Dissociation of liquid water on defective rutile TiO2 (110) surfaces using ab initio molecular dynamics simulations
Hui-Li Wang (王会丽)1,3, Zhen-Peng Hu (胡振芃)1, Hui Li (李晖)2()
1. School of Physics, Nankai University, Tianjin 300071, China 2. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China 3. Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
In order to obtain a comprehensive understanding of both thermodynamics and kinetics of water dissociation on TiO2, the reactions between liquid water and perfect and defective rutile TiO2 (110) surfaces were investigated using ab initio molecular dynamics simulations. The results showed that the free-energy barrier (~4.4 kcal/mol) is too high for a spontaneous dissociation of water on the perfect rutile (110) surface at a low temperature. The most stable oxygen vacancy (Vo1) on the rutile (110) surface cannot promote the dissociation of water, while other unstable oxygen vacancies can significantly enhance the water dissociation rate. This is opposite to the general understanding that Vo1 defects are active sites for water dissociation. Furthermore, we reveal that water dissociation is an exothermic reaction, which demonstrates that the dissociated state of the adsorbed water is thermodynamically favorable for both perfect and defective rutile (110) surfaces. The dissociation adsorption of water can also increase the hydrophilicity of TiO2.
. [J]. Frontiers of Physics, 2018, 13(3): 138107.
Hui-Li Wang (王会丽), Zhen-Peng Hu (胡振芃), Hui Li (李晖). Dissociation of liquid water on defective rutile TiO2 (110) surfaces using ab initio molecular dynamics simulations. Front. Phys. , 2018, 13(3): 138107.
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