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The effects of antimony doping on the surface structure of rutile TiO2(110)

机译：锑掺杂对金红石型TiO2（110）表面结构的影响

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Titanium dioxide represents a very important wide bandgap photocatalyst that is known to be sensitized to visible light by transition metal doping. Antimony doping has been demonstrated to provide photocatalytic activity when codoped with chromium at an optimum dopant ratio [Sb]/[Cr] of about 1.5. Here, the role of antimony doping on the surface structure of rutile TiO2(110) is studied using non-contact atomic force microscopy (NC-AFM) under ultra-high vacuum conditions. At first glance, the surface structure of antimony-doped iO2(110) resembles the structure of pristine TiO2(110). However, in contrast to what is found in pristine TiO2(110), a dense layer of protruding features is observed upon antimony doping, which is tentatively ascribed to antimony-rich clusters. Moreover, homogeneously distributed holes are found on the surface, which differ in depth and shape depending on the preparation conditions. Holes with depths ranging from a few up to more than a hundred onatomic steps are observed. These holes are explained by surface segregation of antimony during annealing, as the ionic radius of Sb3+ is considerably larger than the ionic radius of Ti4+. Our finding provides an indication of why an antimony concentration larger than the optimum atio results in decreased photocatalytic activity. Moreover, controlling annealing temperature seems to constitute a promising strategy for creating nanosized holes on TiO2 surfaces.
机译：二氧化钛代表一种非常重要的宽带隙光催化剂，已知它通过过渡金属掺杂而对可见光敏感。已经证明，当以约1.5的最佳掺杂比[Sb] / [Cr]与铬共掺杂时，锑掺杂可提供光催化活性。在这里，使用非接触原子力显微镜（NC-AFM）在超高真空条件下研究了锑掺杂对金红石TiO2（110）表面结构的作用。乍看之下，掺锑的iO2（110）的表面结构类似于原始的TiO2（110）的结构。但是，与原始的TiO2（110）相比，锑掺杂时会观察到致密的突出特征层，这暂时归因于富含锑的团簇。此外，在表面上发现均匀分布的孔，其深度和形状根据制备条件而不同。观察到的孔的深度范围从几步到一百多步。这些孔由退火过程中锑的表面偏析来解释，因为Sb3 +的离子半径大大大于Ti4 +的离子半径。我们的发现提供了为什么锑浓度大于最佳比率会导致光催化活性降低的指示。此外，控制退火温度似乎是在TiO2表面上形成纳米孔的有前途的策略。

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