Thiolate-Protected Hollow Gold Nanospheres

Citation: XU Wenwu, GAO Yi. Thiolate-Protected Hollow Gold Nanospheres[J]. Acta Physico-Chimica Sinica, 2018, 34(7): 770-775. doi: 10.3866/PKU.WHXB201711061 shu

巯基保护的中空金纳米球

许文武 ,
高嶷 ^,

.
中国科学院上海应用物理研究所水科学与技术研究室，微观界面物理与探测重点实验室，上海 201800

通讯作者: 高嶷, gaoyi@sinap.ac.cn

基金项目:
国家自然科学基金 21773287

国家自然科学基金 11504396

国家自然科学基金(11504396, 21773287)资助项目

摘要: 基于全统一模型和密度泛函理论(DFT)计算，我们提出了具有高对称性和稳定性的巯基保护的中空金纳米球Au₆₀(SR)₂₀的原子结构。Au₆₀(SR)₂₀由一个二十面体Au₅₀富勒烯中空笼子(由20个四面体Au₄融合构成)和10个[―RS―Au―SR―]订书针结构组成，并遵循“分离和保护”规则。DFT计算表明，这种空心Au₆₀(SR)₂₀纳米球具有大的带隙(1.3 eV)以及在笼中心的核独立化学位移(NICS)为负值(−5)，表明其高度的化学稳定性。此外，四面体Au₄单元中心的NICS值远大于空心笼中心的NICS值，表明Au₆₀(SR)₂₀的总体稳定性可能来自每个四面体Au₄单元的局部稳定性。正的谐波振动频率说明Au₆₀(SR)₂₀纳米球至少是势能表面的局部最小值。另外，我们还通过融合四面体Au₄层设计了双层中空金纳米球，表明调整中空金纳米球壳层厚度是可行的。最后，我们还介绍了更大的中空金纳米球Au₁₈₀(SR)₆₀的设计。这项工作提供了可控设计中空金纳米球的新策略。

关键词:

English

Thiolate-Protected Hollow Gold Nanospheres

XU Wenwu ,
GAO Yi ^,

Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, P. R. China

Corresponding author: GAO Yi, gaoyi@sinap.ac.cn

Received Date: 11 October 2017
Accepted Date: 02 November 2017
Revised Date: 01 November 2017
Available Online: 15 July 2018
Fund Project:

The project was supported by the National Natural Science Foundation of China (11504396, 21773287)

Abstract: We present the atomic structure of thiolate-protected hollow Au nanosphere (HAuNS), Au₆₀(SR)₂₀, with high symmetry and stability based on the grand unified model (GUM; Nat. Commun. 2016, 7, 13574) and density-functional theory (DFT) calculations. Using C₂₀ fullerene (with I_h symmetry) as a template, 20 tetrahedral Au₄ units were used to replace the C atoms of C₂₀, and three Au atoms of each Au₄ were fused with three neighboring Au₄ units by sharing one Au atom to form an icosahedral Au₅₀ fullerene cage as the inner core. Subsequently, the unfused Au atom in each Au₄ was bonded with the [―RS―Au―SR―] staple to form the completely hollow Au₆₀(SR)₂₀ nanosphere. Therefore, the Au₆₀(SR)₂₀ is composed of an icosahedral Au₅₀ fullerene hollow cage (constructed by fusing 20 tetrahedral Au₄ units) with 10 [―RS―Au―SR―] staples, obeying the "divide and protect" rule. Each Au₄ unit has 2e valence electrons, namely, the tetrahedral Au₄(2e) elementary block in the grand unified model. The DFT calculations showed that this hollow Au₆₀(SR)₂₀ nanosphere had a large HOMO–LUMO (HOMO: the highest occupied molecular orbital; LUMO: the lowest unoccupied molecular orbital) gap (1.3 eV) and a negative nucleus-independent chemical shift (NICS) value (−5) at the center of the hollow cage, indicating its high chemical stability. Furthermore, the NICS values in the center of the tetrahedral Au₄ units were much more negative than that in the center of the hollow cage, revealing that the overall stability of Au₆₀(SR)₂₀ likely stemmed from the local stability of each tetrahedral Au₄ unit. The harmonic vibrational frequencies were all positive, suggesting that the HAuNS corresponded to the local minimum of the potential energy surface. In addition, the bilayer HAuNS was designed by fusing the tetrahedral Au₄ layers, indicating the feasibility of tuning the thickness of the shell of HAuNS. In bilayer HAuNS, each tetrahedral Au₄ unit in the first layer shared four Au atoms, while those in the second layer shared one Au atom. The other three Au atoms of each tetrahedral unit bonded with the SR groups, demonstrating that each tetrahedral Au₄ unit has 2e valence electrons (namely the tetrahedral Au₄(2e) elementary block in GUM). The HOMO-LUMO gap of the bilayer Au₁₄₀(SH)₆₀ nanosphere is 1.5 eV, indicating its chemical stability. The thicknesses of the shells in monolayer and bilayer HAuNS are about 0.2 and 0.4 nm, respectively. This process could be easily understood in terms of the local stabilities of the tetrahedral Au₄(2e) elementary block in GUM. Finally, the design of larger HAuNS, Au₁₈₀(SR)₆₀, has also been presented. The HOMO-LUMO gap of Au₁₈₀(SH)₆₀ was 0.9 eV, which showed that it was also a stable HAuNS. This work provides a new strategy to controllably design the HAuNS.

