Tailoring the Electronic and Catalytic Properties of Au25 Nanoclusters via Ligand Engineering

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• 作者：Gao Li ; Hadi Abroshan ; Chong Liu ; Shuo Zhuo ; Zhimin Li ; Yan Xie ; Hyung J. Kim ; Nathaniel L. Rosi ; Rongchao Jin
• 刊名：ACS Nano
• 出版年：2016
• 出版时间：August 23, 2016
• 年：2016
• 卷：10
• 期：8
• 页码：7998-8005
• 全文大小：369K
• 年卷期：0
• ISSN：1936-086X

文摘

To explore the electronic and catalytic properties of nanoclusters, here we report an aromatic-thiolate-protected gold nanocluster, [Au₂₅(SNap)₁₈]⁻ [TOA]⁺, where SNap = 1-naphthalenethiolate and TOA = tetraoctylammonium. It exhibits distinct differences in electronic and catalytic properties in comparison with the previously reported [Au₂₅(SCH₂CH₂Ph)₁₈]⁻, albeit their skeletons (i.e., Au₂₅S₁₈ framework) are similar. A red shift by ∼10 nm in the HOMO–LUMO electronic absorption peak wavelength is observed for the aromatic-thiolate-protected nanocluster, which is attributed to its dilated Au₁₃ kernel. The unsupported [Au₂₅(SNap)₁₈]⁻ nanoclusters show high thermal and antioxidation stabilities (e.g., at 80 °C in the present of O₂, excess H₂O₂, or TBHP) due to the effects of aromatic ligands on stabilization of the nanocluster’s frontier orbitals (HOMO and LUMO). Furthermore, the catalytic activity of the supported Au₂₅(SR)₁₈/CeO₂ (R = Nap, Ph, CH₂CH₂Ph, and n-C₆H₁₃) is examined in the Ullmann heterocoupling reaction between 4-methyl-iodobenzene and 4-nitro-iodobenzene. Results show that the activity and selectivity of the catalysts are largely influenced by the chemical nature of the protecting thiolate ligands. This study highlights that the aromatic ligands not only lead to a higher conversion in catalytic reaction but also markedly increase the yield of the heterocoupling product (4-methyl-4′-nitro-1,1′-biphenyl). Through a combined approach of experiment and theory, this study sheds light on the structure–activity relationships of the Au₂₅ nanoclusters and also offers guidelines for tailoring nanocluster properties by ligand engineering for specific applications.