Wang Dong, Wang Haifeng, Hu P
Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China.
Phys Chem Chem Phys. 2015 Jan 21;17(3):1549-55. doi: 10.1039/c4cp04159c. Epub 2014 Nov 12.
Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.
使用采用HSE 06泛函的密度泛函理论计算方法，我们获得了金红石型TiO2(110)上自旋极化自由基的结构，这对于在原子水平上理解光氧化过程至关重要，并且进一步计算了这些自由基的热力学稳定性。通过分析结果，我们确定了系统中空穴俘获的结构特征，并揭示了几何结构、俘获空穴态的能级及其空穴俘获能力之间的相互影响。此外，将HSE 06泛函的结果与DFT + U的结果进行了比较，并测试了自由基相对于板层数的稳定性趋势。研究并讨论了俘获空穴对析氧反应两个重要步骤（即水的解离和氧的去除）的影响。