Key words:

1. [1]
  Skrabalak, S. E.; Chen, J.; Sun, Y.; Lu, X.; Au, L.; Cobley, C. M.; Xia, Y. Acc. Chem. Res. 2008, 41, 1587. doi: 10.1021/ar800018v
2. [2]
  Dreaden, E. C.; Mackey, M. A.; Huang, X.; Kangy, B.; El-Sayed, M. A. Chem. Soc. Rev. 2010, 40, 3391. doi: 10.1039/C0CS00180E
3. [3]
  Kennedy, L. C.; Bickford, L. R.; Lewinski, N. A.; Coughlin, A. J.; Hu, Y.; Day, E. S.; West, J. L.; Drezek, R. A. Small 2011, 7, 169. doi: 10.1002/smll.201000134
4. [4]
  Melancon, M. P.; Zhou, M.; Li, C. Acc. Chem. Res. 2011, 44, 947. doi: 10.1021/ar200022e
5. [5]
  Dreaden, E. C.; Alkilany, A. M.; Huang, X.; Murphy, C. J.; El-Sayed, M. A. Chem. Soc. Rev. 2012, 41, 2740. doi: 10.1021/ar200022e
6. [6]
  Doane, T. L.; Burda, C. Chem. Soc. Rev. 20] 41, 2885. doi: 10.1039/C2CS15260F
7. [7]
  Johansson, M. P.; Sundholm, D.; Vaara, J. Angew. Chem. Int. Ed. 2004, 43, 2678. doi: 10.1039/C2CS15260F
8. [8]
  Gao, Y.; Zeng, X. C. J. Am. Chem. Soc. 2005, 127, 3698. doi: 10.1021/ja050435s
9. [9]
  Bulusu, S.; Li, X.; Wang, L. S.; Zeng, X. C. Proc. Natl. Acad. Sci. USA 2006, 103, 8326. doi: 10.1021/ja050435s
10. [10]
  Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.; Kornberg, R. D. Science 2007, 318, 430. doi: 10.1126/science.1148624
11. [11]
  Das, A.; Liu, C.; Byun, H. Y.; Nobusada, K.; Zhao, S.; Rosi, N. L.; Jin, R. Angew. Chem. Int. Ed. 2015, 54, 3140. doi: 10.1002/ange.201410161
12. [12]
  Chen, S.; Wang, S.; Zhong, J.; Song, Y.; Zhang, J.; Sheng, H.; Pei, Y.; Zhu, M. Angew. Chem. Int. Ed. 2015, 54, 3145. doi: 10.1002/anie.201410295
13. [13]
  Zeng, C.; Liu, C.; Chen, Y.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2014, 136, 11922. doi: 10.1021/ja506802n
14. [14]
  Das, A.; Li, T.; Nobusada, K.; Zeng, C.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2013, 135, 18264. doi: 10.1021/ja409177s
15. [15]
  Crasto, D.; Barcaro, G.; Stener, M.; Sementa, L.; Fortunelli, A.; Dass, A. J. Am. Chem. Soc. 2014, 136, 14933. doi: 10.1021/ja507738e
16. [16]
  Das, A.; Li, T.; Li, G.; Nobusada, K.; Zeng, C.; Rosi, N. L.; Jin, R. Nanoscale 2014, 6, 6458. doi: 10.1039/C4NR01350F
17. [17]
  Zhu, M.; Aikens, C. M.; Hollander, F. J.; Schatz, G. C.; Jin, R. J. Am. Chem. Soc. 2008, 130, 5883. doi: 10.1021/ja801173r
18. [18]
  Heaven, M. W.; Dass, A.; White, P. S.; Holt, K. M.; Murray, R. W. J. Am. Chem. Soc. 2008, 130, 3754. doi: 10.1021/ja800561b
19. [19]
  Zeng, C.; Li, T.; Das, A.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2013, 135, 10011. doi: 10.1021/ja404058q
20. [20]
  Chen, Y.; Liu, C.; Tang, Q.; Zeng, C.; Higaki, T.; Das, A.; Jiang, D.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2016, 138, 1482. doi: 10.1021/ja404058q
21. [21]
  Crasto, D.; Malola, S.; Brosofsky, G.; Dass, A.; Häkkinen, H. J. Am. Chem. Soc. 2014, 136, 5000. doi: 10.1021/ja412141j
