Citation: Wang Wenyuan, Zhang Jiefu, Li Zhe, Shao Xiang. Atomic Structure and Adsorption Property of the Singly Dispersed Au/Cu(111) Surface Alloy[J]. Acta Physico-Chimica Sinica, ;2020, 36(8): 191103. doi: 10.3866/PKU.WHXB201911035 shu

Atomic Structure and Adsorption Property of the Singly Dispersed Au/Cu(111) Surface Alloy

Department of Chemical Physics, CAS Key Laboratory of Urban Pollutant Conversion, Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei 230026, P. R. China

Corresponding author: Shao Xiang, shaox@ustc.edu.cn
Received Date: 19 November 2019
Revised Date: 25 December 2019
Accepted Date: 27 December 2019
Available Online: 13 January 2020
Fund Project: the National Natural Science Foundation of China 21872130the National Key Research and Development Program of China 2017YFA0205003the National Natural Science Foundation of China 91545128The project was supported by the National Natural Science Foundation of China (21872130, 91545128) and the National Key Research and Development Program of China (2017YFA0205003)

Atomic-scale characterization of the atomic structure as well as molecular adsorption on an alloy surface plays a vital role in elucidating the catalytic mechanism of effective catalysts. Au-Cu alloy nanoparticles have important applications in catalyzing CO oxidation and CO₂ reduction. However, the atomic-scale properties of Au-Cu alloy surfaces are rarely investigated. In particular, the physical and chemical properties of singly-dispersed doping atoms, either Au in Cu or vice versa, as well as their influence on the overall surface properties, have not been studied in detail. In response, we first prepared low-coverage bimetallic Au/Cu(111) and Cu/Au(111) films, which were then annealed at high temperature to realize single atomically-dispersed Au/Cu(111) and Cu/Au(111) surface alloys (SA). We characterized the surface structures and adsorption properties by low-temperature scanning tunneling microscopy and spectroscopy (LT-STM/STS). For the SA-Au/Cu(111) system, we found that Au atoms can be incorporated in both the skin and subsurface layer of the Cu(111) substrate. These species can be readily distinguished from the topography contrast in STM. Moreover, STS measurements showed clear differences between the electronic states of doped Au atoms and the Cu host. In particular, we found that Au in the skin layer was strengthened while the subsurface Au showed weakened filled states at approximately −0.5 eV compared with the Cu(111) surface, which corresponds to the characteristic Shockley state of an Au surface. These altered electronic properties at the sites of doped atoms are also reflected by changes in the interactions with probe molecules. Adsorption experiments showed that Au atoms in the top surface prevented the binding of CO molecules, causing various adsorption vacancies in the CO adlayer. In contrast, the subsurface Au atoms had little influence on surface binding with CO molecules. For the SA-Cu/Au(111) system, we found that Cu atoms tend to aggregate into small clusters in the subsurface region of the Au(111) substrate. Only few Cu atoms can be stabilized at the elbow positions of the reconstructed top surface of Au(111). Adsorption experiments showed that only Cu atoms in the skin layer can adsorb CO molecules at liquid nitrogen temperature, while the subsurface Cu atoms cannot. On the other hand, the Au atoms around the doped Cu atoms do not seem to be influenced at all, possibly because of the weak effect of Cu. These experimental results provide details on the atomistic aspects of Au-Cu alloy surfaces, which can improve our understanding of the catalytic mechanism of Au-Cu alloy catalysts.
