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Selective Butene Formation in Direct Ethanol-to-C3+-Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated Hydrogen
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    Selective Butene Formation in Direct Ethanol-to-C3+-Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated Hydrogen
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    • Michael J. Cordon
      Michael J. Cordon
      Manufacturing Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
    • Junyan Zhang
      Junyan Zhang
      Manufacturing Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
      Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742, United States
      More by Junyan Zhang
    • Stephen C. Purdy
      Stephen C. Purdy
      Department of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
    • Evan C. Wegener
      Evan C. Wegener
      Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    • Kinga A. Unocic
      Kinga A. Unocic
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
    • Lawrence F. Allard
      Lawrence F. Allard
      Material Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
    • Mingxia Zhou
      Mingxia Zhou
      Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
      More by Mingxia Zhou
    • Rajeev S. Assary
      Rajeev S. Assary
      Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    • Jeffrey T. Miller
      Jeffrey T. Miller
      Department of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
    • Theodore R. Krause
      Theodore R. Krause
      Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    • Fan Lin
      Fan Lin
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Fan Lin
    • Huamin Wang
      Huamin Wang
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Huamin Wang
    • A. Jeremy Kropf
      A. Jeremy Kropf
      Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    • Ce Yang
      Ce Yang
      Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
      More by Ce Yang
    • Dongxia Liu
      Dongxia Liu
      Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742, United States
      More by Dongxia Liu
    • Zhenglong Li*
      Zhenglong Li
      Manufacturing Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
      *Email: [email protected]
      More by Zhenglong Li
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    ACS Catalysis

    Cite this: ACS Catal. 2021, 11, 12, 7193–7209
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    https://doi.org/10.1021/acscatal.1c01136
    Published June 4, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    The selective production of C3+ olefins from renewable feedstocks, especially via C1 and C2 platform chemicals, is a critical challenge for obtaining economically viable low-carbon middle-distillate transportation fuels (i.e., jet and diesel). Here, we report a multifunctional catalyst system composed of Zn–Y/Beta and “single-atom” alloy (SAA) Pt–Cu/Al2O3, which selectively catalyzes ethanol-to-olefin (C3+, ETO) valorization in the absence of cofed hydrogen, forming butenes as the primary olefin products. Beta zeolites containing predominately isolated Zn and Y metal sites catalyze ethanol upgrading steps (588 K, 3.1 kPa ethanol, ambient pressure) regardless of cofed hydrogen partial pressure (0–98.3 kPa H2), forming butadiene as the primary product (60% selectivity at an 87% conversion). The Zn–Y/Beta catalyst possesses site-isolated Zn and Y Lewis acid sites (at ∼7 wt % Y) and Brønsted acidic Y sites, the latter of which have been previously uncharacterized. A secondary bed of SAA Pt–Cu/Al2O3 selectively hydrogenates butadiene to butene isomers at a consistent reaction temperature using hydrogen generated in situ from ethanol to butadiene (ETB) conversion. This unique hydrogenation reactivity at near-stoichiometric hydrogen and butadiene partial pressures is not observed over monometallic Pt or Cu catalysts, highlighting these operating conditions as a critical SAA catalyst application area for conjugated diene selective hydrogenation at high reaction temperatures (>573 K) and low H2/diene ratios (e.g., 1:1). Single-bed steady-state selective hydrogenation rates, associated apparent hydrogen and butadiene reaction orders, and density functional theory (DFT) calculations of the Horiuti–Polanyi reaction mechanisms indicate that the unique butadiene selective hydrogenation reactivity over SAA Pt–Cu/Al2O3 reflects lower hydrogen scission barriers relative to monometallic Cu surfaces and limited butene binding energies relative to monometallic Pt surfaces. DFT calculations further indicate the preferential desorption of butene isomers over SAA Pt–Cu(111) and Cu(111) surfaces, while Pt(111) surfaces favor subsequent butene hydrogenation reactions to form butane over butene desorption events. Under operating conditions without hydrogen cofeeding, this combination of Zn–Y/Beta and SAA Pt–Cu catalysts can selectively form butenes (65% butenes, 78% C3+ selectivity at 94% conversion) and avoid butane formation using only in situ-generated hydrogen, avoiding costly hydrogen cofeeding requirements that hinder many renewable energy processes.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.1c01136.

    • XRD patterns, N2 adsorption isotherms, XAS fitting details and associated figures, STEM images, NH3–TPD spectra, additional product distributions and selectivity plots, DFT-calculated adsorption images, additional plots of butene formation rates as a function of butadiene and hydrogen partial pressures, transient butadiene selective hydrogenation profiles, DFT-calculated energy differences and activation energy barriers, additional reaction coordinate diagrams, product distribution plots of preliminary optimization strategies, and comparison of presented ETO pathway relative to literature observations (PDF)

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    This article is cited by 19 publications.

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    ACS Catalysis

    Cite this: ACS Catal. 2021, 11, 12, 7193–7209
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.1c01136
    Published June 4, 2021
    Copyright © 2021 American Chemical Society

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