Intraparticle Diffusional Effects vs. Site Effects on Reaction Pathways in Liquid-Phase Cross Aldol Reactions


Chemo- and regioselectivity in a heterogeneously catalyzed cross aldol reaction were directed by tuning the nature of the sites, textural properties and reaction conditions. Catalysts included sulfonic-acid functionalized resins or SBA-15 with varying particle size or pore diameter, H-BEA zeolites, and Sn-BEA zeotype; conditions were 25 °C to 170 °C in organic media. Benzaldehyde and 2-butanone yielded branched (reaction at -CH2- of butanone) and linear (reaction at -CH3) addition and condensation products; and fission of the branched aldol led to β-methyl styrene and acetic acid. Strong acids promoted the dehydration step, and regioselectivity originated from preferred formation of the branched aldol. Both, resins and functionalized SBA-15 materials yielded predominantly the branched condensation product, unless particle morphology or temperature moved the reaction into the diffusion-limited regime, in which case more fission products were formed, corresponding to Wheeler Type II selectivity. For Hform zeolites, fission of the branched aldol competed with dehydration of the linear aldol, possibly because weaker acidity or steric restrictions prevented dehydration of the branched aldol.

Publication DOI:
Dataset DOI:
Divisions: College of Engineering & Physical Sciences > Energy and Bioproducts Research Institute (EBRI)
College of Engineering & Physical Sciences
Additional Information: Copyright © 2018 by John Wiley & Sons. This is the peer reviewed version of the following article: Intraparticle Diffusional Effects vs. Site Effects on Reaction Pathways in Liquid-Phase Cross Aldol Reactions Ponnuru, K., Manayil, J. C., Cho, H. J., Fan, W., Wilson, K. & Jentoft, F. 7 Jan 2018 In : ChemPhysChem., which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. Funding: NSF award 1560519. EPSRC (EP/K000616/2)
Uncontrolled Keywords: acid-base catalysis,C-C bond cleavage,C-C coupling,Biomass Conversion
Publication ISSN: 1439-7641
Last Modified: 06 May 2024 07:23
Date Deposited: 15 Jan 2018 11:40
Full Text Link:
Related URLs: http://doi.wile ... /cphc.201701219 (Publisher URL)
PURE Output Type: Article
Published Date: 2018-02-19
Published Online Date: 2018-01-07
Accepted Date: 2018-01-02
Authors: Ponnuru, Koushik
Manayil, Jinesh C (ORCID Profile 0000-0002-9864-3332)
Cho, Hong Je
Fan, Wei
Wilson, Karen
Jentoft, Friederike



Version: Accepted Version

| Preview

Export / Share Citation


Additional statistics for this record