Kuo Chun-Hong, Huang Michael H
Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
J Am Chem Soc. 2008 Sep 24;130(38):12815-20. doi: 10.1021/ja804625s. Epub 2008 Aug 30.
We report a simple approach for the fabrication of cuprous oxide (Cu 2O) nanocages and nanoframes possessing an unusual truncated rhombic dodecahedral structure. An aqueous solution containing CuCl 2, sodium dodecyl sulfate (SDS) surfactant, NH 2OH.HCl reductant, HCl, and NaOH was prepared, with the reagents introduced in the order listed. Rapid seed-particle aggregation and surface reconstruction of the intermediate structure resulted in the growth of type-I nanoframes, which have only {110} skeleton faces and empty {100} faces, 45 min after mixing the reagents. Continued crystal growth for additional 75 min produced nanocages with filled {100} faces. The nanocages have diameters of 350-400 nm, and their walls are thicker than those of the nanoframes. Selective acidic etching over the {110} faces of the nanocages by HCl via the addition of ethanol followed by sonication of the solution led to the formation of type-II nanoframes, which have elliptical pores on the {110} faces. The morphologies of these nanoframes were carefully examined by electron microscopy. Without addition of ethanol, random etching of the nanocages can occur at a slow rate. Octahedral gold nanocrystals and high-aspect-ratio gold nanorods were successfully encapsulated in the interiors of these Cu 2O nanocages by adding the gold nanostructures into the reaction solution. The formation process for such core-cage composite structures was studied. These composite materials should display interesting properties and functions.
我们报道了一种制备具有异常截顶菱形十二面体结构的氧化亚铜(Cu₂O)纳米笼和纳米框架的简单方法。制备了一种含有CuCl₂、十二烷基硫酸钠(SDS)表面活性剂、NH₂OH·HCl还原剂、HCl和NaOH的水溶液,试剂按所列顺序加入。试剂混合45分钟后,快速的种子粒子聚集和中间结构的表面重构导致了I型纳米框架的生长,其仅有{110}骨架面和空的{100}面。再持续晶体生长75分钟产生了具有填充{100}面的纳米笼。这些纳米笼的直径为350 - 400 nm,其壁比纳米框架的壁厚。通过加入乙醇后用HCl对纳米笼的{110}面进行选择性酸性蚀刻,随后对溶液进行超声处理,导致形成II型纳米框架,其在{110}面上具有椭圆形孔。通过电子显微镜仔细检查了这些纳米框架的形态。不添加乙醇时,纳米笼会以缓慢的速率发生随机蚀刻。通过将金纳米结构加入反应溶液中,八面体金纳米晶体和高纵横比的金纳米棒成功地封装在这些Cu₂O纳米笼的内部。研究了这种核 - 笼复合结构的形成过程。这些复合材料应表现出有趣的性质和功能。