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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

Show Author's information Chaolei Zhang1,2Yongdong Chen1( )Hong Wang1Zhimin Li2Kai Zheng2Shujun Li1Gao Li2( )
College of Chemistry and Chemical EngineeringSouthwest Petroleum UniversityChengdu610500China
Gold Catalysis Research CenterState Key Laboratory of CatalysisDalian Institute of Chemical PhysicsChinese Academy of SciencesDalian116023China

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.

Keywords: oxidation, gold nanoclusters, transition metal, heteroatom dopant, alcohol

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Publication history
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Acknowledgements

Publication history

Received: 09 July 2017
Revised: 20 August 2017
Accepted: 29 August 2017
Published: 19 March 2018
Issue date: April 2018

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany 2017

Acknowledgements

Acknowledgements

We are thankful for the generous support of "Thousand Youth Talents Plan" (G. L.) and Opening Project of State Key Laboratory of Catalysis (Grant N-16-04) and National Undergraduate Training Program for Innovation and Entrepreneurship (No. 201610615011) and Scientific Research Starting Project of SWPU (No. 2014QHZ016) and Sixteenth Period College Students' Extracurricular Open Experiment in Southwest Petroleum University (No. KSZ16069) (Y. D. C.).

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