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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 |
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Abstract 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.
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Keywords
ab initio molecular dynamics
rutile (110)
free energy barrier
spontaneous reaction
exothermic reaction
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Corresponding Author(s):
Hui Li (李晖)
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Issue Date: 19 April 2018
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1 |
A. Fujishima and K. Honda, Electrochemical photolysis of water at a semiconductor electrode, Nature 238(5358), 37 (1972)
https://doi.org/10.1038/238037a0
|
2 |
X. Chen, L. Liu, P. Y. Yu, and S. S. Mao, Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals, Science 331(6018), 746 (2011)
https://doi.org/10.1126/science.1200448
|
3 |
S. J. Tan, F. Hao, Y. F. Ji, Y. Wang, J. Zhao, A. D. Zhao, B. Wang, Y. Luo, J. L. Yang, and J. G. Hou, Observation of photocatalytic dissociation of water on terminal Ti sites of TiO2 (110)-1×1 Surface, J. Am. Chem. Soc. 134(24), 9978 (2012)
https://doi.org/10.1021/ja211919k
|
4 |
J. H. Liang, N. Wang, Q. X. Zhang, B. F. Liu, X. B. Kong, C. C. Wei, D. K. Zhang, B. J. Yan, Y. Zhao, and X. D. Zhang, Exploring the mechanism of a pure and amorphous black-blue TiO2:H thin film as a photoanode in water splitting, Nano Energy 42, 151 (2017)
https://doi.org/10.1016/j.nanoen.2017.10.062
|
5 |
V. E. Henrich and P. A. Cox, The Surface Science of Metal Oxides, Cambridge: Cambridge University Press, 1994
|
6 |
H. J. Freund, Introductory lecture: Oxide surfaces, Faraday Discuss. 114, 1 (1999)
https://doi.org/10.1039/a907182b
|
7 |
M. Ramamoorthy, D. Vanderbilt, and R. D. King-Smith, First-principles calculations of the energetics of stoichiometric TiO2 surfaces, Phys. Rev. B 49(23), 16721 (1994)
https://doi.org/10.1103/PhysRevB.49.16721
|
8 |
U. Diebold, The surface science of titanium dioxide, Surf. Sci. Rep. 48(5–8), 53 (2003)
https://doi.org/10.1016/S0167-5729(02)00100-0
|
9 |
M. A. Henderson, An HREELS and TPD study of water on TiO2 (110): the extent of molecular versus dissociative adsorption, Surf. Sci. 355(1–3), 151 (1996)
https://doi.org/10.1016/0039-6028(95)01357-1
|
10 |
I. M. Brookes, C. A. Muryn, and G. Thornton, Imaging water dissociation on TiO2 (110), Phys. Rev. Lett. 87(26), 266103 (2001)
https://doi.org/10.1103/PhysRevLett.87.266103
|
11 |
R. Schaub, R. Thostrup, N. Lopez, E. Laegsgaard, I. Stensgaard, J. K. Norskov, and F. Besenbacher, Oxygen vacancies as active sites for water dissociation on rutile TiO2 (110), Phys. Rev. Lett. 87(26), 266104 (2001)
https://doi.org/10.1103/PhysRevLett.87.266104
|
12 |
O. Bikondoa, C. L. Pang, R. Ithnin, C. A. Muryn, H. Onishi, and G. Thornton, Direct visualization of defect-mediated dissociation of water on TiO2 (110), Nat. Mater. 5(3), 189 (2006)
https://doi.org/10.1038/nmat1592
|
13 |
S. Wendt, J. Matthiesen, R. Schaub, E. K. Vestergaard, E. Lægsgaard, F. Besenbacher, and B. Hammer, Formation and splitting of paired hydroxyl groups on reduced TiO2 (110), Phys. Rev. Lett. 96(6), 066107 (2006)
https://doi.org/10.1103/PhysRevLett.96.066107
|
14 |
M. A. Henderson, A surface science perspective on TiO2 photocatalysis, Surf. Sci. Rep. 66(6–7), 185 (2011)
https://doi.org/10.1016/j.surfrep.2011.01.001
|
15 |
C. L. Pang, R. Lindsay, and G. Thornton, Structure of clean and adsorbate-covered single-crystal rutile TiO2 surfaces., Chem. Rev. 113(6), 3887 (2013)
https://doi.org/10.1021/cr300409r
|
16 |
M. B. Hugenschmidt, L. Gamble, and C. T. Campbell, The interaction of H2O with a TiO2 (110) surface, Surf. Sci. 302(3), 329 (1994)
https://doi.org/10.1016/0039-6028(94)90837-0
|
17 |
L. E. Walle, A. Borg, P. Uvdal, and A. Sandell, Experimental evidence for mixed dissociative and molecular adsorption of water on a rutile TiO2 (110) surface without oxygen vacancies, Phys. Rev. B 80(23), 235436 (2009)
https://doi.org/10.1103/PhysRevB.80.235436
|
18 |
H. H. Kristoffersen, J. Ø. Hansen, U. Martinez, Y. Y. Wei, J. Matthiesen, R. Streber, R. Bechstein, E. Lægsgaard, F. Besenbacher, B. Hammer, and S. Wendt, Role of steps in the dissociative adsorption of water on rutile TiO2 (110), Phys. Rev. Lett. 110(14), 146101 (2013)
