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DOE OSTI · 2007307

Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

Rodriguez Quiroz, Natalia·Chen, Tso-Hsuan·Chen, Tai-Ying·Caratzoulas, Stavros·Vlachos, Dionisios G.
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Abstract

Biphasic dehydration of fructose to 5-hydroxymethylfurfural (HMF) has shown unprecedented increases in productivity, but a mechanistic understanding is lacking. Herein, we couple fast experimental reaction kinetics, multiscale modeling (phase behavior, classical molecular dynamics(MD), and quantum mechanics/molecular mechanics MD), in situ sampling, and IR and 13 C-NMR spectroscopy to elucidate the complex effects of nonpolar extracting organic solvents on the kinetics of fructose dehydration. We show that these organic solvents can reach significant mutual solubility with water at reaction temperatures, enabling the partition of the sugar and catalyst into the extracting phase. In the organic-rich environment, the dehydration of fructose proceeds faster and more selectively than in water due to increased relative abundance of the reactive furanose isomer, enhanced water–catalyst–substrate interactions driven by nanophase separation, and higher product stability stemming from preferential solvation. Furthermore, we demonstrate that these solvent effects impact other critical biphasic reactions in biomass upgrading and provide qualitative principles for solvent selection.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYQM/MMacid catalystsaldehydesbiomass conversionbiphasiccarbohydratesdehydrationmolecular dynamicsreaction kineticssolvation free energysolvent effectssolventswater

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Rodriguez Quiroz, Natalia, Chen, Tso-Hsuan, Chen, Tai-Ying, Caratzoulas, Stavros, Vlachos, Dionisios G.. 2023-05-30. Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems. https://doi.org/10.1021/acscatal.3c00894

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