Citation: ZHAO Wei-Na, LIN Hua-Xiang, LI Yi, ZHANG Yong-Fan, HUANG Xin, CHEN Wen-Kai. Coverage-Dependent Adsorption of X Clusters (X=Pt-Au, Au-Au) on the Defect-Free (3×2) TiO₂(110) Surface[J]. Acta Physico-Chimica Sinica, ;2012, 28(08): 1861-1868. doi: 10.3866/PKU.WHXB201205214 shu

Coverage-Dependent Adsorption of X Clusters (X=Pt-Au, Au-Au) on the Defect-Free (3×2) TiO₂(110) Surface

1.
1. College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350116, P. R. China;
2. Fujian Provincial Key Laboratory of Photocatalysis-State Key Laboratory Breeding Base, Fuzhou University, Fuzhou 350002, Fujian, P. R. China

Received Date: 20 March 2012
Available Online: 21 May 2012
Fund Project: 国家自然科学基金(90922022) (90922022)华中科技大学煤燃烧国家重点实验室开放基金(FSKLCC1110)资助项目 (FSKLCC1110)

Based on spin-polarized density functional theory and generalized gradient approximation (DFT-GGA) calculations, the coverage-dependent adsorption of X bimetallic clusters (X=Pt-Au, Au-Au) on the (3 × 2) TiO₂(110) surface has been investigated utilizing periodic supercell models in the absence of oxygen vacancy sites. Only the ground-state structures corresponding to the given coverage patterns (θ= 1/6-1 ML) for X clusters are discussed in this work. The unambiguous results reveal that the adsorption energies increase with coverage up to 1/2 ML and then decrease except for when saturated coverage is reached. According to the interaction with X clusters, it is more feasible at all coverage levels to create a monolayer film of Pt-Au bimetallic clusters on the TiO₂(110) surface than it is to create a monolayer of Au- Au clusters, even though the adsorption energy of the Pt-Au/TiO₂ adsorption system is smaller in comparison with that of the Au-Au/TiO₂ system. Importantly, especially for the half and saturated coverages, there is a broadening of X peaks overlapping with the TiO₂ state ranging from -3.0 eV to the Fermi level, suggesting a strong interaction between the surface and bimetallic cluster. Also of particular interest is the adsorptive mechanism where the X-TiO₂ interaction is the main driving force at the initial stage of the adsorption process, whereas the X-X interaction controls the process as the coverage increases.
- Density functional theory,
- TiO₂ (110) surface,
- Bimetallic cluster
1. [1]
  
