Acid site densities and reactivity of oxygen-modified transition metal carbide catalysts

Sullivan, Mark M.; Bhan, Aditya

doi:10.1016/j.jcat.2016.09.012

Title: Acid site densities and reactivity of oxygen-modified transition metal carbide catalysts

Journal Article · Wed Sep 28 00:00:00 EDT 2016 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2016.09.012· OSTI ID:1533927

Sullivan, Mark M. ^[1]; Bhan, Aditya ^[1]

University of Minnesota, Minneapolis, MN (United States)

In this report acidic properties of β-Mo₂C, α-Mo₂C, W₂C, and WC were quantified by assessing the kinetics of isopropanol (IPA) dehydration at 415 K either (i) under inert He/Ar atmosphere or (ii) with 13 kPa O₂ co-feed. Dehydration kinetics were zero-order with respect to IPA for all catalysts and under all reaction conditions. Intrinsic activation energies were similar across all catalysts (89–104 kJ mol^-1). Acid site densities calculated via in situ 2,6-di-tert-butylpyridine (DTBP) titration were used to normalize dehydration turnover frequencies (TOF). O₂ co-feed increased dehydration rates per gram by an order of magnitude for all catalysts tested, but TOF remained invariant within a factor of ~2. Mo- and W-based carbides showed similar dehydration kinetics regardless of O₂ co-feed, and O₂ co-feed did not alter bulk carbidic structure as noted by X-ray diffraction. Brønsted acid site provenance results from the oxophilicity of Mo and W carbides.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0008418

OSTI ID:: 1533927

Alternate ID(s):: OSTI ID: 1359264

Journal Information:: Journal of Catalysis, Vol. 344, Issue C; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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Title: Acid site densities and reactivity of oxygen-modified transition metal carbide catalysts

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