- Au/Cu(111),
- Single atom,
- Surface alloy,
- CO adsorption,
- Electronic property,
- Scanning tunneling microscopy
1. [1]
  Kim, D.; Resasco, J.; Yu, Y.; Asiri, A. M.; Yang, P. D. Nat. Commun. 2014, 5, 4948. doi: 10.1038/ncomms5948 doi: 10.1038/ncomms5948
2. [2]
  Liu, X. Y.; Wang, A. Q.; Zhang, T.; Su, D. S.; Mou, C. Y. Catal. Today 2011, 160, 103. doi: 10.1016/j.cattod.2010.05.019 doi: 10.1016/j.cattod.2010.05.019
3. [3]
  Haruta, M. Catal. Today 1997, 36, 153. doi: 10.1016/S0920-5861(96)00208-8 doi: 10.1016/S0920-5861(96)00208-8
4. [4]
  Thomas, J. M.; Saghi, Z.; Gai, P. L. Top. Catal. 2011, 54, 588. doi: 10.1007/s11244-011-9677-y doi: 10.1007/s11244-011-9677-y
5. [5]
  Qiao, B.; Wang, A.; Yang, X.; Allard, L. F.; Jiang, Z.; Cui, Y.; Liu, J.; Li, J.; Zhang, T. Nat. Chem. 2011, 3, 634. doi: 10.1038/nchem.1095 doi: 10.1038/nchem.1095
6. [6]
  Ranocchiari, M.; Lothschutz, C.; Grolimund, D.; van Bokhoven, J. A. Proc. Roy. Soc. A 2012, 468, 1985. doi: 10.1098/rspa.2012.0078 doi: 10.1098/rspa.2012.0078
7. [7]
  Flytzani-Stephanopoulos, M.; Gates, B. C. Annu. Rev. Chem. Biomol. 2012, 3, 545. doi: 10.1146/annurev-chembioeng-062011-080939 doi: 10.1146/annurev-chembioeng-062011-080939
8. [8]
  Chen, J. G.; Menning, C. A.; Zellner, M. B. Surf. Sci. Rep. 2008, 63, 201. doi: 10.1016/j.surfrep.2008.02.001 doi: 10.1016/j.surfrep.2008.02.001
9. [9]
  Greeley, J.; Mavrikakis, M. Nat. Mater. 2004, 3, 810. doi: 10.1038/nmat1223 doi: 10.1038/nmat1223
10. [10]
  Rodriguez, J. Surf. Sci. Rep. 1996, 24, 223. doi: 10.1016/0167-5729(96)00004-0 doi: 10.1016/0167-5729(96)00004-0
11. [11]
  Alexeev, O. S.; Gates, B. C. Ind. Eng. Chem. Res. 2003, 42, 1571. doi: 10.1021/ie020351h doi: 10.1021/ie020351h
12. [12]
  Ponec, V. Appl. Catal. A 2001, 222, 31. doi: 10.1016/S0926-860X(01)00828-6 doi: 10.1016/S0926-860X(01)00828-6
13. [13]
  Huang, L.; Shao, X. Acta Phys. -Chim. Sin. 2018, 34, 1390. doi: 10.3866/PKU.WHXB201804191
14. [14]
  Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. J. Catal. 1989, 115, 301. doi: 10.1016/0021-9517(89)90034-1 doi: 10.1016/0021-9517(89)90034-1
15. [15]
  Haruta, M.; Tsubota, S.; Kobayashi, T.; Kageyama, H.; Genet, M. J.; Delmon, B. J. Catal. 1993, 144, 175. doi: 10.1006/jcat.1993.1322 doi: 10.1006/jcat.1993.1322
16. [16]
  Haruta, M. Catal. Today 1997, 36, 153. doi: 10.1016/S0920-5861(96)00208-8 doi: 10.1016/S0920-5861(96)00208-8
17. [17]
  Grisel, R. J. H.; Kooyman, P. J.; Nieuwenhuys, B. E. J. Catal. 2000, 191, 430. doi: 10.1006/jcat.1999.2787 doi: 10.1006/jcat.1999.2787
18. [18]
  Linke, R.; Schneider, U.; Busse, H.; Becker, C.; Schröder, U.; Castro, G. R.; Wandelt, K. Surf. Sci. 1994, 307, 407. doi: 10.1016/0039-6028(94)90427-8 doi: 10.1016/0039-6028(94)90427-8
19. [19]
  Qi, Y.; Bian, T.; Choi, S. I.; Jiang, Y.; Jin, C.; Fu, M.; Zhang, H.; Yang, D. Chem. Commun. 2014, 50, 560. doi: 10.1039/c3cc48061e doi: 10.1039/c3cc48061e