  (1) Harada, M.; Asakura, K.; Toshima, N. J. Phys. Chem. 1993, 97,5103. doi: 10.1021/j100121a042
2. [2]
  (2) Luo, J.; Maye, M. M.; Petkov, V.; Kariuki, N. N.;Wang, L. Y.;Njoki, P.; Mott, D.; Lin, Y.; Zhong, C. J. Chem. Mater. 2005, 17,3086. doi: 10.1021/cm050052t
3. [3]
  (3) Scott, R.W. J.; Sivadinarayana, C.;Wilson, O. M.; Yan, Z.; odman, D.W.; Crooks, R. M. J. Am. Chem. Soc. 2005, 127,1380. doi: 10.1021/ja044446h
4. [4]
  (4) Wang, Y.; Toshima, N. J. Phys. Chem. B 1997, 101, 5301. doi: 10.1021/jp9704224
5. [5]
  (5) Belloni, J.; Mostafavi, M.; Remita, H.; Marignier, J. L.;Delcourt, M. O. New J. Chem. 1998, 22, 1239. doi: 10.1039/a801445k
6. [6]
  (6) Link, S.;Wang, Z. L.; El-Sayed, M. A. J. Phys. Chem. B 1999,103, 3529. doi: 10.1021/jp990387w
7. [7]
  (7) Fang, Y. H.; Liu, Z. P. J. Am. Chem. Soc. 2010, 132, 18214. doi: 10.1021/ja1069272
8. [8]
  (8) Notoya, F.; Su, C.; Sasaoka, E. Ind. Eng. Chem. Res. 2001, 40,3732. doi: 10.1021/ie000972f
9. [9]
  (9) Diebold, U. Surf. Sci. Rep. 2003, 48, 53. doi: 10.1016/S0167-5729(02)00100-0
10. [10]
  (10) Pang, C. L.; Lindsay, R.; Thornton, G. Chem. Soc. Rev. 2008,37, 2328. doi: 10.1039/b719085a
11. [11]
  (11) Wang, C. M.; Fan, K. N.; Liu, Z. P. J. Am. Chem. Soc. 2007,129, 2642. doi: 10.1021/ja067510z
12. [12]
  (12) ng, X. Q.; Liu, Z. P.; Raval, R.; Hu, P. J. Am. Chem. Soc.2004, 126, 8. doi: 10.1021/ja030392k
13. [13]
  (13) Yudanov, I.; Pacchioni, G.; Neyman, K.; Ro1sch, N. J. Phys. Chem. B 1997, 101, 2786. doi: 10.1021/jp962487x
14. [14]
  (14) Rodriguez, J. A.; Liu, G.; Jirsak, T.; Hrbek, J.; Chang, Z.;Dvorak, J.; Maiti, A. J. Am. Chem. Soc. 2002, 124, 5242. doi: 10.1021/ja020115y
15. [15]
  (15) Pabisiak, T.; Kiejna, A. Surf. Sci. 2011, 605, 668. doi: 10.1016/j.susc.2010.12.033
16. [16]
  (16) Henderson, M. A. Surf. Sci. Rep. 2002, 46, 1. doi: 10.1016/S0167-5729(01)00020-6
17. [17]
  (17) Chen, S. H.; Xu, Y.; Lü, B. L.;Wu, D. Acta Phys. -Chim. Sin.2011, 27, 2933. [陈淑海, 徐耀, 吕宝亮, 吴东. 物理化学学报, 2011, 27, 2933.] doi: 10.3866/PKU.WHXB20112933
18. [18]
  (18) Dong, H, Q.; Pan, X.; Xie, Q.; Meng, Q. Q.; Gao, J. R.;Wang, J.G. Acta Phys. -Chim. Sin. 2012, 28, 44. [董华青, 潘西,谢琴, 孟强强, 高建荣, 王建国. 物理化学学报, 2012, 28,44.] doi: 10.3866/PKU.WHXB20122844
19. [19]
  (19) Thompson, T. L.; Yates, J. T. Chem. Rev. 2006, 106, 4428.
20. [20]
  (20) Ganduglia-Pirovano, M. V.; Hofmanna, A.; Sauer, J. Surf. Sci. Rep. 2007, 62, 219. doi: 10.1016/j.surfrep.2007.03.002
21. [21]
  (21) Tomohito, T.; Matsunaga, K.; Ikuhara, Y.; Yamamoto, T. Phys. Rev. B 2003, 68, 205213. doi: 10.1103/PhysRevB.68.205213
22. [22]
  (22) Perron, H.; Domain, C.; Roques, J.; Drot, R.; Simoni, E.;Catalette, H. Theor. Chem. Acc. 2007, 117, 565. doi: 10.1007/s00214-006-0189-y
23. [23]
  (23) Ramamoorthy, M.; Vanderbilt, D.; King-Smith, R. D. Phys. Rev. B 1994, 49, 16721. doi: 10.1103/PhysRevB.49.16721
24. [24]
  (24) Cui, H. F.; Ye, J. S.; Liu, X.; Zhang,W. D.; Sheu, F. S.Nanotechnology 2006, 17, 2334. doi: 10.1088/0957-4484/17/9/043
25. [25]
  (25) Qian, L.; Yang, X. R. J. Phys. Chem. B 2006, 110, 16672. doi: 10.1021/jp063302h
26. [26]
  (26) Wu, M. L.; Chen, D. H.; Huang, T. C. Chem. Mater. 2001, 13,599. doi: 10.1021/cm0006502
27. [27]
  (27) Lu, Y.; Yuan, J. Y.; Polzer, F.; Drechsler, M.; Preussner, J. Nano2010, 4, 7078.
28. [28]
  (28) Hernández-Fernández, P.; Rojas, S.; Ocón, P.; Gómez de laFuente, J. L.; San Fabián, J.; Sanza, J.; Peña, M. A.; García-García, F. J.; Terreros, P.; Fierro, J. L. G. J. Phys. Chem. C2007, 111, 2913. doi: 10.1021/jp066812k
29. [29]
  (29) Tenney, S. A.; Ratliff, J. S.; Roberts, C. C.; He,W.; Ammal, S.C.; Heyden, A.; Chen, D. A. J. Phys. Chem. C 2010, 114, 21652.doi: 10.1021/jp108939h
30. [30]
  (30) Park, J. B.; Conner, S. F.; Chen, D. A. J. Phys. Chem. C 2008,112, 5490. doi: 10.1021/jp076027n
31. [31]