22. [22]
  Zeng, C.; Qian, H.; Li, T.; Li, G.; Rosi, N. L.; Yoon, B.; Barnett, R. N.; Whetten, R. L.; Landman, U.; Jin, R. Angew. Chem. Int. Ed. 2012, 51, 13114. doi: 10.1002/ange.201207098
23. [23]
  Qian, H.; Eckenhoff, W. T.; Zhu, Y.; Pintauer, T.; Jin, R. J. Am. Chem. Soc. 2010, 132, 8280. doi: 10.1002/ange.201207098
24. [24]
  Tian, S.; Li, Y.; Li, M.; Yuan, J.; Yang, J.; Wu, Z.; Jin, R. Nat. Commun. 2015, 6, 8667. doi: 10.1038/ncomms9667
25. [25]
  Zeng, C.; Chen, Y.; Liu, C.; Nobusada, K.; Rosi, N. L.; Jin, R. Sci. Adv. 2015, 1, e1500425. doi: 10.1126/sciadv.1500425
26. [26]
  Chen, Y.; Zeng, C.; Liu, C.; Kirschbaum, K.; Gayathri, C.; Gil, R. R.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2015, 137, 10076. doi: 10.1021/jacs.5b05378
27. [27]
  Dass, A.; Theivendran, S.; Nimmala, P. R.; Kumara, C.; Jupally, V. R.; Fortunelli, A.; Sementa, L.; Barcaro, G.; Zuo, X.; Noll, B. C. J. Am. Chem. Soc. 2015, 137, 4610. doi: 10.1021/ja513152h
28. [28]
  Zeng, C.; Chen, Y.; Kirschbaum, K.; Appavoo, K.; Sfeir, M. Y.; Jin, R. Sci. Adv. 2015, 1, e1500045. doi: 10.1126/sciadv.1500045
29. [29]
  Zeng, C.; Chen, Y.; Kirschbaum, K.; Lambright, K.; Jin, R. Science 2016, 354, 1580. doi: 10.1126/science.aak9750
30. [30]
  Häkkinen, H.; Walter, M.; Gronbeck, H. J. Phys. Chem. B 2006, 110, 9927. doi: 10.1021/jp0619787
31. [31]
  Häkkinen, H. Nat. Chem. 2012, 4, 443. doi: 10.1021/jp0619787
32. [32]
  Pei, Y.; Zeng, X. C. Nanoscale 2012, 4, 4054. doi: 10.1039/C2NR30685A
33. [33]
  Jin, R. Nanoscale 2015, 7, 1549. doi: 10.1039/C4NR05794E
34. [34]
  Liu, C.; Pei, Y.; Sun, H.; Ma, J. J. Am. Chem. Soc. 2015, 137, 15809. doi: 10.1021/jacs.5b09466
35. [35]
  Jiang, D.; Overbury, S. H.; Dai, S. J. Am. Chem. Soc. 2013, 135, 8786. doi: 10.1021/ja402680c
36. [36]
  Pei, Y.; Gao, Y.; Shao, N.; Zeng, X. C. J. Am. Chem. Soc. 2009, 131, 13619. doi: 10.1021/ja905359b
37. [37]
  Pei, Y.; Tang, J.; Tang, X.; Huang, Y.; Zeng, X. C. J. Phys. Chem. Lett. 2015, 6, 1390. doi: 10.1021/acs.jpclett.5b00364
38. [38]
  Pei, Y.; Pal, R.; Liu, C.; Gao, Y.; Zhang, Z.; Zeng, X. C. J. Am. Chem. Soc. 2012, 134, 3015. doi: 10.1021/ja208559y
39. [39]
  Akola, J.; Walter, M.; Whetten, R. L.; Häkkinen, H.; Grönbeck, H. J. Am. Chem. Soc. 2008, 130, 3756. doi: 10.1021/ja800594p
40. [40]
  Pei, Y.; Gao, Y.; Zeng, X. C. J. Am. Chem. Soc. 2008, 130, 7830. doi: 10.1021/ja802975b
41. [41]
  Malola, S.; Lehtovaara, L.; Knoppe, S.; Hu, K.; Palmer, R. E.; Bürgi, T.; Häkkinen, H. J. Am. Chem. Soc. 2012, 134, 19560. doi: 10.1021/ja309619n
42. [42]
  Pei, Y.; Lin, S. S.; Su, J.; Liu, C. J. Am. Chem. Soc. 2013, 135, 19060. doi: 10.1021/ja409788k
43. [43]
  Xu, W. W.; Gao, Y.; Zeng, X. C. Sci. Adv. 2015, 1, e1400211. doi: 10.1126/sciadv.1400211
44. [44]
