Topics in Catalysis

, Volume 55, Issue 1–2, pp 53–69 | Cite as

Aqueous Phase Glycerol Reforming by PtMo Bimetallic Nano-Particle Catalyst: Product Selectivity and Structural Characterization

  • Paul J. Dietrich
  • Rodrigo J. Lobo-Lapidus
  • Tianpin Wu
  • Aslihan Sumer
  • M. Cem Akatay
  • Bradley R. Fingland
  • Neng Guo
  • James A. Dumesic
  • Christopher L. Marshall
  • Eric Stach
  • Julius Jellinek
  • W. Nicholas Delgass
  • Fabio H. Ribeiro
  • Jeffrey T. Miller
Original Paper


A carbon supported PtMo aqueous phase reforming catalyst for producing hydrogen from glycerol was characterized by analysis of the reaction products and pathway, TEM, XPS and XAS spectroscopy. Operando X-ray absorption spectroscopy (XAS) indicates the catalyst consists of bimetallic nano-particles with a Pt rich core and a Mo rich surface. XAS of adsorbed CO indicates that approximately 25% of the surface atoms are Pt. X-ray photoelectron spectroscopy indicates that there is unreduced and partially reduced Mo oxide (MoO3 and MoO2), and Pt-rich PtMo bimetallic nano-particles. The average size measured by transmission electron microscopy of the fresh PtMo nano-particles is about 2 nm, which increases in size to 5 nm after 30 days of glycerol reforming at 31 bar and 503 K. The catalyst structure differs from the most energetically stable structure predicted by density functional theory (DFT) calculations for metallic Pt and Mo atoms. However, DFT indicates that for nano-particles composed of metallic Pt and Mo oxide, the Mo oxide is at the particle surface. Subsequent reduction would lead to the experimentally observed structure. The aqueous phase reforming reaction products and intermediates are consistent with both C–C and C–OH bond cleavage to generate H2/CO2 or the side product CH4. While the H2 selectivity at low conversion is about 75%, cleavage of C–OH bonds leads to liquid products with saturated carbon atoms. At high conversions (to gas), these will produced additional CH4 reducing the H2 yield and selectivity.


Aqueous glycerol reforming Biomass reforming PtMo nano-particles Operando XAS Density functional theory of bimetallic nano-particles 



This material is based upon work supported as part of the Institute for Atom-efficient Chemical Transformations (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Use of the Advanced Photon Source is supported by the U. S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. J.J. was also supported by the Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, U.S. Department of Energy under Contract No. DE-AC02-06CH11357. This research used the resources of the National Energy Research Scientific Computing Center (NERSC), which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 and of the Laboratory Computing Resource Center (Fusion/LCRC) at Argonne National Laboratory. EAS acknowledges support the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.


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Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Paul J. Dietrich
    • 1
  • Rodrigo J. Lobo-Lapidus
    • 2
  • Tianpin Wu
    • 2
  • Aslihan Sumer
    • 2
  • M. Cem Akatay
    • 3
  • Bradley R. Fingland
    • 1
  • Neng Guo
    • 2
  • James A. Dumesic
    • 4
  • Christopher L. Marshall
    • 2
  • Eric Stach
    • 5
  • Julius Jellinek
    • 2
  • W. Nicholas Delgass
    • 1
  • Fabio H. Ribeiro
    • 1
  • Jeffrey T. Miller
    • 2
  1. 1.Department of Chemical EngineeringPurdue UniversityWest LafayetteUSA
  2. 2.Chemical Science and EngineeringArgonne National LaboratoryArgonneUSA
  3. 3.School of Materials EngineeringPurdue UniversityWest LafayetteUSA
  4. 4.Department of Chemical and Biological EngineeringUniversity of Wisconsin-MadisonMadisonUSA
  5. 5.Center for Functional NanomaterialsBrookhaven National LaboratoryUptonUSA

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