Original Paper

Topics in Catalysis

, Volume 55, Issue 1, pp 53-69

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

  • Paul J. DietrichAffiliated withDepartment of Chemical Engineering, Purdue University
  • , Rodrigo J. Lobo-LapidusAffiliated withChemical Science and Engineering, Argonne National Laboratory
  • , Tianpin WuAffiliated withChemical Science and Engineering, Argonne National Laboratory
  • , Aslihan SumerAffiliated withChemical Science and Engineering, Argonne National Laboratory
  • , M. Cem AkatayAffiliated withSchool of Materials Engineering, Purdue University
  • , Bradley R. FinglandAffiliated withDepartment of Chemical Engineering, Purdue University
  • , Neng GuoAffiliated withChemical Science and Engineering, Argonne National Laboratory
  • , James A. DumesicAffiliated withDepartment of Chemical and Biological Engineering, University of Wisconsin-Madison
  • , Christopher L. MarshallAffiliated withChemical Science and Engineering, Argonne National Laboratory
    • , Eric StachAffiliated withCenter for Functional Nanomaterials, Brookhaven National Laboratory
    • , Julius JellinekAffiliated withChemical Science and Engineering, Argonne National Laboratory
    • , W. Nicholas DelgassAffiliated withDepartment of Chemical Engineering, Purdue University
    • , Fabio H. RibeiroAffiliated withDepartment of Chemical Engineering, Purdue University Email author 
    • , Jeffrey T. MillerAffiliated withChemical Science and Engineering, Argonne National Laboratory Email author 

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Abstract

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.

Keywords

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