Mono-Mercury Doping of Au25 and the HOMO/LUMO Energies Evaluation Employing Differential Pulse Voltammetry

Lingwen Liao; Shiming Zhou; Yafei Dai; Liren Liu; Chuanhao Yao; Cenfeng Fu; Jinlong Yang; Zhikun Wu

doi:10.1021/jacs.5b03483

Mono-Mercury Doping of Au25 and the HOMO/LUMO Energies Evaluation Employing Differential Pulse Voltammetry

J Am Chem Soc. 2015 Aug 5;137(30):9511-4. doi: 10.1021/jacs.5b03483. Epub 2015 Jul 27.

Authors

Lingwen Liao¹, Shiming Zhou², Yafei Dai², Liren Liu², Chuanhao Yao¹, Cenfeng Fu², Jinlong Yang², Zhikun Wu¹

Affiliations

¹ †Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences (CAS), Hefei, 230031, China.
² ‡Hefei National Laboratory for Physics Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.

PMID: 26196263
DOI: 10.1021/jacs.5b03483

Abstract

Controlling the bimetal nanoparticle with atomic monodispersity is still challenging. Herein, a monodisperse bimetal nanoparticle is synthesized in 25% yield (on gold atom basis) by an unusual replacement method. The formula of the nanoparticle is determined to be Au24Hg1(PET)18 (PET: phenylethanethiolate) by high-resolution ESI-MS spectrometry in conjunction with multiple analyses including X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). X-ray single-crystal diffraction reveals that the structure of Au24Hg1(PET)18 remains the structural framework of Au25(PET)18 with one of the outer-shell gold atoms replaced by one Hg atom, which is further supported by theoretical calculations and experimental results as well. Importantly, differential pulse voltammetry (DPV) is first employed to estimate the highest occupied molecular orbit (HOMO) and the lowest unoccupied molecular orbit (LUMO) energies of Au24Hg1(PET)18 based on previous calculations.