Title: CO oxidation over ceria supported Au₂₂ nanoclusters: Shape effect of the support

Abstract

Gold (Au) nanoclusters have recently emerged as ideal models for understanding Au catalysis, because the nanosized Au particles have precise atomic numbers and uniform size. Here, in this work, we studied for the first time the support shape effect on the catalysis of Au nanoclusters by using CO oxidation as a model reaction. Au₂₂(L⁸)₆ (L = 1,8-bis(diphenylphosphino) octane) nanoclusters were supported on CeO₂ rods or cubes, then pretreated at different temperatures (up to 673 K), allowing the gradual removal of the organic phosphine ligands. CO oxidation test over these differently pretreated samples shows that CeO₂ rods are much better supports than cubes for Au₂₂ nanoclusters in enhancing the reaction rate. In situ IR spectroscopy coupled with CO adsorption indicates that the shape of CeO₂ support can impact the nature and quantity of exposed Au sites, as well as the efficiency of organic ligand removal. Although CeO₂ rods are helpful in exposing a greater percentage of total Au sites upon ligands removal, the percentage of active Au sites (denoted by Au^δ+, 0 < δ < 1) is lower than that on CeO₂ cubes. The in situ extended X-ray absorption spectroscopy (EXAFS) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) resultsmore » show that the Au nanoclusters bound more strongly to the CeO₂ rods than to the cubes where the Au nanoclusters show more sintering. Considering the typical redox mechanism for CO oxidation over supported Au nanoclusters and nanoparticles, it is concluded that the reactivity of the lattice oxygen of CeO₂ is the determining factor for CO oxidation over Au₂₂/CeO₂. Lastly, CeO₂ rods offer more reactive lattice oxygen and abundant oxygen vacancies than the cubes and thus make the rods a superior support for Au nanoclusters in catalyzing low temperature CO oxidation.« less

Authors:

Wu, Zili  ^[1];

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Mullins, David R.  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-3495-7188"
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Allard, Lawrence Frederick  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-4552-8277"
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Zhang, Qianfan ^[3]; Wang, Laisheng ^[3]

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+ Show Author Affiliations

1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Science Division and Center for Nanophase Materials Sciences
2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
3. Brown Univ., Providence, RI (United States). Department of Chemistry

Publication Date:

2018-01-31

Research Org.:

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:

1468071

Alternate Identifier(s):

OSTI ID: 1582758

Grant/Contract Number:  

AC05-00OR22725; AC02-76SF00515; SC0012335; De-SC0012335

Resource Type:

Accepted Manuscript

Journal Name:

Chinese Chemical Letters

Additional Journal Information:

Journal Volume: 29; Journal Issue: 6; Journal ID: ISSN 1001-8417

Publisher:

Elsevier

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Gold nanoclusters; Ceria; Ligands; Support shape; CO oxidation