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Title: Influence of dioxygen on the promotional effect of Bi during Pt-catalyzed oxidation of 1,6-hexanediol

In this study, a series of carbon-supported, Bi-promoted Pt catalysts with various Bi/Pt atomic ratios was prepared by selectively depositing Bi on Pt nanoparticles. The catalysts were evaluated for 1,6-hexanediol oxidation activity in aqueous solvent under different dioxygen pressures. The rate of diol oxidation on the basis of Pt loading over a Bi-promoted catalyst was 3 times faster than that of an unpromoted Pt catalyst under 0.02 MPa of O2, whereas the unpromoted catalyst was more active than the promoted catalyst under 1 MPa of O2. After liquid-phase catalyst pretreatment and 1,6-hexanediol oxidation, migration of Bi on the carbon support was observed. The reaction order in O2 was 0 over Bi-promoted Pt/C in comparison to 0.75 over unpromoted Pt/C in the range of 0.02–0.2 MPa of O2. Under low O2 pressure, rate measurements in D2O instead of H2O solvent revealed a moderate kinetic isotope effect (rateH2O/rateD2O) on 1,6-hexanediol oxidation over Pt/C (KIE = 1.4), whereas a negligible effect was observed on Bi-Pt/C (KIE = 0.9), indicating that the promotional effect of Bi could be related to the formation of surface hydroxyl groups from the reaction of dioxygen and water. No significant change in product distribution or catalyst stability was observedmore » with Bi promotion, regardless of the dioxygen pressure.« less
 [1] ;  [1] ;  [1] ;  [2] ;  [3] ;  [2] ;  [1]
  1. Univ. of Virginia, Charlottesville, VA (United States)
  2. Univ. of New Mexico, Albuquerque, NM (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
OSTI Identifier:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 2155-5435
American Chemical Society
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY alcohol oxidation; Bi; catalyst restructuring; dioxygen pressure; heterogeneous catalysts; isotope effect; promotional effect; Pt