Zhang Dong Ri, Cha Hyun Gil, Kang Young Soo
Department of Chemistry, Sogang University, #1 Shinsu-dong, Mapo-gu, Seoul 121-742, Korea.
J Nanosci Nanotechnol. 2011 Jul;11(7):6007-12. doi: 10.1166/jnn.2011.4323.
Anatase TiO2 nanorods with high crystallinity were synthesized using ammonia solution (28%) as a solvent by through the hydrothermal method. The X-ray diffraction pattern confirmed the product's anatase phase and high crystallinity, and the transmission electron microscope (TEM) image demonstrated the unique morphologies of the two ends of the TiO2 nanorods (two tringle-horn shapes and one round-horn shape), whose lengths and widths were within the ranges of 200-300 and 60-110 nm, respectively. The high-resolution TEM image clearly displayed the crystal lattices of the (101) planes lying along the direction of the lengthes of the TiO2 nanorods. The energy dispersive X-ray spectrum of a TiO2 nanorod revealed the presence of about 4 atm% nitrogen element as a trace in the anatase TiO2 nanorod. The Raman spectrum of the TiO2 nanorods also showed the typical bands of anatase TiO2 and very weak peaks resulting from the TiN first-order defect-induced Raman scattering. The UV-vis diffuse-reflectance spectra showed a slight red shift (about 3 nm) of the anatase TiO2 nanorods compared with P25, which probably resulted from the trace of TiN on the surfaces of the anatase TiO2 nanorods. A three-stage-process mechanism model is proposed for the formation of the nanorods: Rhombus crystallites bounded by four {101} faces are first formed through anisotropic growth, then longer rhombus crystallites are grown via oriented attachment, finally, nanorods with a unique morphology are self-assembled by Van Der Waals forces.
以28%的氨水溶液为溶剂,采用水热法合成了高结晶度的锐钛矿型TiO₂纳米棒。X射线衍射图谱证实了产物的锐钛矿相和高结晶度,透射电子显微镜(TEM)图像展示了TiO₂纳米棒两端独特的形貌(两个三角角形状和一个圆头形状),其长度和宽度分别在200 - 300 nm和60 - 110 nm范围内。高分辨率TEM图像清晰地显示了沿TiO₂纳米棒长度方向的(101)晶面的晶格。TiO₂纳米棒的能量色散X射线光谱显示在锐钛矿型TiO₂纳米棒中存在约4 atm%的痕量氮元素。TiO₂纳米棒的拉曼光谱也显示了锐钛矿型TiO₂的典型谱带以及由TiN一阶缺陷诱导拉曼散射产生的非常弱的峰。紫外可见漫反射光谱表明,与P25相比,锐钛矿型TiO₂纳米棒有轻微的红移(约3 nm),这可能是由于锐钛矿型TiO₂纳米棒表面的TiN痕量所致。提出了纳米棒形成的三阶段过程机制模型:首先通过各向异性生长形成由四个{101}面界定的菱形微晶,然后通过定向附着生长出更长的菱形微晶,最后,具有独特形貌的纳米棒通过范德华力自组装而成。