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

Journal Article · · ACS Catalysis
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Washington State Univ., Pullman, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
+ Show Author Affiliations
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.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1634996
Report Number(s):
PNNL-SA--150163
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 7 Vol. 10; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY