Citation: HUANG Lili, SHAO Xiang. CO Induced Single and Multiple Au Adatoms Trapped by Melem Self-Assembly[J]. Acta Physico-Chimica Sinica, ;2018, 34(12): 1390-1396. doi: 10.3866/PKU.WHXB201804191 shu

CO Induced Single and Multiple Au Adatoms Trapped by Melem Self-Assembly

HUANG Lili ,
SHAO Xiang ^,

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: 2 April 2018
Revised Date: 16 April 2018
Accepted Date: 17 April 2018
Available Online: 23 December 2018
Fund Project: The project was supported by the National Natural Science Foundation of China (21333001, 91545128, 91227117), the Ministry of Science and Technology of China (2017YFA0205003), and the Thousand Talent Program for Young Outstanding Scientists of the Chinese Governmentthe National Natural Science Foundation of China 21333001the National Natural Science Foundation of China 91227117the National Natural Science Foundation of China 91545128the Ministry of Science and Technology of China 2017YFA0205003

The controllability of metal adatoms has been attracting ever-growing attention because the metal species in particular single-atom metals can play an important role in various surface processes, including heterogeneous catalytic reactions. On the other hand, organic self-assembly films have been regarded as an efficient and versatile bottom-up method to fabricate surface nanostructures, whose functionality and periodicity can be highly designable. In this work, we have developed a novel strategy to steer the generation and distribution of metal adatoms by combining the surface self-assemblies with exposure to small inorganic gaseous molecules. More specifically, we have prepared a honeycomb structure of melem (triamino-s-heptazine) on the Au(111) surface based on a well-structured hydrogen bonding network. The achieved melem self-assembly contains periodic hexagonal pores having diameters as large as around 1 nm. More importantly, the peripheries of the nanopores are decorated with heterocyclic N atoms that can probably form strong interactions with the metal species. Upon exposing the melem self-assembly to a CO atmosphere at room temperature, a fair number of Au adatoms were produced and trapped inside the nanopores encircled by the melem molecules. Single or clustered Au vacancies were concomitantly formed that were also trapped by the melem pores and stabilized by the surrounding molecules, as confirmed by high-resolution scanning tunneling microscopy (STM) images. Both types of added species showed positive correlations with the CO exposure and saturated at around 0.01 monolayer. In addition, owing to the large pore size, as well as the presence of multiple docking sites inside the nanopores, more than one Au adatom can reside in a melem nanopore; they can be distributed in a variety of configurations for bi-Au (two Au adatoms) and tri-Au (three Au adatoms) species, whose population can be manipulated with the CO exposure. Moreover, control experiments demonstrated that these CO-induced Au species, including the adatoms and vacancies, can survive annealing treatments up to the temperature at which the melem molecules start to desorb, indicating a substantial thermal stability. The formed Au species may hold great potential for serving as active sites for surface reactions. More interestingly, the bi-Au and tri-Au species have moderate Au-Au intervals, and can be potentially active for certain structurally sensitive bimolecular reactions. Considering all these aspects, we believe that this work presents a fresh approach to utilizing organic self-assembly films and has demonstrated a rather novel strategy for preparing various single-atom metal species on substrate surfaces.