20. [20]
  Liu, X.; Wang, A.; Wang, X.; Mou, C. Y.; Zhang, T. Chem. Commun. 2008, 3187. doi: 10.1039/b804362k doi: 10.1039/b804362k
21. [21]
  Liu, X.; Wang, A.; Li, L.; Zhang, T.; Mou, C. Y.; Lee, J. F. J. Catal. 2011, 278, 288. doi: 10.1016/j.jcat.2010.12.016 doi: 10.1016/j.jcat.2010.12.016
22. [22]
  Chimentão, R. J.; Medina, F.; Fierro, J. L. G.; Llorca, J.; Sueiras, J. E.; Cesteros, Y.; Salagre, P. J. Mater. Chem. A-Chem. 2007, 274, 159. doi: 10.1016/j.molcata.2007.05.008 doi: 10.1016/j.molcata.2007.05.008
23. [23]
  Della Pina, C.; Falletta, E.; Rossi, M. J. Catal. 2008, 260, 384. doi: 10.1016/j.jcat.2008.10.003 doi: 10.1016/j.jcat.2008.10.003
24. [24]
  Kyriakou, G.; Boucher, M. B.; Jewell, A. D.; Lewis, E. A.; Lawton, T. J.; Baber, A. E.; Tierney, H. L.; Stephanopoulos, M. F.; Sykes, E. C. H. Science 2012, 335, 1209. doi: 10.1126/science.1215864 doi: 10.1126/science.1215864
25. [25]
  Marcinkowski, M.; Jewell, A. D.; Stamatakis, M.; Boucher, M. B.; Lewis, E. A.; Murphy, C. J.; Kyriakou, G.; Sykes, E. C. H. Nat. Mater. 2013, 12, 523. doi: 10.1038/nmat3620 doi: 10.1038/nmat3620
26. [26]
  Baber, A. E.; Tierney, H. L.; Sykes, E. C. H. ACS Nano 2010, 4, 1637. doi: 10.1021/nn901390y doi: 10.1021/nn901390y
27. [27]
  Han, P.; Axnanda, S.; Lyubinetsky, I.; Goodman, D. W. J. Am. Chem. Soc. 2007, 129, 14355. doi: 10.1021/ja074891n doi: 10.1021/ja074891n
28. [28]
  Shi, H. X.; Wang, W. Y.; Li, Z.; Wang, L.; Shao, X. Chin. J. Chem. Phys. 2017, 30, 443. doi: 10.1063/1674-0068/30/cjcp1704078 doi: 10.1063/1674-0068/30/cjcp1704078
29. [29]
  Umezawa, K.; Nakanishi, S. Phys. Rev. B 2000, 63, 035402. doi: 10.1103/PhysRevB.63.035402 doi: 10.1103/PhysRevB.63.035402
30. [30]
  Wang, L.; Li, P.; Shi, H. X.; Li, Z. Y.; Wu, K.; Shao, X. J. Phys. Chem. C 2017, 121, 7977. doi: 10.1021/acs.jpcc.7b00938 doi: 10.1021/acs.jpcc.7b00938
31. [31]
  Zhao, X. Y.; Liu, P.; Hrbek, J.; Rodriguez, J. A.; Pérez, M. Surf. Sci. 2005, 592, 25. doi: 10.1016/j.susc.2005.06.035 doi: 10.1016/j.susc.2005.06.035
32. [32]
  Hwang, R. Q.; Schröder, J.; Günther, C.; Behm, R. J. Phys. Rev. Lett. 1991, 67, 3279. doi: 10.1103/PhysRevLett.67.3279 doi: 10.1103/PhysRevLett.67.3279
33. [33]
  Brune, H.; Röder, H.; Bromann, K.; Kern, K. Thin Solid Films 1995, 264, 230. doi: 10.1016/0040-6090(94)05821-0 doi: 10.1016/0040-6090(94)05821-0
34. [34]
  Wang, W.; Shi, H.; Wang, L.; Li, Z.; Shi, H.; Wu, K.; Shao, X. J. Phys. Chem. C 2018, 122, 19551. doi: 10.1021/acs.jpcc.8b04783 doi: 10.1021/acs.jpcc.8b04783
35. [35]
  Meunier, I.; Tréglia, G.; Gay, J. M.; Aufray, B. Phys. Rev. B 1999, 59, 10910. doi: 10.1103/PhysRevB.59.10910 doi: 10.1103/PhysRevB.59.10910
36. [36]
  Castro, G. R.; Doyen, G. Surf. Sci. 1994, 307, 384. doi: 10.1016/0039-6028(94)90423-5 doi: 10.1016/0039-6028(94)90423-5
