Thiolate-Protected Hollow Gold Nanospheres
文献类型：期刊论文
| 作者 | Xu, WW; Gao, Y |
| 刊名 | ACTA PHYSICO-CHIMICA SINICA
 |
| 出版日期 | 2018 |
| 卷号 | 34期号:7页码:770-775 |
| 关键词 | Effective Core Potentials X-ray Crystallography Crystal-structure Optical-properties Molecular Calculations Theoretical-analysis Electronic-properties Structural Evolution Nanoparticles Nanoclusters |
| ISSN号 | 1000-6818 |
| DOI | 10.3866/PKU.WHXB201711061 |
| 文献子类 | 期刊论文 |
| 英文摘要 | We present the atomic structure of thiolate-protected hollow Au nanosphere (HAuNS), Au-60(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 C-20 fullerene (with I-h symmetry) as a template, 20 tetrahedral Au-4 units were used to replace the C atoms of C-20, and three Au atoms of each Au-4 were fused with three neighboring Au-4 units by sharing one Au atom to form an icosahedral Au-50 fullerene cage as the inner core. Subsequently, the unfused Au atom in each Au-4 was bonded with the [-RS-Au-SR-] staple to form the completely hollow Au-60(SR)(20) nanosphere. Therefore, the Au-60(SR)(20) is composed of an icosahedral Au-50 fullerene hollow cage (constructed by fusing 20 tetrahedral Au-4 units) with 10 [-RS-Au-SR-] staples, obeying the "divide and protect" rule. Each Au-4 unit has 2e valence electrons, namely, the tetrahedral Au-4(2e) elementary block in the grand unified model. The DFT calculations showed that this hollow Au-60(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 Au-4 units were much more negative than that in the center of the hollow cage, revealing that the overall stability of Au-60(SR)(20) likely stemmed from the local stability of each tetrahedral Au-4 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 Au-4 layers, indicating the feasibility of tuning the thickness of the shell of HAuNS. In bilayer HAuNS, each tetrahedral Au-4 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 Au-4 unit has 2e valence electrons (namely the tetrahedral Au-4(2e) elementary block in GUM). The HOMO-LUMO gap of the bilayer Au-140(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 Au-4(2e) elementary block in GUM. Finally, the design of larger HAuNS, Au-180(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. |
| 语种 | 英语 |
| WOS记录号 | WOS:000429142800008 |
| 源URL | [http://ir.sinap.ac.cn/handle/331007/29189]  |
| 专题 | 上海应用物理研究所_中科院上海应用物理研究所2011-2017年 |
| 作者单位 | 1.Xu, WW 2.Gao, Y |
| 推荐引用方式 GB/T 7714 | Xu, WW,Gao, Y. Thiolate-Protected Hollow Gold Nanospheres[J]. ACTA PHYSICO-CHIMICA SINICA,2018,34(7):770-775. |
| APA | Xu, WW,&Gao, Y.(2018).Thiolate-Protected Hollow Gold Nanospheres.ACTA PHYSICO-CHIMICA SINICA,34(7),770-775. |
| MLA | Xu, WW,et al."Thiolate-Protected Hollow Gold Nanospheres".ACTA PHYSICO-CHIMICA SINICA 34.7(2018):770-775. |
入库方式： OAI收割
来源：上海应用物理研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。