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Aqueous Phase Glycerol Reforming with Pt and PtMo Bimetallic Nanoparticle Catalysts: The Role of the Mo Promoter

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Abstract

The turnover rate (TOR, normalized to sites measured by CO chemisorption before reaction) and selectivity for the aqueous phase reforming of glycerol have been determined for Pt/C and PtMo/C catalysts. While the TOR of PtMo/C is higher than that of Pt/C by about 4 times at comparable conversion, the selectivity to C–O bond cleavage is higher, thus reducing the H2 yield at high conversion. Under reaction conditions on Pt/C, CO is observed as the most abundant Pt surface species with a fractional coverage of about 0.6 using operando X-ray absorption spectroscopy. Since there is little CO in the effluent (CO2:CO ratios > 100:1, when CO is detected), it is thought that surface CO is converted to H2 and CO2 by the water gas shift reaction. DFT calculations suggest that the role of metallic Mo is to alter the electronic properties of Pt lowering the binding energy of CO and reducing the activation energies of dehydrogenation and C–O bond cleavage. Because the activation energy for C–O cleavage is lowered more than for dehydrogenation, the selectivity for C–O bond cleavage is increased, ultimately lowering the H2 yield compared to Pt/C.

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Acknowledgments

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 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 DE-AC02-05CH11231 and of the Laboratory Computing Resource Center (Fusion/LCRC) at Argonne National Laboratory. The authors would like to thank M. Cem Akatay for his assistance with the TEM images.

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Authors and Affiliations

  1. School of Chemical Engineering, Purdue University, W. Lafayette, IN, 47907, USA

    Paul J. Dietrich, W. Nicholas Delgass & Fabio H. Ribeiro

  2. Argonne National Laboratory, Chemical Science and Engineering, Argonne, IL, 60439, USA

    Tianpin Wu, Aslihan Sumer, Julius Jellinek & Jeffrey T. Miller

  3. Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI, 53706, USA

    James A. Dumesic

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  1. Paul J. Dietrich
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  2. Tianpin Wu
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  3. Aslihan Sumer
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  4. James A. Dumesic
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Correspondence to Fabio H. Ribeiro or Jeffrey T. Miller.

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Dietrich, P.J., Wu, T., Sumer, A. et al. Aqueous Phase Glycerol Reforming with Pt and PtMo Bimetallic Nanoparticle Catalysts: The Role of the Mo Promoter. Top Catal 56, 1814–1828 (2013). https://doi.org/10.1007/s11244-013-0115-1

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