37. [37]
  Castro, G. R.; Schneider, U.; Busse, H.; Janssens, T.; Wandelt, K. Surf. Sci. 1992, 269, 321. doi: 10.1016/0039-6028(92)91268-G doi: 10.1016/0039-6028(92)91268-G
38. [38]
  Besenbacher, F.; Chorkendorff, I.; Clausen, B. S.; Hammer, B.; Molenbroek, A. M.; Nørskov, J. K.; Stensgaard, I. Science 1998, 279, 1913. doi: 10.1126/science.279.5358.1913 doi: 10.1126/science.279.5358.1913
39. [39]
  Kim, M. J.; Na, H. J.; Lee, K. C.; Yoob, E. A.; Lee, M. Y. J. Mater. Chem. 2003, 13, 1789. doi: 10.1039/b304006m doi: 10.1039/b304006m
40. [40]
  Liu, M.; Zhou, W.; Wang, T.; Wang, D.; Liu, L.; Ye, J. Chem. Commun. 2016, 52, 4694. doi: 10.1039/c6cc00717a doi: 10.1039/c6cc00717a
41. [41]
  Kuhn, M.; Sham, T. K. Phys. Rev. B 1994, 49, 1647. doi: 10.1103/PhysRevB.49.1647 doi: 10.1103/PhysRevB.49.1647
42. [42]
  Hammer, B. J. K. N.; Nørskov, J. K. Surf. Sci. 1995, 343, 211. doi: 10.1016/0039-6028(96)80007-0 doi: 10.1016/0039-6028(96)80007-0
43. [43]
  Libisch, F.; Geringer, V.; Subramaniam, D.; Burgdörfer, J.; Morgenstern, M. Phys. Rev. B 2014, 90, 035442. doi: 10.1103/PhysRevB.90.035442 doi: 10.1103/PhysRevB.90.035442
44. [44]
  Chen, W.; Madhavan, V.; Jamneala, T.; Crommie, M. F. Phys. Rev. Lett. 1998, 80, 1469. doi: 10.1103/PhysRevLett.80.1469 doi: 10.1103/PhysRevLett.80.1469
45. [45]
  Bartels, L.; Meyer, G.; Rieder, K. H. Surf. Sci. 1999, 432, 621. doi: 10.1016/S0039-6028(99)00640-8 doi: 10.1016/S0039-6028(99)00640-8
46. [46]
  Heinrich, A. J.; Lutz, C. P.; Gupta, J. A.; Eigler, D. M. Science 2002, 298, 1381. doi: 10.1126/science.1076768 doi: 10.1126/science.1076768
47. [47]
  Neef, M.; Doll, K. Surf. Sci. 2006, 600, 1085. doi: 10.1016/j.susc.2005.12.036 doi: 10.1016/j.susc.2005.12.036
48. [48]
  Li, W.; Kong, L.; Feng, B.; Fu, H.; Li, H.; Zeng, X. C.; Wu, K.; Chen, L. Nat. Commun. 2018, 9, 198. doi: 10.1038/s41467-017-02634-6 doi: 10.1038/s41467-017-02634-6
49. [49]
  Hammer, B.; Morikawa, Y.; Nørskov, J. K. Phys. Rev. Lett. 1996, 76, 2141. doi: 10.1103/PhysRevLett.76.2141 doi: 10.1103/PhysRevLett.76.2141
50. [50]
  Mavrikakis, M.; Hammer, B.; Nørskov, J. K. Phys. Rev. Lett. 1998, 81, 2819. doi: 10.1103/PhysRevLett.81.2819 doi: 10.1103/PhysRevLett.81.2819
51. [51]
  Rodriguez, J. A.; Goodman, D. W. Science 1992, 257, 897. doi: 10.1126/science.257.5072.897 doi: 10.1126/science.257.5072.897
52. [52]
  Campbell, R. A.; Rodriguez, J. A.; Goodman, D. W. Surf. Sci. 1991, 256, 272. doi: 10.1016/0039-6028(91)90870-X doi: 10.1016/0039-6028(91)90870-X
53. [53]
  Rodriguez, J. A.; Goodman, D. W. J. Phys. Chem. 1991, 95, 4196. doi: 10.1021/j100164a008 doi: 10.1021/j100164a008
54. [54]
  Chen, M. S.; Goodman, D. W. Science 2004, 306, 252. doi: 10.1126/science.1102420 doi: 10.1126/science.1102420
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