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Title: Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen

Here, the ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml –1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s –1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participation in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [6] ;  [7] ;  [3] ; ORCiD logo [3]
  1. Fudan Univ., Shanghai (China); Northwestern Polytechnical Univ., Shaansi (China)
  2. Northwestern Polytechnical Univ., Shaansi (China); Northwestern Univ., Evanston, IL (United States)
  3. Northwestern Polytechnical Univ., Shaansi (China)
  4. Arizona State Univ., Tempe, AZ (United States)
  5. Northwestern Polytechnical Univ., Shaansi (China); Univ. Federal da Bahia, Bahia (Brazil); Ciencia e Tecnologica da Bahia, Bahia (Brazil)
  6. Northwestern Univ., Evanston, IL (United States)
  7. Univ. Federal da Bahia, Bahia (Brazil)
Publication Date:
Grant/Contract Number:
FG02-03ER15457
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Northwestern Polytechnical Univ., Shaansi (China)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical engineering; green chemistry; heterogeneous catalysis; homogeneous catalysis
OSTI Identifier:
1361195