  (31) Wen, D.; Guo, S.;Wang, Y.; Dong, S. Langmuir 2010, 26,11401. doi: 10.1021/la100869r
32. [32]
  (32) Boronat, M.; Corma, A. Langmuir 2010, 26, 16607. doi: 10.1021/la101752a
33. [33]
  (33) Payne, M.; Teter, M.; Allan, D.; Arias, T.; Joannopoulos, J. Rev. Mod. Phys. 1992, 64, 1045. doi: 10.1103/RevModPhys.64.1045
34. [34]
  (34) Hohenberg, P.; Kohn,W. Phys. Rev. B 1964, 136, 864. doi: 10.1103/PhysRev.136.B864
35. [35]
  (35) Jones, R.; Gunnarsson, O. Rev. Mod. Phys. 1989, 61, 689. doi: 10.1103/RevModPhys.61.689
36. [36]
  (36) Kohn,W.; Sham, L. Phys. Rev. 1965, 140, 1133. doi: 10.1103/PhysRev.140.A1133
37. [37]
  (37) Perdew, J. P.;Wang, Y. Phys. Rev. B 1992, 45, 13244. doi: 10.1103/PhysRevB.45.13244
38. [38]
  (38) Delley, B. J. Chem. Phys. 1990, 92, 508. doi: 10.1063/1.458452
39. [39]
  (39) Delley, B. J. Chem. Phys. 2000, 113, 7756. doi: 10.1063/1.1316015
40. [40]
  (40) niakowski, J.; Holender, J. M.; Kantorovich, L. N.; Gillan,M. J. Phys. Rev. B 1996, 53, 957. doi: 10.1103/PhysRevB.53.957
41. [41]
  (41) Sanz, J. F.; Márquez, A. J. Phys. Chem. C 2007, 111, 3949. doi: 10.1021/jp0639952
42. [42]
  (42) niakowski, J.; Gillan, M. J. Surf. Sci. 1996, 350, 145. doi: 10.1016/0039-6028(95)01252-4
43. [43]
  (43) White, J. A.; Bird, D. M.; Payne, M. C.; Stich, I. Phys. Rev. Lett.1994, 73, 1404. doi: 10.1103/PhysRevLett.73.1404
44. [44]
  (44) Versluis, L.; Zeigler, T. J. Chem. Phys. 1988, 88, 322. doi: 10.1063/1.454603
45. [45]
  (45) von Barth, U.; Hedin, L. J. Phys. C 1972, 5, 1629. doi: 10.1088/0022-3719/5/13/012
46. [46]
  (46) Matsuzawa, N.; Seto, J. E.; Dixon, D. A. J. Phys. Chem. A 1997,101, 9391. doi: 10.1021/jp952465v
47. [47]
  (47) Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188. doi: 10.1103/PhysRevB.13.5188
48. [48]
  (48) Fernandez, S.; Markovits, A.; Miont, C. J. Phys. Chem. C 2008,112, 14010. doi: 10.1021/jp800708u
49. [49]
  (49) Zou, X. J.; Ding, K. N.; Zhang, Y. F.; Li, J. Q. Int. J. Quantum Chem. 2011, 111, 915. doi: 10.1002/qua.22454
50. [50]
  (50) Zhu, J.; Jin, H.; Chen,W. J.; Li, Y.; Zhang, Y. F.; Ning, L. X;Huang, X.; Ding, K. N; Chen,W. K. J. Phys. Chem. C 2009,113, 17509. doi: 10.1021/jp906194t
51. [51]
  (51) Mazheika, A. S.; Matulis, V. E.; Ivashkevich, O. A. J. Mol. Struct. 2009, 909, 75.
52. [52]
  (52) Zeng, Q. S.; Chen,W. K.; Dai,W. X.; Zhang, Y. F.; Li, Y.; Guo,X. Chin. J. Catal. 2010, 31, 423. [曾庆松, 陈文凯, 戴文新,章永凡, 李奕, 郭欣. 催化学报, 2010, 31, 423.]
53. [53]
  (53) Lopez, N.; Nørskov, J. K. Surf. Sci. 2002, 515, 175. doi: 10.1016/S0039-6028(02)01873-3
54. [54]
  (54) Markovits, A.; Paniagua, J. C.; López, N.; Minot, C.; Illas, F.Phys. Rev. B 2003, 67, 115417. doi: 10.1103/PhyRevB.67.115417
55. [55]
  (55) Labat, F.; Baranek, P.; Domain, C.; Minot, C.; Adamo, C.J. Chem. Phys. 2007, 126, 154703. doi: 10.1063/1.2717168
56. [56]
  (56) Burdett, J. K.; Hughbanks, T.; Miller, G. J.; Richardson, J.W.,Jr.; Smith, J. V. J. Am. Chem. Soc. 1987, 109, 3639. doi: 10.1021/ja00246a021
57. [57]
  (57) Thiên-Nga, L.; Paxon, A. T. Phys. Rev. B 1998, 58, 13233. doi: 10.1103/PhysRevB.58.13233
58. [58]
  (58) Yang, Z.;Wu, R.; odman, D.W. Phys. Rev. B 2000, 61,14066. doi: 10.1103/PhysRevB.61.14066
59. [59]
  (59) Lai, X.; Clair, T. P. S.; Valden, M.; odman, D.W. Prog. Surf. Sci. 1998, 59, 25. doi: 10.1016/S0079-6816(98)00034-3
60. [60]
  (60) Bates, S. P.; Kresse, G.; Gillan, M. J. Surf. Sci. 1997, 385, 386.doi: 10.1016/S0039-6028(97)00265-3
61. [61]
  (61) Mattsson, A. E.; Jennison, D. R. Surf. Sci. 2002, 520, L611.
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Coverage-Dependent Adsorption of X Clusters (X=Pt-Au, Au-Au) on the Defect-Free (3×2) TiO2(110) Surface

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通讯作者: 陈斌, bchen63@163.com

Coverage-Dependent Adsorption of X Clusters (X=Pt-Au, Au-Au) on the Defect-Free (3×2) TiO₂(110) Surface