Research Article

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2018, 11(4): 2139–2148

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https://doi.org/10.1007/s12274-017-1831-9

Transition metal-mediated catalytic properties of gold nanoclusters in aerobic alcohol oxidation

Chaolei Zhang1,2, Yongdong Chen1 (*), Hong Wang1, Zhimin Li2, Kai Zheng2, Shujun Li1, and gao Li2 (*)

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1 College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
2 Gold Catalysis Research Center, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Keywords: gold nanoclusters, heteroatom dopant, transition metal, oxidation, alcohol
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ABSTRACT Heteroatom dopants can greatly modify the electronic and physical properties and catalytic performance of gold nanoclusters. In this study, we investigate the catalytic activity of [Au25−x(PET)18−xM]NH3 (PET = 2-phenylethanethiolate, and M = Cu, Co, Ni, and Zn) nanoclusters in aerobic alcohol oxidation. The [Au25−x(PET)18−xM]NH3 nanoclusters are thoroughly characterized by matrix assisted laser desorption ionization (MALDI) mass spectrometry, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and inductively coupled plasma–mass spectrometry (ICP-MS). The XPS analyses suggest that the transition metals strongly interact with the gold atoms of the nanoclusters. The CeO2-supported nanoclusters show catalytic activity, based on the conversion of benzyl alcohol, in the order, [Au25−x(PET)18−xNi] > [Au25−x(PET)18−xCu] > [Au25−x(PET)18−xZn] > [Au25−x(PET)18−xCo]. Regarding product selectivity, the [Au25−x(PET)18−xZn] and [Au25−x(PET)18−xCo] catalysts preferably yield benzaldehyde, [Au25−x(PET)18−xCu] yields benzaldehyde and benzyl acid, and [Au25−x(PET)18−xNi] yields benzyl acid. The exposed metal atoms are considered as the catalytic active sites. Also, the catalytic performance (including activity and selectivity) of the [Au25−x(PET)18−xM] catalysts is greatly turned and mediated by the transition metal type.
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Transition metal-mediated catalytic properties of gold nanoclusters in aerobic alcohol oxidation. Nano Res. 2018, 11(4): 2139–2148 https://doi.org/10.1007/s12274-017-1831-9

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