- Au adatom,
- CO,
- Melem,
- Self-assembly,
- STM
1. [1]
  Yang, X. F.; Wang, A.; Qiao, B.; Li, J.; Liu, J.; Zhang, T. Acc. Chem. Res. 2013, 46, 1740. doi: 10.1021/ar300361m doi: 10.1021/ar300361m
2. [2]
  Pan, M.; Gong, J.; Dong, G.; Mullins, C. B. Acc. Chem. Res. 2014, 47, 750. doi: 10.1021/ar400172u doi: 10.1021/ar400172u
3. [3]
  Campbell, C. T. Annul. Rev. Phys. Chem. 1990, 41, 775. doi: 10.1146/annurev.pc.41. 100190.004015 doi: 10.1146/annurev.pc.41.100190.004015
4. [4]
  Herzing, A. A.; Kiely, C. J.; Carley, A. F.; Landon, P.; Hutchings, G. J. Science 2008, 321, 1331. doi: 10.1126/science.1159639 doi: 10.1126/science.1159639
5. [5]
  Hackett, S. F. J.; Brydson, R. M.; Gass, M. H.; Harvey, I.; Newman, A. D.; Wilson, K.; Lee, A. F. Angew. Chem. Int. Ed. 2007, 46, 8593. doi: 10.1002/anie.200790227 doi: 10.1002/anie.200790227
6. [6]
  Qiao, B.; Wang, A.; Yang, X.; Allard, L. F.; Zheng, J.; Cui, Y.; Liu, J.; Li, J.; Zhang, T. Nat. Chem. 2011, 3, 634. doi: 10.1038/nchem.1095 doi: 10.1038/nchem.1095
7. [7]
  Zhang, H.; Watanabe, T.; Okumura, M.; Haruta M.; Toshima, N. Nat. Mater. 2012, 11, 49. doi: 10.1038/nmat3143 doi: 10.1038/nmat3143
8. [8]
  Yang, B.; Pan, Y.; Lin, X.; Nilius, N.; Freund, H. J.; Hulot, C.; Graud, A.; Blechert, S.; Tosoni, S.; Sauer, J. J. Am. Chem. Soc. 2012, 134, 11161. doi: 10.1021/ja300304s doi: 10.1021/ja300304s
9. [9]
  Giesen, M. Prog. Surf. Sci. 2001, 68, 1. doi: 10.1016/S0079-6816(00)00021-6 doi: 10.1016/S0079-6816(00)00021-6
10. [10]
  Kern, K.; Niehus, H.; Schatz, A.; Zeppenfeld, P.; Goerge, J.; Comsa, G. Phys. Rev. Lett. 1991, 67, 855. doi: 10.1103/PhysRevLett.67.855 doi: 10.1103/PhysRevLett.67.855
11. [11]
  Carlisle, C. I.; Fujimoto, T.; Sim, W. S.; King, D. A. Surf. Sci. 2000, 470, 15. doi: 10.1016/S0039-6028(00)00831-1 doi: 10.1016/S0039-6028(00)00831-1
12. [12]
  Nakagoe, O.; Watanabe, K.; Takagi, N.; Matsumoto, Y. Phys. Rev. Lett. 2003, 90, 226105. doi: 10.1103/PhysRevLett.90.226105 doi: 10.1103/PhysRevLett.90.226105
13. [13]
  Wang, L.; Li, P.; Shi, H.; Li, Z.; Wu, K.; Shao, X. J. Phys. Chem. C 2017, 121, 7977. doi: 10.1021/acs.jpcc.7b00938 doi: 10.1021/acs.jpcc.7b00938
14. [14]
  Agrawal, P. M.; Rice, B. M.; Thompson, D. L. Surf. Sci. 2002, 515, 21. doi: 10.1016/S0039-6028(02)01916-7 doi: 10.1016/S0039-6028(02)01916-7
15. [15]
  Devyatko, Y. N.; Rogozhkin, S. V.; Fadeev, A. V. Phys. Rev. B 2001, 63, 193401. doi: 10.1103/PhysRevB.63.193401 doi: 10.1103/PhysRevB.63.193401
16. [16]
  Pawin, G.; Wong, K. L.; Kim, D.; Sun, D.; Bartels, L.; Hong, S.; Rahman, T. S.; Carp, C.; Marsella, M. A. Angew. Chem. Int. Ed. 2008, 47, 8442. doi: 10.1002/anie.200802543 doi: 10.1002/anie.200802543
