Medium-sized Au40(SR)24 and Au52(SR)32 nanoclusters with distinct gold-kernel structures and spectroscopic features

Wen Wu Xu; Yadong Li; Yi Gao; Xiao Cheng Zeng

doi:10.1039/C5NR07810E

Medium-sized Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ nanoclusters with distinct gold-kernel structures and spectroscopic features†

Wen Wu Xu,^a Yadong Li,^ab Yi Gao

*^acd and Xiao Cheng Zeng*^de

Author affiliations

* Corresponding authors

^a Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China
E-mail: gaoyi@sinap.ac.cn

^b University of Chinese Academy of Sciences, Beijing 100049, China

^c Shanghai Science Research Center, Chinese Academy of Sciences, Shanghai 201204, China

^d Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE 68588, USA
E-mail: xzeng1@unl.edu

^e Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China, Hefei, Anhui 230026, China

Abstract

We have analyzed the structures of two medium-sized thiolate-protected gold nanoparticles (RS-AuNPs) Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ and identified the distinct structural features in their Au kernels [Sci. Adv., 2015, 1, e1500425]. We find that both Au kernels of the Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ nanoclusters can be classified as interpenetrating cuboctahedra. Simulated X-ray diffraction patterns of the RS-AuNPs with the cuboctahedral kernel are collected and then compared with the X-ray diffraction patterns of the RS-AuNPs of two other prevailing Au-kernels identified from previous experiments, namely the Ino-decahedral kernel and icosahedral kernel. The distinct X-ray diffraction patterns of RS-AuNPs with the three different types of Au-kernels can be utilized as signature features for future studies of structures of RS-AuNPs. Moreover, the simulated UV/Vis absorption spectra and Kohn–Sham orbital energy-level diagrams are obtained for the Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂, on the basis of time-dependent density functional theory computation. The extrapolated optical band-edges of Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ are 1.1 eV and 1.25 eV, respectively. The feature peaks in the UV/Vis absorption spectra of the two clusters can be attributed to the d → sp electronic transition. Lastly, the catalytic activities of the Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ are examined using CO oxidation as a probe. Both medium-sized thiolate-protected gold clusters can serve as effective stand-alone nanocatalysts.

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Article information

DOI: https://doi.org/10.1039/C5NR07810E
Article type: Communication
Submitted: 07 Nov 2015
Accepted: 08 Dec 2015
First published: 09 Dec 2015
This article is Open Access

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Nanoscale, 2016,8, 1299-1304

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Medium-sized Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ nanoclusters with distinct gold-kernel structures and spectroscopic features

W. W. Xu, Y. Li, Y. Gao and X. C. Zeng, Nanoscale, 2016, 8, 1299 DOI: 10.1039/C5NR07810E

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