Shi Yongliang, Sun Huijuan, Saidi Wissam A, Nguyen Manh Cuong, Wang Cai Zhuang, Ho Kaiming, Yang Jinlong, Zhao Jin
ICQD/Hefei National Laboratory for Physical Sciences at Microscale and Key Laboratory of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, and Department of Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.
College of Physics, Qingdao University , Qingdao 266071, China.
J Phys Chem Lett. 2017 Apr 20;8(8):1764-1771. doi: 10.1021/acs.jpclett.7b00181. Epub 2017 Apr 6.
In contrast with theoretical predictions in which anatase TiO(001) and its (1 × 4) reconstructed surfaces are highly reactive, recent experimental results show this surface to be inert except for the defect sites. In this report, based on a systematic study of anatase TiO(001)-(1 × 4) surface using first-principles calculations, the tensile stress is shown to play a crucial role on the surface reactivity. The predicted high reactivity based on add-molecule model is due to the large surface tensile stress, which can be easily suppressed by a stress-release mechanism. We show that various surface defects can induce stress release concomitantly with surface passivation. Thus the synthesis of anatase(001) surface with few defects is essential to improve the reactivity, which can be achieved, for example, via HO adsorption. Our study provides a uniform interpretation of controversial experimental observations and theoretical predictions on anatase TiO(001) surface and further proposes new insights into the origin of surface reactivity.
与理论预测中锐钛矿型TiO(001)及其(1×4)重构表面具有高反应活性相反，最近的实验结果表明，除了缺陷位点外，该表面是惰性的。在本报告中，基于对锐钛矿型TiO(001)-(1×4)表面的系统第一性原理计算研究，拉伸应力被证明在表面反应活性中起关键作用。基于添加分子模型预测的高反应活性是由于大的表面拉伸应力，而这种应力可以通过应力释放机制轻易抑制。我们表明，各种表面缺陷可伴随着表面钝化诱导应力释放。因此，合成具有少量缺陷的锐钛矿(001)表面对于提高反应活性至关重要，这可以通过例如HO吸附来实现。我们的研究对关于锐钛矿型TiO(001)表面有争议的实验观察和理论预测提供了统一的解释，并进一步对表面反应活性的起源提出了新的见解。
