Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations

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Hierarchical zeolites containing both micropores and mesopores are valuable catalysts for facilitating reactions of large molecules. Furan acylation by fatty acids is a promising reaction for valorizing biomass, and the self-pillared pentasil (SPP) zeolite was found to perform particularly well for this reaction. To better understand the distribution of molecules in hierarchical zeolites at the elevated temperature (T=523 K) and the elevated pressure (p>1 bar) associated with typical reaction conditions, unary and binary adsorption were predicted using Monte Carlo simulations in the isothermal–isobaric Gibbs ensemble. Adsorption of six species (furan, hexanoic acid, n-hexane, n-decane, n-tetradecane, and 3,6-diethyloctane) was investigated from vapor, liquid, and supercritical phases, and loadings into the micropores, onto the mesopore surface, and in the mesopore interior of SPP were obtained. As pressure increases, n-alkanes fill the micropores before loading the surface and then the interior of the mesopore, while furan and hexanoic acid adsorb strongly to the mesopore surface due to hydrogen bonding interactions with surface silanols. Hydrogen bonding interactions also draw hexanoic acid molecules in the micropore region toward the pore mouths, so their carboxylic acid group forms H-bonds with silanols, while the alkyl tails interact with the micropore walls. Mesopore condensation is observed for molecules below their critical point, and occurs when the Gibbs free energy of transfer into the mesopore interior and onto the mesopore surface converge. When hexanoic acid adsorption occurs in the presence of alkane solvents, then the selectivity and spatial distribution of hexanoic acid in the micropores and on the surface can be tuned by adjusting the fluid pressure and the alkane length and/or branching.

Original languageEnglish (US)
Article number101267
JournalJournal of Computational Science
StatePublished - Jan 2021

Bibliographical note

Funding Information:
This research was primarily supported by the Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, United States under Award DE-FG02-17ER16362 (TRJ, MT, and JIS). Preliminary simulations were supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy , Office of Science, United States , Basic Energy Sciences, United States , under Award No. DE-SC0001004 (TRJ, PJD, MT, and JIS). Computer resources were provided through DE-FG02-17ER16362 and the Minnesota Supercomputing Institute at the University of Minnesota.


  • Gibbs ensemble Monte Carlo
  • Mesopore condensation
  • Multi-component adsorption

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