Chen Yongfen, Johnson Eric, Peng Xiaogang
Department of Chemistry & Biochemistry, University of Arkansas, Fayetteville, Arkansas 72701, USA.
J Am Chem Soc. 2007 Sep 5;129(35):10937-47. doi: 10.1021/ja073023n. Epub 2007 Aug 14.
Formation of nearly monodiperse MnO nanocrystals by simple heating of Mn stearate in octadecene was studied systematically and quantitatively as a model for non-injection synthesis of nanocrystals. For controlling the shape of the nanocrystals, that is, rice, rods, peanuts, needles, and dots, either an activation reagent (ocadecanol) or an inhibitor (stearic acid) might be added prior to heating. The quantitative results of this typical non-injection system reveal that the formation of nearly monodisperse nanocrystals did not follow the well-known "focusing of size distribution" mechanism. A new growth mechanism, self-focusing enabled by inter-particle diffusion, is proposed. Different from the traditional "focusing of size distribution", self-focusing not only affects the growth process of the nanocrystals, but may also play a role in controlling nucleation. Because of the simplicity of the reaction system, it was possible to also identify the chemical reactions associated with the growth and ripening of MnO nanocrystals with a variety of shapes. Through a recycling reaction path, water was identified as a decisive component in determining the kinetics for both growth and ripening in this system, although the reaction occurred at around 300 degrees C.
通过在十八碳烯中简单加热硬脂酸锰来制备近单分散的MnO纳米晶体,作为纳米晶体非注射合成的模型进行了系统和定量的研究。为了控制纳米晶体的形状,即米粒状、棒状、花生状、针状和点状,在加热前可以添加活化剂(十八醇)或抑制剂(硬脂酸)。这个典型非注射系统的定量结果表明,近单分散纳米晶体的形成并不遵循众所周知的“尺寸分布聚焦”机制。提出了一种新的生长机制,即通过粒子间扩散实现的自聚焦。与传统的“尺寸分布聚焦”不同,自聚焦不仅影响纳米晶体的生长过程,还可能在控制成核中发挥作用。由于反应系统的简单性,还能够确定与各种形状的MnO纳米晶体生长和熟化相关的化学反应。通过循环反应路径,水被确定为决定该系统中生长和熟化动力学的决定性成分,尽管反应在约300℃发生。