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

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• 作者：Lingwen Liao ; Shiming Zhou ; Yafei Dai ; Liren Liu ; Chuanhao Yao ; Cenfeng Fu ; Jinlong Yang ; Zhikun Wu
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：August 5, 2015
• 年：2015
• 卷：137
• 期：30
• 页码：9511-9514
• 全文大小：397K
• ISSN：1520-5126

文摘

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.