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.

doi:10.1021/acscatal.3c00894

Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

Journal Article · Tue May 30 00:00:00 EDT 2023 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.3c00894· OSTI ID:2007307

^[1]; ^[2]; Chen, Tai-Ying ^[2]; ^[2]; ^[2]

University of Delaware, Newark, DE (United States); University of Delaware
University of Delaware, Newark, DE (United States)

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 ¹³C-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.

View Accepted Manuscript (DOE)

Research Organization:: RAPID Manufacturing Institute, New York, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO)

Grant/Contract Number:: EE0007888; AC02-05CH11231

OSTI ID:: 2007307

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 13; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

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