往有比较好的(光)化学稳定性；硫化物及氧硫化物虽然能够显示较理想的可见光响应特性，但作为光催化材料容易产生光化学腐蚀；氮化物及氧氮化物也具有较好的可见光吸收特性，其材料本身光催化效果不尽理想。寻找新型高效光催化剂一直是光催化技术领域一项长期而艰巨的任务，它是光催化技术能够得以大规模推广应用的核心。
发明内容
本发明所要解决的技术问题是针对现有技术的不足提供一种纳米管状溴化亚铜光催化材料的制备方法及其应用。
本发明的技术方案如下：
一种纳米管状溴化亚铜光催化材料的制备方法，将CuBr2和三乙烯二胺的混合物溶于甲醇和水体积比为4∶2的甲醇溶液中并用磁力搅拌器搅拌，CuBr2和三乙烯二胺摩尔比为5∶3；搅拌过程中滴加高氯酸调节溶液的pH值；30分钟后将混合液转移到带有聚四氟乙烯衬底的反应釜中，置于100℃烘箱内加热保持96小时；再以每小时5℃的速度冷却到室温，过滤并水洗即得。
所述的纳米管状溴化亚铜光催化材料在光催化降解有机染料中的应用。
本发明采用溶剂热方法来合成该纳米管状溴化亚铜光催化材料，只需一步反应即可得到其纳米颗粒，避免了高温烧结的晶粒粗化与团聚，并且原料廉价易得，制备工艺操作简单、条件温和；反应过程中的参数可调，易于控制产物的结晶度与物相组成。其化学组成为(Me2DABCO)3(H3O)4(Cu15Br24)Br，光学能带隙为3.42eV，实验证明该材料对有机染料有很好的光催化降解效果。
附图说明
图1(a)为配合物1的配位环境图，图1(b)为龟壳型Cu5Br10簇，图1(c)为配合物1沿b轴方向的一维管，图1(d)为配合物1沿c轴方向的一维管，图1(e)为配合物1沿c轴方向的堆积图；
图2为配合物1的态密度图；
图3为配合物1紫外-可见漫反射光谱图；
图4为配合物1的能带图；
图5为配合物1光催化降解四种染料效果比较；
图6为配合物1的粉末衍射图。
具体实施方式
以下结合具体实施例，对本发明进行详细说明。
本发明采用溶剂热方法来合成该纳米管状溴化亚铜光催化材料，并对其进行光催化性能测试。
一、材料制备
将CuBr2和三乙烯二胺(摩尔比为5∶3)的混合物溶于甲醇/水(V∶V＝4∶2)中并用磁力搅拌器搅拌，搅拌过程中滴加高氯酸调节溶液的pH值。大约30分钟后将混合液转移到带有聚四氟乙烯衬底的反应釜中，置于100℃烘箱内加热保持96小时。再以每小时5℃的速度冷却到室温，过滤并水洗得到无色柱状晶体配合物1。
配合物1由完美排列的63螺旋溴化亚铜纳米管组成，原位烷基化的Me2DABCO模板来稳定纳米管。如图1所示，Cu(3)四面体通过μ3-Br(3)原子与两个Cu(1)和两个Cu(2)共边连接形成龟壳型的Cu5Br10簇。Cu5Br10簇进一步通过四个外围的μ2-Br(5)原子连接形成独特的阴离子溴化亚铜纳米管[Cu5Br8]n 3n-。目前，大部分独立的纳米管结构是电中性的，带电荷的纳米管由于静电作用显示更好的性质。阴离子纳米管[Cu5Br8]n 3n-由原位甲基化的DABCO阳离子来稳定，形成3D超分子骨架。
紫外-可见漫反射测定表明配合物1具有半导体行为，能带隙Eg为3.42eV(图3)，比溴化亚铜的带隙2.89eV大点。利用态密度方法进行能带计算，结果显示(图2和4)导带主要由Br4s轨道混合少量Cu4s轨道组成，价带主要由Cu3d轨道混合Br4p轨道组成；Cu3d在价带中较为弥散，有利于电子在材料内部的传输，提高电子导电性及相应的光生电子-孔穴分离能力。
晶体的X射线衍射数据采用SMARTAPEX CCD单晶衍射仪测定，用石墨单色器辐射()，以ω扫描方式收集数据，并进行Lp因子校正和半经验吸收校正。通常先用重原子法或直接法确定金属离子位置，然后用差值函数法和最小二乘法求出全部非氢原子坐标，并用理论加氢法得到氢原子位置，用最小二乘法对结构进行修正。所有计算工作在PC机上用SHELXS-97程序完成。
二、光催化降解有机染料
将本发明所得材料进行光催化降解有机染料甲基橙、胭脂红、次甲基蓝、罗丹明B的研究。紫外灯源为125W的高压汞光灯，催化实验时，将100mg的配合物加到100mL1×10-5mol/L的染料溶液中。如图5所示，染料溶液的浓度随照射时间的增加而减少，表明配合物1可以降解四种有机染料。尤其是降解偶氮染料胭脂红和甲基橙的效率明显高于次甲基蓝和罗丹明B，90分钟后残余浓度分别为：胭脂红(1.25％)＜甲基橙(9.43％)＜次甲基蓝(30.15％)＜罗丹明B(42.10％)。
高氧化电位的羟基自由基(2.80eV)一般在光催化降解染料中起重要作用，但表面吸附、电子-孔穴对和高的反应晶面等因素也与配合物1高效选择性光催化有关。X-射线粉末衍射图(XRD)表明配合物1高的反应晶面(200)，(2，-1，1)和(2，-1，0)是沿Cu5Br8 3-纳米管方向(图6)，烷基化的[Me2DABCO]2+阳离子位于这些反应晶面的两边。由于静电相互作用，羟基优先被吸附，导致羟基自由基的产率较高，因此有利于染料的光催化降解。
应当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (2)
1.一种纳米管状溴化亚铜光催化材料的制备方法，其特征在于，将CuBr2和三乙烯二胺的混合物溶于甲醇和水体积比为4∶2的甲醇溶液中并用磁力搅拌器搅拌，CuBr2和三乙烯二胺摩尔比为5∶3；搅拌过程中滴加高氯酸调节溶液的pH值；30分钟后将混合液转移到带有聚四氟乙烯衬底的反应釜中，置于100℃烘箱内加热保持96小时；再以每小时5℃的速度冷却到室温，过滤并水洗即得。
2.权利要求1制备方法制备的纳米管状溴化亚铜光催化材料在光催化降解有机染料中的应用。
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