Han Wei, Yi Luoxin, Zhao Nan, Tang Aiwei, Gao Mingyuan, Tang Zhiyong
Institute of Chemistry, Chinese Academy of Sciences, Bei Yi Jie 2, Zhong Guan Cun, Beijing 100190, China.
J Am Chem Soc. 2008 Oct 1;130(39):13152-61. doi: 10.1021/ja8046393. Epub 2008 Sep 6.
Heterostructured Cu2S-In2S3 nanocrystals with various shapes and compositions were synthesized by a high-temperature precursor-injection method using the semiconductor nanocrystal Cu1.94S as a catalyst. The intrinsic cationic deficiencies formed at high temperature by Cu ions made the Cu1.94S nanocrystal a good candidate for catalyzing the nucleation and subsequent growth of In 2S3 nanocrystals, eventually leading to the formation of heterostructured Cu2S-In2S3 nanocrystals. Gelification of the reaction systems, which were composed of different types of nanocrystal precursors and solvent, was found to be a very effective measure for controlling the growth kinetics of the heterostructured particles. Consequently, matchsticklike Cu2S3-In2S3 heterostructured nanorods, teardroplike quasi-core/shell Cu2S@In2S3 nanocrystals, and pencil-like In2S3 nanorods were successfully obtained by manipulating the gelification of the reaction system; this formed a solid experimental basis for further discussion of the growth mechanisms for differently shaped and structured nanocrystals. By reaction with 1,10-phenanthroline, a reagent that strongly and selectively binds to Cu(+), a compositional transformation from binary matchsticklike Cu2S-In2S3 nanorods to pure In2S3 nanorods was successfully achieved.
以半导体纳米晶体Cu1.94S为催化剂,通过高温前驱体注入法合成了具有不同形状和组成的异质结构Cu2S-In2S3纳米晶体。高温下由铜离子形成的固有阳离子缺陷使Cu1.94S纳米晶体成为催化In2S3纳米晶体成核及后续生长的良好候选物,最终导致异质结构Cu2S-In2S3纳米晶体的形成。由不同类型的纳米晶体前驱体和溶剂组成的反应体系的凝胶化被发现是控制异质结构颗粒生长动力学的一种非常有效的措施。因此,通过控制反应体系的凝胶化,成功获得了火柴状Cu2S3-In2S3异质结构纳米棒、泪滴状准核壳Cu2S@In2S3纳米晶体和铅笔状In2S3纳米棒;这为进一步探讨不同形状和结构的纳米晶体的生长机制奠定了坚实的实验基础。通过与1,10-菲咯啉(一种能与Cu(+)强烈且选择性结合的试剂)反应,成功实现了从二元火柴状Cu2S-In2S3纳米棒到纯In2S3纳米棒的组成转变。