  周洋, 李志敏, 郑凯, 李杲.物理化学学报, 2018, 34(7), 786. doi: 10.3866/PKU.WHXB201709292Zhou, Y.; Li, Z. M.; Zheng, K.; Li, G. Acta Phys. -Chim. Sin. 2018, 34(7), 786. doi: 10.3866/PKU.WHXB201709292
45. [45]
  祝敏, 李漫波, 姚传好, 夏楠, 赵燕, 闫楠, 廖玲文, 伍志鲲.物理化学学报, 2018, 34(7), 792. doi: 10.3866/PKU.WHXB201710091Zhu, M.; Li, M. B.; Yao, C. H.; Xia, N.; Zhao, Y.; Yan, N.; Liao, L. W.; Wu, Z. Acta Phys. -Chim. Sin. 2018, 34(7), 792. doi: 10.3866/PKU.WHXB201710091
46. [46]
  孙国栋, 康熙, 金山, 李小武, 胡大乔, 汪恕欣, 朱满洲.物理化学学报, 2018, 34(7), 799. doi: 10.3866/PKU.WHXB201710124Sun, G. D.; Kang, X.; Jin, S.; Li, X. W.; Hu, D. Q.; Wang, S. X.; Zhu, M. Z. Acta Phys. -Chim. Sin. 2018, 34(7), 799. doi: 10.3866/PKU.WHXB201710124
47. [47]
  Tominaga, C.; Hikosou, D.; Osaka, I.; Kawasak, H. Acta Phys. -Chim. Sin. 2018, 34(7), 805. doi: 10.3866/PKU.WHXB201710271
48. [48]
  刘鸣华.物理化学学报, 2018, 34(6), 553. doi: 10.3866/PKU.WHXB201710301Liu, M. H. Acta Phys. -Chim. Sin. 2018, 34(6), 553. doi: 10.3866/PKU.WHXB201710301
49. [49]
  Xu, W. W.; Zhu, B.; Zeng, X. C.; Gao, Y. Nat. Commun. 2016, 7, 13574. doi: 10.1038/ncomms13574
50. [50]
  Xu, W. W.; Zeng, X. C.; Gao, Y. Chem. Phys. Lett. 2017, 675, 35. doi: 10.1016/j.cplett.2017.03.001
51. [51]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; et al. Gaussian 09, revision A.02; Gaussian, Inc.: Wallingford, CT, 2009.
52. [52]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865
53. [53]
  Lee, C.; Yang, W.; Parr, R. G. Phys. Re v. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
54. [54]
  Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270. doi: 10.1063/1.448799
55. [55]
  Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284. doi: 10.1063/1.448800
56. [56]
  Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299. doi: 10.1063/1.448975
57. [57]
  Von Ragué Schleyer, P.; Maerker, C.; Dransfeld, A.; Jiao, H.; van Eikema Hommes, N. J. R. J. Am. Chem. Soc. 1996, 118, 6317. doi: 10.1021/ja960582d
58. [58]
  Cheng, L.; Yuan, Y.; Zhang, X.; Yang, J. Angew. Chem. Int. Ed. 2013, 52, 9035. doi: 10.1002/anie.201302926
59. [59]
  Xu, W. W.; Li, Y.; Gao, Y.; Zeng, X. C. Nanoscale 2016, 8, 7396. doi: 10.1039/C6NR00272B
60. [60]
  Delley, B. J. Chem. Phys. 1990, 92, 508. doi: 10.1063/1.458452
61. [61]
  Delley, B. J. Chem. Phys. 2003, 113, 7756. doi: 10.1063/1.1316015

扫一扫看文章

计量

PDF下载量: 6
文章访问数: 1611
HTML全文浏览量: 254

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

巯基保护的中空金纳米球

通讯作者: 高嶷, gaoyi@sinap.ac.cn

English

Thiolate-Protected Hollow Gold Nanospheres

Corresponding author: GAO Yi, gaoyi@sinap.ac.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

巯基保护的中空金纳米球

通讯作者: 高嶷, gaoyi@sinap.ac.cn

English

Thiolate-Protected Hollow Gold Nanospheres

Corresponding author: GAO Yi, gaoyi@sinap.ac.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs