Journal
ACS CATALYSIS
Volume 8, Issue 10, Pages 9056-9065Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.8b01615
Keywords
biomass processing; sugars chemistry; ketalization; acetalization; Gibbs ensemble Monte Carlo; adsorption
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Funding
- Catalysis Center for Energy Innovation, a U.S. Department of Energy - Energy Frontier Research Center [DE-SC0001004]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
- Information Technologies (IT) at the University of Delaware
- Minnesota Supercomputing Institute (MSI) at the University of Minnesota
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While Lewis-acid zeolites, such as Sn-Beta, catalyze glucose isomerization in an alcoholic medium, mesoporous Sn-SPP catalyzes both glucose isomerization to fructose and fructose etherification (formally ketalization) to ethyl fructoside, enabling fructose yields in excess of the glucose/fructose equilibrium. Using periodic density functional theory calculations and force-field-based Monte Carlo simulations, the ketalization reaction mechanism and adsorption behavior were examined. The silanols on the Sn-SPP mesopore surface facilitate the ketalization reaction through hydrogen bonding interactions at the transition state, only possible via a Sn-O-Si-OH moiety, present in Sn-SPP but not in Sn-Beta. Fructose ketalization is favored over glucose acetalization due to differences in stability of the oxonium intermediates, which are stabilized by the Sn-SPP active site. The open site of hydrophobic Sn-Beta cannot perform these reactions because its active site does not contain an adjacent silanol of the right geometry. In addition to the more favorable activation barrier of the catalytic process, the adsorption at the catalytic site in Sn-SPP is also found to be more favorable than for Sn-Beta, in spite of competitive adsorption between fructose and ethanol in the ethanol-saturated zeolites.
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