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Title: Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal

Journal Article · · Nano Letters
 [1];  [2];  [2];  [1];  [3];  [1];  [3];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of California, Riverside, CA (United States)
  3. Brown Univ., Providence, RI (United States)
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Investigation of monodispersed and atomically-precise Au nanoclusters provides a route to understand the roles of coordination, size, and ligand effects in Au catalysis. We have explored the catalytic behavior of a newly-synthesized Au22(L8)6 nanocluster (L = 1,8-bis(diphenylphosphino) octane) with in situ uncoordinated Au sites supported on TiO2, CeO2 and Al2O3. Stability of the supported Au22 nanoclusters was probed structurally by EXAFS and HAADF-STEM, and their adsorption and reactivity for CO oxidation were investigated by IR absorption spectroscopy and temperature programed flow reaction. Low temperature CO oxidation activity was observed for the supported pristine Au22(L8)6 nanoclusters without ligand removal. Isotopically labeled O2 was used to demonstrate that the reaction pathway occurs through a redox mechanism, consistent with the observed support-dependent activity trend: CeO2 > TiO2 > Al2O3. Substantiated by density functional theory (DFT) calculations, we conclude that the uncoordinated Au sites in the intact Au22(L8)6 nanoclusters are capable of adsorbing CO, activating O2 and promoting CO oxidation reaction. Thanks to the presence of the in situ coordination unsaturated Au atoms, this work is the first clear demonstration of a ligand-protected Au nanocluster that are active for gas phase catalysis without the need of ligand removal.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1360045
Journal Information:
Nano Letters, Vol. 16, Issue 10; ISSN 1530-6984
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 70 works
Citation information provided by
Web of Science

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Cited By (14)

The Evolution in Catalytic Activity Driven by Periodic Transformation in the Inner Sites of Gold Clusters journal July 2019
Multi-ligand-directed synthesis of chiral silver nanoclusters journal January 2017
An Au 22 (L 8 ) 6 nanocluster with in situ uncoordinated Au as a highly active catalyst for O 2 activation and CO oxidation journal January 2019
Activation of atom-precise clusters for catalysis journal January 2020
Motif-mediated Au25(SPh)5(PPh3)10X2 nanorods with conjugated electron delocalization journal August 2018
Preparation of gas phase naked silver cluster cations outside a mass spectrometer from ligand protected clusters in solution journal January 2018
Stronger-than-Pt hydrogen adsorption in a Au 22 nanocluster for the hydrogen evolution reaction journal January 2018
Design of atomically precise Au 2 Pd 6 nanoclusters for boosting electrocatalytic hydrogen evolution on MoS 2 journal January 2018
Dual effects of water vapor on ceria-supported gold clusters journal January 2018
Triple 1D1D superatomic bonding. Au 22 (dppo) 6 as a Π 4 - and Δ 2 -triply bonded cluster based on Au 11 assembled units journal January 2020
Ligand-protected atomically precise gold nanoclusters as model catalysts for oxidation reactions journal January 2020
Heterogeneous gold catalysts for selective hydrogenation: from nanoparticles to atomically precise nanoclusters journal January 2019
Structure and reactivity of gold cluster protected by triphosphine ligands: DFT study journal February 2019
Size‐dependent electrophoretic migration and separation of water‐soluble gold nanoclusters by capillary electrophoresis journal February 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY