Tang Zhiyong, Wang Ying, Shanbhag Sachin, Kotov Nicholas A
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109-2136, USA.
J Am Chem Soc. 2006 May 31;128(21):7036-42. doi: 10.1021/ja055366w.
CdTe nanoparticles stabilized by l-cysteine are chemically transformed into CdS nanoparticles of the same diameter via an intermediate CdTeS alloy without any auxiliary source of sulfur. The reaction is induced by ethylenediaminetetraacetic acid dipotassium salt dehydrate (EDTA), which was demonstrated experimentally to act as a catalyst by partially removing thiol stabilizers from the nanoparticle surface. It is hypothesized that addition of EDTA facilitates Te(2-) release, and oxidation of Te(2-) drives the nanoparticle transition process. Unlike many reports on reactions catalyzed by nanocolloids, this is likely to be the first observation of a catalytic reaction in which nanoparticles function as a substrate rather than a catalyst. It opens new pathways for the synthesis of novel nanoscale II-VI and other semiconductors and represents an interesting case of chemical processes in nanocolloids with reactivity increased by depletion of the surface layer of thiol stabilizers. This includes but is not limited to accurate control over the particle composition and crystallization rate. The slow rate of the CdTe --> alloy --> CdS transition is important for minimizing defects in the crystal lattice and results in a substantial increase of the quantum yield of photoluminescence over the course of the transition.
由L-半胱氨酸稳定的碲化镉纳米颗粒通过中间的碲镉硫合金在没有任何硫辅助源的情况下化学转化为相同直径的硫化镉纳米颗粒。该反应由乙二胺四乙酸二钾盐二水合物(EDTA)引发,实验证明它通过从纳米颗粒表面部分去除硫醇稳定剂而起到催化剂的作用。据推测,添加EDTA有助于碲离子(Te(2-))的释放,并且碲离子的氧化驱动了纳米颗粒的转变过程。与许多关于纳米胶体催化反应的报道不同,这可能是首次观察到纳米颗粒作为底物而非催化剂的催化反应。它为新型纳米级II-VI族及其他半导体的合成开辟了新途径,并且代表了纳米胶体中化学过程的一个有趣案例,其中通过硫醇稳定剂表面层的消耗提高了反应活性。这包括但不限于对颗粒组成和结晶速率的精确控制。碲化镉→合金→硫化镉转变的缓慢速率对于最小化晶格缺陷很重要,并且在转变过程中导致光致发光量子产率大幅提高。