Activity and stability of mesoporous CeO2 and ZrO2 catalysts for the self-condensation of cyclopentanone

Li, Gengnan; Dissanayake, Shanka; Suib, Steven L.; Resasco, Daniel E.

doi:10.1016/j.apcatb.2019.118373

Activity and stability of mesoporous CeO₂ and ZrO₂ catalysts for the self-condensation of cyclopentanone

Journal Article · Tue Nov 05 23:00:00 EST 2019 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2019.118373· OSTI ID:1824912

Li, Gengnan ^[1]; Dissanayake, Shanka ^[2]; ^[2]; ^[3]

Univ. of Oklahoma, Norman, OK (United States); University of Oklahoma Norman OK (United States)
Univ. of Connecticut, Storrs, CT (United States)
Univ. of Oklahoma, Norman, OK (United States)

Metal oxides containing acid-base pairs are widely used as catalysts for aldol condensation reactions, but they are often prone to secondary condensation and fast deactivation. In this contribution, high-surface area mesoporous CeO₂ and ZrO₂ have been synthesized and tested as catalysts for the self-condensation of cyclopentanone, an attractive molecular building block for several biomass upgrading strategies. Here, the catalytic activity, stability, and overall kinetics behavior of these two catalysts have been compared in the liquid phase. A detailed kinetics analysis shows that on both oxides, the reaction is controlled by the initial unimolecular α-H abstraction step, in which cyclopentanone forms the crucial enolate intermediate. Subsequently, the enolate couples with another cyclopentanone molecule in a bimolecular C-C coupling step. CO₂-TPD analysis and site titration with probe molecules indicate that initially the most active catalyst is the mesoporous ZrO₂ sample with strong base character. However, this catalyst exhibits a very rapid deactivation. By contrast, the mesoporous CeO₂ prepared in this study has lower basicity strength, which results in lower initial activity, but enhanced stability.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Oklahoma, Norman, OK (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018284

OSTI ID:: 1824912

Alternate ID(s):: OSTI ID: 1778296

Journal Information:: Applied Catalysis B: Environmental, Journal Name: Applied Catalysis B: Environmental Vol. 267; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aldol condensation
biomass conversion
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Activity and stability of mesoporous CeO2 and ZrO2 catalysts for the self-condensation of cyclopentanone

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Activity and stability of mesoporous CeO₂ and ZrO₂ catalysts for the self-condensation of cyclopentanone