CAS OpenIR  > 中科院上海应用物理研究所2011-2020年
Thiolate-Protected Hollow Gold Nanospheres
Xu, WW; Gao, Y
AbstractWe 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.
KeywordEffective Core Potentials X-ray Crystallography Crystal-structure Optical-properties Molecular Calculations Theoretical-analysis Electronic-properties Structural Evolution Nanoparticles Nanoclusters
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WOS IDWOS:000429142800008
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Document Type期刊论文
Affiliation1.Xu, WW
2.Gao, Y
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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.
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