https://doi.org/10.1103/PhysRevLett.110.146101
|
19 |
E. V. Stefanovich and T. N. Truong, Ab initio study of water adsorption on TiO2 (110): molecular adsorption versus dissociative chemisorption, Chem. Phys. Lett. 299(6), 623 (1999)
https://doi.org/10.1016/S0009-2614(98)01295-0
|
20 |
W. Langel, Car-Parrinello simulation of H2O dissociation on rutile, Surf. Sci. 496(1–2), 141 (2002)
https://doi.org/10.1016/S0039-6028(01)01606-5
|
21 |
P. J. D. Lindan, N. M. Harrison, J. M. Holender, and M. J. Gillan, First-principles molecular dynamics simulation of water dissociation on TiO2 (110), Chem. Phys. Lett. 261(3), 246 (1996)
https://doi.org/10.1016/0009-2614(96)00934-7
|
22 |
P. J. D. Lindan, N. M. Harrison, and M. J. Gillan, Mixed dissociative and molecular adsorption of water on the rutile (110) surface, Phys. Rev. Lett. 80(4), 762 (1998)
https://doi.org/10.1103/PhysRevLett.80.762
|
23 |
L. E. Walle, D. Ragazzon, A. Borg, P. Uvdal, and A. Sandell, Competing water dissociation channels on rutile TiO2 (110), Surf. Sci. 621, 77 (2014)
https://doi.org/10.1016/j.susc.2013.11.001
|
24 |
W. H. Zhang, J. L. Yang, Y. Luo, S. Monti, and V. Carravetta, Quantum molecular dynamics study of water on TiO2 (110) surface, J. Chem. Phys. 129(6), 064703 (2008)
https://doi.org/10.1063/1.2955452
|
25 |
L. A. Harris and A. A. Quong, Molecular chemisorption as the theoretically preferred pathway for water adsorption on ideal rutile TiO2 (110), Phys. Rev. Lett. 93(8), 086105 (2004)
https://doi.org/10.1103/PhysRevLett.93.086105
|
26 |
C. Zhang and P. J. D. Lindan, Multilayer water adsorption on rutile TiO2 (110): A first-principles study, J. Chem. Phys. 118(10), 4620 (2003)
https://doi.org/10.1063/1.1543983
|
27 |
N. Kumar, S. Neogi, P. R. C. Kent, A. V. Bandura, J. D. Kubicki, D. J. Wesolowski, D. Cole, and J. O. Sofo, Hydrogen bonds and vibrations of water on (110) rutile, J. Phys. Chem. C 113(31), 13732 (2009)
https://doi.org/10.1021/jp901665e
|
28 |
L. M. Liu, C. J. Zhang, G. Thornton, and A. Michaelides, Structure and dynamics of liquid water on rutile TiO2 (110), Phys. Rev. B 82(16), 161415 (2010)
https://doi.org/10.1103/PhysRevB.82.161415
|
29 |
H. Hussain, G. Tocci, T. Woolcot, X. Torrelles, C. L. Pang, D. S. Humphrey, C. M. Yim, D. C. Grinter, G. Cabailh, O. Bikondoa, R. Lindsay, J. Zegenhagen, A. Michaelides, and G. Thornton, Structure of a model TiO2 photocatalytic interface, Nat. Mater. 16(4), 461 (2017)
https://doi.org/10.1038/nmat4793
|
30 |
J. VandeVondele, M. Krack, F. Mohamed, M. Parrinello, T. Chassaing, and J. Hutter, Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach, Comput. Phys. Commun. 167(2), 103 (2005)
https://doi.org/10.1016/j.cpc.2004.12.014
|
31 |
A. D. Becke, Density-functional exchange-energy approximation with correct asymptotic behavior, Phys. Rev. A 38(6), 3098 (1988)
https://doi.org/10.1103/PhysRevA.38.3098
|
32 |
C. Lee, W. Yang, and R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B 37(2), 785 (1988)
https://doi.org/10.1103/PhysRevB.37.785
|
33 |
A. R. Khoei, P. Ghahremani, M. J. Abdolhosseini Qomi, and P. Banihashemi, Stability and sizedependency of temperature-related Cauchy-Born hypothesis, Comput. Mater. Sci. 50(5), 1731 (2011)
https://doi.org/10.1016/j.commatsci.2011.01.004
|
34 |
J. Oviedo, M. A. San Miguel, and J. F. Sanz, Oxygen vacancies on TiO2 (110) from first principles calculations, J. Chem. Phys. 121(15), 7427 (2004)
https://doi.org/10.1063/1.1796253
|
35 |
L. A. Harris and A. A. Quong, Molecular chemisorption as the theoretically preferred pathway for water adsorption on ideal rutile TiO2 (110), Phys. Rev. Lett. 93, 086105 (2004)
https://doi.org/10.1103/PhysRevLett.93.086105
|
36 |
P. J. D. Lindan and C. Zhang, Exothermic water dissociation on the rutile TiO2 (110) surface, Phys. Rev. B 72, 075439 (2005)
https://doi.org/10.1103/PhysRevB.72.075439
|
37 |
A. Laio and M. Parrinello, Escaping free-energy minima, PNAS 99(20), 12562 (2002)
https://doi.org/10.1073/pnas.202427399
|
38 |
D. Branduardi, G. Bussi, and M. Parrinello, Metadynamics with adaptive Gaussians, J. Chem. Theory Comput. 8(7), 2247 (2012)
https://doi.org/10.1021/ct3002464
|
39 |
N. G. Petrik and G. A. Kimmel, Reaction kinetics of water molecules with oxygen vacancies on rutile TiO2 (110), J. Phys. Chem. C 119(40), 23059 (2015)
https://doi.org/10.1021/acs.jpcc.5b07526
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