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Rational catalyst design and optimal solvent selection are key to advancing biorefining. Here, we explored the organocatalytic isomerization of d-fructose to a valuable rare monosaccharide, d-allulose, as a function of solvent. The isomerization of d-fructose to d-allulose competes with its isomerization to d-glucose and sugar degradation. In both water and DMF, the catalytic activity of amines towards d-fructose is correlated with their basicity. Solvents impact the selectivity significantly by altering the tautomeric distribution of d-fructose. Our results suggest that the furanose tautomer of d-fructose is isomerized to d-allulose, and the fractional abundance of this tautomer increases as follows: water < MeOH < DMF ≈ DMSO. Reaction rates are also higher in aprotic than in protic solvents. The best d-allulose yield, 14 %, was obtained in DMF with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst. The reaction kinetics and mechanism were explored using operando NMR spectroscopy.
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Selective production of 5-hydroxymethylfurfural from fructose in the presence of an acid-functionalized SBA-15 catalyst modified with a sulfoxide polymer
Biomass is a renewable carbon feedstock that can be converted to 5-hydroxymethylfurfural (HMF), a useful platform chemical that can be modified to produce valuable chemicals and fuels. Previous research has shown that high HMF selectivity can be achieved in organic solvents such as dimethyl sulfoxide (DMSO) because of its capability to stabilize HMF in solution, but DMSO is an undesirable solvent to use industrially as product separation from the reaction solution is difficult. Surface functionalization of porous catalysts has been shown as a method to introduce solvent-effects at the surface of heterogeneous catalysts, thus avoiding the need for high boiling solvents like DMSO. Poly(ethylene sulfoxide) (PESO) is added to the surface of sulfonic acid (SA) functionalized SBA-15 silica to obtain the bifunctional catalyst SA-PESO-SBA-15. Co-localization of the sulfoxide polymer with sulfonic acid groups inside the catalyst pores (SA-PESO-SBA-15) increased HMF selectivity to 51% from 26% obtained by monofunctional SA-SBA-15 at 27% fructose conversion in water. Additionally, this bifunctional catalyst performs best in 4 : 1 (w/w) THF : water cosolvent, a more industrially preferred cosolvent system, obtaining 79% HMF selectivity at 87% fructose conversion. Overall, these materials are promising for the selective conversion of fructose to HMF.
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- PAR ID:
- 10136925
- Date Published:
- Journal Name:
- Molecular Systems Design & Engineering
- Volume:
- 5
- Issue:
- 1
- ISSN:
- 2058-9689
- Page Range / eLocation ID:
- 257 to 268
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9ME00093C