17. [17]
  Dong, L.; Sun, Q.; Zhang, C.; Li, Z.; Sheng, K.; Kong, H.; Tan, Q.; Pan, Y.; Hu A.; Xu, W. Chem. Commun. 2013, 49, 1735. doi: 10.1039/C2CC37316E doi: 10.1039/C2CC37316E
18. [18]
  Rosei, F.; Schunack, M.; Jiang, P.; Gourdon, A.; Lægsgaard, E.; Stensgaard, I.; Joachim, C.; Besenbacher, F. Science 2002, 296, 328. doi: 10.1126/science.1069157 doi: 10.1126/science.1069157
19. [19]
  Shi, H.; Wang, W.; 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
20. [20]
  Kudernac, T.; Lei, S.; Elemans, J. A.; De Feyter, S. Chem. Soc. Rev. 2009, 38, 402. doi: 10.1039/b708902n doi: 10.1039/b708902n
21. [21]
  Liu, X. H.; Mo, Y. P.; Yue, J. Y.; Zheng, Q. N.; Yan, H. J.; Wang, D.; Wan, L. J. Small 2014, 10, 4934. doi: 10.1002/smll.201400899 doi: 10.1002/smll.201400899
22. [22]
  Niu, L.; Ma, X.; Liu, L.; Mao, X.; Wu, D.; Yang, Y.; Zeng, Q. D.; Wang, C. Phys. Chem. Chem. Phys. 2010, 12, 11683. doi: 10.1039/C0CP90090G doi: 10.1039/C0CP90090G
23. [23]
  Ciesielski, A.; Palma, C. A.; Bonini, M.; Samorì, P. Adv. Mater. 2010, 22, 3506. doi: 10.1002/adma.201001582 doi: 10.1002/adma.201001582
24. [24]
  Barth, J. V. Annul. Rev. Phys. Chem. 2007, 58, 375. doi: 10.1146/annurev.physchem.56. 092503.141259 doi: 10.1146/annurev.physchem.56.092503.141259
25. [25]
  Bonifazi, D.; Mohnani, S.; Llanes-Pallas, A. Chem. Eur. J. 2009, 15, 7004. doi: 10.1002/chem.200900900 doi: 10.1002/chem.200900900
26. [26]
  Stepanow, S.; Lingenfelder, M.; Dmitriev, A.; Spillmann, H.; Delvigne, E.; Lin, N.; Deng, X. B.; Cai, C. Z.; Barth, J. V.; Kern, K. Nat. Mater. 2004, 3, 229. doi: 10.1038/nmat1088 doi: 10.1038/nmat1088
27. [27]
  Iancu, V.; Braun, K. F.; Schouteden, K.; Van Haesendonck, C. Phys. Rev. Lett. 2014, 113, 106102. doi: 10.1103/PhysRevLett.113.106102 doi: 10.1103/PhysRevLett.113.106102
28. [28]
  Zhou, X.; Yang, W.; Chen, Q.; Geng, Z.; Shao, X.; Li, J.; Wang, Y.; Dai, D.; Chen, W; Xu, G.; Yang, X.; Wu, K. J. Phys. Chem. C 2016, 120, 1709. doi: 10.1021/acs.jpcc.5b11362 doi: 10.1021/acs.jpcc.5b11362
29. [29]
  Zhou, X.; Shen, Q.; Yuan, K.; Yang, W.; Chen, Q.; Geng, Z.; Zhang, J.; Shao, X.; Chen, W.; Xu, G.; Yang, X.; Wu, K. J. Am. Chem. Soc. 2018, 140, 554. doi: 10.1021/jacs.7b10394 doi: 10.1021/jacs.7b10394
30. [30]
  Brown, M. A.; Fujimori, Y.; Ringleb, F.; Shao, X.; Stavale, F.; Nilius, N.; Sterrer, M.; Freund, H. J. J. Am. Chem. Soc. 2011, 133, 10668. doi: 10.1021/ja204798z doi: 10.1021/ja204798z
31. [31]
  Yim, W. L.; Nowitzki, T.; Necke, M.; Schnars, H.; Nickut, A.; Shamery, K.; Klüner, T.; Bäumer, M. J. Phys. Chem. C 2007, 111, 445. doi: 10.1021/jp0665729 doi: 10.1021/jp0665729
