气体气泡对胶体氧化铁纳米晶体形成的影响。
Gas-bubble effects on the formation of colloidal iron oxide nanocrystals.
机构信息
Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
出版信息
J Am Chem Soc. 2011 Aug 17;133(32):12664-74. doi: 10.1021/ja2032597. Epub 2011 Jul 22.
This paper reports that gas bubbles can be used to tailor the kinetics of the nucleation and growth of inorganic-nanocrystals in a colloidal synthesis. We conducted a mechanistic study of the synthesis of colloidal iron oxide nanocrystals using gas bubbles generated by boiling solvents or artificial Ar bubbling. We identified that bubbling effects take place through absorbing local latent heat released from the exothermic reactions involved in the nucleation and growth of iron oxide nanocrystals. Our results show that gas bubbles display a stronger effect on the nucleation of iron oxide nanocrystals than on their growth. These results indicate that the nucleation and growth of iron oxide nanocrystals may rely on different types of chemical reactions between the iron-oleate decomposition products: the nucleation relies on the strongly exothermic, multiple-bond formation reactions, whereas the growth of iron oxide nanocrystals may primarily depend upon single-bond formation reactions. The identification of exothermic reactions is further consistent with our results in the synthesis of iron oxide nanocrystals with boiling solvents at reaction temperatures ranging from 290 to 365 °C, by which we determined the reaction enthalpy in the nucleation of iron oxide nanocrystals to be -142 ± 12 kJ/mol. Moreover, our results suggest that a prerequisite for effectively suppressing secondary nucleation in a colloidal synthesis is that the primary nucleation must produce a critical amount of nuclei, and this finding is important for a priori design of colloidal synthesis of monodispersed nanocrystals in general.
本文报道了可以利用气泡来调整胶体合成中无机纳米晶体成核和生长的动力学。我们通过沸腾溶剂或人工氩气鼓泡产生的气泡,对胶体氧化铁纳米晶体的合成进行了机理研究。我们确定,鼓泡效应是通过吸收铁氧化物纳米晶成核和生长过程中放热反应释放的局部潜热来实现的。结果表明,气泡对氧化铁纳米晶成核的影响比生长更强。这些结果表明,铁氧化物纳米晶的成核和生长可能依赖于油酸铁分解产物之间不同类型的化学反应:成核依赖于强烈放热的多键形成反应,而铁氧化物纳米晶的生长可能主要依赖于单键形成反应。放热反应的鉴定与我们用沸腾溶剂在 290 至 365°C 的反应温度下合成氧化铁纳米晶的结果进一步一致,通过该实验确定了氧化铁纳米晶成核的反应焓为-142±12 kJ/mol。此外,我们的结果表明,在胶体合成中有效抑制二次成核的前提条件是初级成核必须产生一定数量的晶核,这一发现对于一般单分散纳米晶体的胶体合成的先验设计具有重要意义。