Ghosh Moumita, Pralong V, Wattiaux A, Sleight A W, Subramanian M A
Oregon State University Materials Institute and Department of Chemistry, Oregon State University, Corvallis, OR 97331 (USA), Fax: (+1) 541-737-2062.
Laboratoire CRISMAT, ENSICAEN, 6 bd Marechal Juin, 14050 CAEN Cedex (France).
Chem Asian J. 2009 Jun 2;4(6):881-885. doi: 10.1002/asia.200900028.
During our exploration of compounds in the Sn(II)-Ti(IV)-O system, we discovered that hydrolysis of titanium alkoxide solution in the presence of Sn(II) salts resulted in stable deep-yellow colored anatase nanoparticles. The samples were characterized by X-ray powder diffraction, electron microprobe, thermal analysis, transmission electron microscopy, and (119)Sn Mössbauer spectroscopy. Mössbauer data of the yellow colored samples showed the presence of both Sn(II) and Sn(IV) in a distorted environment as expected in the anatase structure. It is suggested that the cationic charge imbalance is compensated by oxygen vacancies and/or hydroxyl groups as evidenced by Mössbauer data which show two types of Sn(II) environments. When heated in air to 300 degrees C the samples changed color to completely white and (119)Sn Mössbauer data of these samples showed only the presence of Sn(IV). These observations indicate that the origin of the yellow color in our Sn doped anatase nanoparticles arises from filled Sn 5s states just above the O 2p band, thus decreasing the band gap. The Sn(II) doped anatase TiO(2) nanoparticles reported here can potentially lead to environmentally benign yellow pigments. The simplistic nature of the synthetic procedure could easily be adapted to large-scale industrial manufacture.
在我们对Sn(II)-Ti(IV)-O体系中的化合物进行探索期间,我们发现,在Sn(II)盐存在的情况下,钛醇盐溶液发生水解会生成稳定的深黄色锐钛矿纳米颗粒。通过X射线粉末衍射、电子微探针、热分析、透射电子显微镜和(119)Sn穆斯堡尔谱对样品进行了表征。黄色样品的穆斯堡尔数据表明,正如在锐钛矿结构中所预期的那样,在畸变环境中同时存在Sn(II)和Sn(IV)。有迹象表明,阳离子电荷不平衡由氧空位和/或羟基补偿,穆斯堡尔数据显示出两种类型的Sn(II)环境,这证明了这一点。当在空气中加热到300℃时,样品颜色变为完全白色,这些样品的(119)Sn穆斯堡尔数据表明只存在Sn(IV)。这些观察结果表明,我们的Sn掺杂锐钛矿纳米颗粒中黄色的来源是刚好位于O 2p能带之上的充满的Sn 5s态,从而减小了带隙。本文报道的Sn(II)掺杂锐钛矿TiO₂纳米颗粒可能会产生对环境无害的黄色颜料。合成过程的简单性质可以很容易地适用于大规模工业生产。