Department of Chemical and Biomolecular Engineering, KAUST-NUS GCR Program, and Minerals, Metals, and Materials Technology Center, Faculty of Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260.
J Am Chem Soc. 2010 May 5;132(17):6131-44. doi: 10.1021/ja100151f.
In this work, we describe a solution-based synthesis of monodisperse Cu(2)O nanocrystals with controllable sizes in the nanoscale regime. Two types of nanocrystals, cubes and rhombic dodecahedra unifaceted with either {001} or {110} crystal planes, have been prepared at a 100% morphological yield. In particular, synthetic parameters and formation processes of the Cu(2)O nanocrystals have been investigated in detail, and a range of well-oriented supercrystals/superlattices built from the two types of nanobuilding blocks have been attained for the first time. It has been revealed that n-hexadecylamine used in the present work plays multiple roles: it serves as a chelating ligand to form Cu(NH(2)C(16)H(33))(4) complex precursor, as a phase-transferring agent to transfer divalent Cu(2+) ions into the organic phase, as a reducing agent to generate monovalent Cu(+) (i.e., Cu(2)O), as a passivating adsorbate to control crystal morphology, and as a surface capping agent to generate self-assemblies of nanocrystals via van der Waals interaction. Apart from synthesis and self-assembly, disassembly and reassembly of Cu(2)O nanocrystals have also been investigated. The disassembly processes are accompanied with aggregative growths of nanocrystals, which can be attributed to a combined process of "oriented attachment" and Ostwald ripening, leading to permanent engagement and enlargement of nanocrystals. Finally, our self-assembled nanocrystals of Cu(2)O show a lower detection limit, lower operating temperature, and higher sensitivity in ethanol vapor detection, compared with other Cu(2)O-based alcohol sensors reported in the recent literature. A greater depletion layer of carrier and a relatively small contact potential may account for the observed sensing enhancement in the sensors made from the organized Cu(2)O nanocrystals.
在这项工作中,我们描述了一种基于溶液的方法,可在纳米范围内合成具有可控尺寸的单分散 Cu(2)O 纳米晶体。已经以 100%的形态产率制备了两种纳米晶体,即立方体和具有 {001} 或 {110} 晶面的菱形十二面体单面对称纳米晶体。特别是,详细研究了 Cu(2)O 纳米晶体的合成参数和形成过程,并首次获得了由这两种纳米构建块构建的一系列取向良好的超晶体/超晶格。结果表明,本工作中使用的十六烷基胺具有多种作用:它作为螯合配体形成 Cu(NH(2)C(16)H(33))(4) 配合物前体,作为相转移剂将二价 Cu(2+)离子转移到有机相中,作为还原剂生成单价 Cu(+)(即 Cu(2)O),作为钝化吸附剂控制晶体形态,以及作为表面封端剂通过范德华相互作用生成纳米晶体的自组装体。除了合成和自组装之外,还研究了 Cu(2)O 纳米晶体的拆卸和再组装。拆卸过程伴随着纳米晶体的聚集生长,这可以归因于“取向附着”和奥斯特瓦尔德熟化的联合过程,导致纳米晶体的永久结合和增大。最后,与最近文献中报道的其他基于 Cu(2)O 的酒精传感器相比,我们自组装的 Cu(2)O 纳米晶体在乙醇蒸气检测中具有更低的检测限、更低的工作温度和更高的灵敏度。载流子的耗尽层更大和接触电势较小可能是由有序 Cu(2)O 纳米晶体制成的传感器中观察到的传感增强所导致的。