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Motif-mediated Au_(25)(SPh)_5(PPh_3)_(10)X_2 nanorods with conjugated electron delocalization

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Zheng Kai 1,2   Zhang Jiangwei 1   Zhao Dan 3   Yang Yong 4   Li Zhimin 1,2   Li Gao 1 *  
文摘 We developed a general and effective strategy to afford rod-like [Au_(25)(SPh)_5(PPh_3)_(10)X_2]X_2 (X = Cl/Br) nanoclusters, capped by conjugated delocalized pπ electron mediated ligands. The detailed atomic structure of these materials was resolved by synchrotron radiation X-ray diffraction (SRXRD) combined with electrospray ionization mass spectrometry (ESI-MS) and UV-vis analyses. The Au_(17)(SR)_3(PPh_3)_6X_2 minimum asymmetric unit, with exposed Au atoms at the center, can serve as an important model to understand the transformation of homogold nanoclusters into alloy nanoclusters. The conjugated delocalized pπ electrons of the thiolate ligands can effectively tune the electronic properties of the Au_(25) kernel, as qualitatively evidenced by the energy gaps measured by UV-vis experiments and density functional theory (DFT) calculations. The delocalized electrons distinctly flow to the orbitals of the Au_(25) kernel via the S atoms of the aromatic thiolates. The ESI-MS analysis indicates that Au_3 clusters are formed during the etching reactions, which provide an opportunity to gain insight into the intriguing conversion pathway of the Au_n(PPh_3)_mX_y precursor to the final Au_(25) nanorods. Finally, the thiophenol-protected Au_(25) nanorods, immobilized on activated carbon, show good catalytic activity in the aerobic oxidation of glucose to gluconic acid (74% glucose conversion and 100% selectivity for gluconic acid), much higher than that of the aliphatic Au_(25) analogue. The Au_(25)(SPh)_5(PPh_3)_(10)X_2 catalyst yields a turnover frequency (TOF) of 13.5 s~(-1), higher than that of commercial catalysts such as Pd/activated carbon (AC) and Pd-Bi/AC. The insight obtained from this study will support the development and design of efficient nanogold catalysts for special oxidation reactions.
来源 Nano Research ,2019,12(3):501-507 【核心库】
DOI 10.1007/s12274-018-2147-0
关键词 gold clusters ; Au_(25) nanorod ; synchrotron radiation X-ray diffraction (SRXRD) ; aerobic oxidation Address
地址

1. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, State Key Laboratory of Catalysis, Dalian, 116023  

2. University of Chinese Academy of Sciences, Beijing, 100049  

3. Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang, 110034  

4. Department of Materials Science & Engineering, College of Engineering, Peking University, Beijing, 100871

语种 英文
文献类型 研究性论文
ISSN 1998-0124
学科 物理学
基金 support by the National Natural Science Foundation of China ;  Liaoning Natural Science Foundation ;  open project Foundation of State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University ;  Shanxi Province Hundred Talent Project ;  National Facility for Protein Science in Shanghai, Shanghai Synchrotron Radiation Facility for providing the beam time
文献收藏号 CSCD:6455321

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