Gan Zibao, Chen Jishi, Liao Lingwen, Zhang Hongwen, Wu Zhikun
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences , Hefei, 230031, China.
J Phys Chem Lett. 2018 Jan 4;9(1):204-208. doi: 10.1021/acs.jpclett.7b02982. Epub 2017 Dec 26.
Surface single-atom tailoring of a gold nanoparticle, that is, adding, removing, or replacing one surface atom on a structure-resolved nanoparticle in a controlled manner, is very exciting yet challenging and has not been hitherto achieved. Herein we report the first realization of the introduction of a single sulfur atom onto the surface of the structure-unraveled AuS(SCHPh) nanoparticle. Single-crystal X-ray crystallography reveals that the as-obtained nanoparticle consists of one Au kernel protected by one AuS(SCHPh) and one unprecedented AuS(SCHPh) motif with the introduced sulfur atom included as a tetrahedral-coordinated μ-S. The introduced sulfur leads to the changes of both internal structure and crystallographic arrangement. Unlike the case of 6HLH arrangement in AuS(SCHPh) crystals, the "ABAB" arrangement in AuS(SCHPh) crystals enhances the solid photoluminescence of amorphous AuS(SCHPh) and brings a slight redshift of the maximum emission. The extensive near-infrared emission provides AuS(SCHPh) potential applications in some fields such as anticounterfeiting, imaging, etc.
金纳米颗粒的表面单原子剪裁，即通过可控方式在结构解析的纳米颗粒上添加、移除或替换一个表面原子，这一过程极具吸引力，但也充满挑战，且迄今为止尚未实现。在此，我们报道了首次在结构未解析的AuS(SCHPh)纳米颗粒表面引入单个硫原子。单晶X射线晶体学表明，所得到的纳米颗粒由一个被一个AuS(SCHPh)保护的金核以及一个前所未有的AuS(SCHPh)基序组成，其中引入的硫原子作为四面体配位的μ-S包含在内。引入的硫导致了内部结构和晶体学排列的变化。与AuS(SCHPh)晶体中的6HLH排列不同，AuS(SCHPh)晶体中的“ABAB”排列增强了非晶态AuS(SCHPh)的固体光致发光，并使最大发射略有红移。广泛的近红外发射为AuS(SCHPh)在防伪、成像等一些领域提供了潜在应用。
