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

  • 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
  • Libor Kovarik
    Libor Kovarik
    Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
  • Berlin Sudduth
    Berlin Sudduth
    The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States
  • 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
  • Feng Gao*
    Feng Gao
    Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
    *E-mail: [email protected] (F.G.).
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  • , and 
  • 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.).
    More by Yong Wang
Cite this: ACS Catal. 2020, 10, 7, 4268–4279
Publication Date (Web):February 20, 2020
https://doi.org/10.1021/acscatal.9b04654
Copyright © 2020 American Chemical Society
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Abstract

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.

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  • 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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