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Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration

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    Research Article

    Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration
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    • Fan Lin
      Fan Lin
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Fan Lin
    • Yuan Chen
      Yuan Chen
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Yuan Chen
    • Lu Zhang
      Lu Zhang
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Lu Zhang
    • Donghai Mei
      Donghai Mei
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Donghai Mei
      Orcidhttp://orcid.org/0000-0002-0286-4182
    • Libor Kovarik
      Libor Kovarik
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Libor Kovarik
      Orcidhttp://orcid.org/0000-0002-2418-6925
    • Berlin Sudduth
      Berlin Sudduth
      The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States
      More by Berlin Sudduth
    • Huamin Wang*
      Huamin Wang
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      *E-mail: [email protected] (H.W.).
      More by Huamin Wang
      Orcidhttp://orcid.org/0000-0002-3036-2649
    • Feng Gao*
      Feng Gao
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      *E-mail: [email protected] (F.G.).
      More by Feng Gao
      Orcidhttp://orcid.org/0000-0002-8450-3419
    • Yong Wang*
      Yong Wang
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States
      *E-mail: [email protected] (Y.W.).
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      Orcidhttp://orcid.org/0000-0002-8460-7410
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    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 7, 4268–4279
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    https://doi.org/10.1021/acscatal.9b04654
    Published February 20, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Alkanol dehydration on Lewis acid–base pairs of transition metal oxide catalysts is a reaction of importance in oxygen removal from biomass-derived feedstocks and their conversion to chemicals in general. However, catalysts with a high degree of structural heterogeneity, such as commercial TiO2 powders, are not well-suited to establish rigorous structure–function relationships at an atomic level. Here, we provide compelling evidence for the effects of surface orientation of TiO2 catalyst on elimination reactions of alcohols. Two anatase titania model catalysts, with preferential exposure of (101) and (001) facets, were synthesized and studied for 2-propanol dehydration using kinetic, isotopic, microscopic, and spectroscopic measurements, coupled with DFT calculations. Surface Lewis acid sites were found to be active for 2-propanol dehydration, and (101) facets are more reactive than (001) facets under the reaction conditions studied. On both anatase surfaces, 2-propanol was found to dehydrate via concerted E2 elimination pathways, but with different initial states and thus also different intrinsic activation barriers. Molecular 2-propanol dehydration dominates on TiO2 (101) while on TiO2 (001), 2-propanol simultaneously converts to more stable 2-propoxide before dehydration, which then requires higher activation energies for E2 elimination.

    Copyright © 2020 American Chemical Society

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.9b04654.

    • Additional information on DFT calculation, derivation of rate constant, characterization results of the catalysts (XRD, XPS, and Pyridine-DRIFTS), impact of H2O, and impact of addition of 2,6-DTBP (PDF)

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    Cited By

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    This article is cited by 39 publications.

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    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 7, 4268–4279
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.9b04654
    Published February 20, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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