32. [32]
  Eren, B.; Zherebetskyy, D.; Patera, L. L.; Wu, H. C.; Bluhm, H.; Africh, C.; Wang, L.; Somorjai, G. A.; Salmeron, M. Science 2016, 351, 4758. doi: 10.1126/science.aad8868 doi: 10.1126/science.aad8868
33. [33]
  Eren, B.; Liu, Z.; Stacchiola, D.; Somorjai, A. G.; Salmeron, M. J. Phys. Chem. C 2016, 120, 8227. doi: 10.1021/acs.jpcc.6b02143 doi: 10.1021/acs.jpcc.6b02143
34. [34]
  Wang, L.; Chen, Q.; Shi, H.; Liu, H.; Ren, X.; Wang, B.; Wu, K.; Shao, X. Phys. Chem. Chem. Phys. 2016, 18, 2324. doi: 10.1039/c5cp0 5976c doi: 10.1039/c5cp05976c
35. [35]
  Wang, L.; Shi, H. X.; Wang, W. Y.; Shi, H.; Shao, X. Acta Phys. -Chim. Sin. 2017, 33, 393. doi: 10.3866/PKU.WHXB201611033
36. [36]
  Eichhorn, J.; Lotsch, V. B.; Schnick, W.; Lackinger, H. M. Cryst. Eng. Commun. 2011, 13, 5559. doi: 10.1039/c1ce05342f doi: 10.1039/c1ce05342f
37. [37]
  Uemura, S.; Aono, M.; Sakata, K.; Komatsu, T.; Kunitake, M. J. Phys. Chem. C 2013, 117, 24815. doi: 10.1021/jp406810c doi: 10.1021/jp406810c
38. [38]
  Uemura, S.; Sakata, K.; Aono, M.; Nakamura, Y.; Kunitake, M. Front. Chem. Sci. Eng. 2016, 10, 294. doi: 10.1007/s11705-016-1564-4 doi: 10.1007/s11705-016-1564-4
39. [39]
  Bao, M.; Wei, X.; Cai, L.; Sun, Q.; Liu. Z.; Xu, W. Phys. Chem. Chem. Phys. 2017, 19, 18704. doi: 10.1039/C7CP03862C doi: 10.1039/C7CP03862C
40. [40]
  Chen, M.; Kumar, D.; Yi, C. W; Goodman W. D. Science 2015, 310, 291. doi: 10.1126/science.1115800 doi: 10.1126/science.1115800
41. [41]
  Greeley, J.; Mavrikakis, M. Nat. Mater. 2004, 3, 810. doi: 10.1038/nmat1223 doi: 10.1038/nmat1223
42. [42]
  Ma, Y.; Diemant, T.; Bansmann, J.; Behm, R. J. Phys. Chem. Chem. Phys. 2011, 13, 10741. doi: 10.1039/c1cp00009h doi: 10.1039/c1cp00009h
43. [43]
  Tao, F.; Dag, S.; Wang, L.; Liu, Z.; Butcher, D. R.; Bluhm, H.; Salmeron, M.; Somorjai, G. A. Science 2010, 327, 850. doi: 10.1126/science.1182122 doi: 10.1126/science.1182122
44. [44]
  Inukai, J.; Tryk, D. A.; Abe, T.; Wakisaka, M.; Uchida, H.; Watanabe, M. J. Am. Chem. Soc. 2013, 135, 1476. doi: 10.1021/ja309886p doi: 10.1021/ja309886p
45. [45]
  Toyoshima, R.; Yoshida, M.; Monya, Y.; Suzuki, K.; Amemiya, K.; Mase, K.; Simon Munc, B.; Kondoh, H. Phys. Chem. Chem. Phys. 2014, 16, 23564. doi: 10.1039/c4cp04318a doi: 10.1039/c4cp04318a
46. [46]
  Piccolo, L.; Loffreda, D.; Cadete Santos Aires, F. J.; Deranlot, C.; Jugnet, Y.; Sautet, P.; Bertolini, J. C. Surf. Sci. 2004, 566, 995. doi: 10.1016/j.susc.2004.06.042 doi: 10.1016/j.susc.2004.06.042
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