透射电子显微镜诱导的非晶态铁氧化物纳米颗粒的结构演变

TEM-induced structural evolution in amorphous Fe oxide nanoparticles.

作者信息

Latham Andrew H, Wilson Mark J, Schiffer Peter, Williams Mary Elizabeth

机构信息

Departments of Chemistry and Physics, The Pennsylvania State University, University Park, PA 16802, USA.

出版信息

J Am Chem Soc. 2006 Oct 4;128(39):12632-3. doi: 10.1021/ja064666q.

Abstract

Exposure to the high energy electron beam of a TEM changes the morphology of amorphous Fe oxide nanoparticles from solid spheres to hollow shells. Amorphous Fe oxide nanoparticles prepared via high-temperature methods using hexadecylamine and trioctylphosphine oxide surfactants were compared to crystalline gamma-Fe2O3 particles of similar size. Both sets of particles are fully characterized via SQUID magnetometry, X-ray powder diffraction, BET surface analysis, EPR spectroscopy, high-resolution transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS). Time-resolved TEM images reveal that the amorphous Fe oxide particles evolve from solid spheres into hollow shells in <2 min, whereas crystalline gamma-Fe2O3 are unaffected by the electron beam. The resulting nanocrystalline Fe oxide shells bear striking resemblance to core-shell nanocrystals, but are a result of a morphology change attributed to restructuring of particle voids and defects induced by quasi-melting in the TEM. These results thus imply that caution is necessary when using TEM to analyze nanoparticle core-shell and heterostructured nanoparticles.

摘要

暴露于透射电子显微镜(TEM)的高能电子束下会使非晶态氧化铁纳米颗粒的形态从实心球体变为空心壳。将使用十六胺和三辛基氧化膦表面活性剂通过高温方法制备的非晶态氧化铁纳米颗粒与尺寸相似的结晶γ-Fe₂O₃颗粒进行了比较。两组颗粒均通过超导量子干涉仪磁力测定法、X射线粉末衍射、BET表面分析、电子顺磁共振光谱、高分辨率透射电子显微镜(TEM)和电子能量损失光谱(EELS)进行了全面表征。时间分辨TEM图像显示,非晶态氧化铁颗粒在不到2分钟的时间内从实心球体演变成空心壳,而结晶γ-Fe₂O₃不受电子束影响。所得的纳米晶氧化铁壳与核壳纳米晶体极为相似,但这是由于TEM中准熔化引起的颗粒空隙和缺陷重组导致的形态变化所致。因此,这些结果表明,在使用TEM分析纳米颗粒核壳和异质结构纳米颗粒时必须谨慎。

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