5-hydroxymethylfurfural and hydronium-ion

The addition of aprotic solvents results in higher reactivities and selectivities in many key aqueous phase biomass reactions, including the acid-catalyzed conversion of fructose to 5-hydroxyl methyl furfural (HMF). The addition of certain co-solvents inhibits the formation of humins via preferential solvation of key functional groups and can alter reaction kinetics. An important factor in this context is the relative stability of the hydronium ion (the catalyst) in the vicinity of the biomass moiety as compared to that in bulk, as it could determine its efficacy in the protonation step. Hence, in the present work, molecular dynamics (MD) simulations of HMF (the model product) and fructose (the model reactant) in acidic water and water-DMSO mixtures are performed to analyze their interaction with the hydronium ions. We show that the presence of DMSO favors the interaction of the hydronium ion with fructose, whereas it has a detrimental effect on the interaction of hydronium ion with HMF. Well-tempered metadynamics (WT-MTD) simulations are performed to determine the relative stability of the hydronium ion in the immediate vicinity of fructose and HMF, as compared to that in the bulk solvent phase, as a function of solvent composition. We find that DMSO improves the stabilization of the hydronium ions in the first solvation shell of fructose compared to that in the bulk solvent. On the other hand, hydronium ions become less stable in the immediate vicinity of HMF, as the concentration of DMSO increases.

Topics: Biomass; Catalysis; Dimethyl Sulfoxide; Fructose; Furaldehyde; Hydrogen-Ion Concentration; Molecular Dynamics Simulation; Onium Compounds; Solvents; Water

A series of defect pyrochlores of the composition (H3O)1+pSb1+pTe1-pO6 have been prepared by ion exchange from K-containing pyrochlores K1+pSb1+pTe1-pO6 in sulfuric acid at 280 °C for 24 h. The structural characterization of the hydronium-containing pyrochlores, including the location of the H3O+ units within the three-dimensional framework, was possible from neutron powder diffraction data in undeuterated samples. The crystal structure for all the compounds is defined in the Fd3[combining macron]m space group, and consists of a covalent framework of SbVO6 and TeVIO6 octahedra distributed at random and connected by their vertices with (Sb,Te)-O1-(Sb,Te) angles close to 136°, conforming to large cages where the hydronium species are located off-center. The absence of K+ ions in the ion-exchanged pyrochlores was confirmed by inductively coupled plasma optical emission spectroscopy and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. The shape and size of the hydronium units evolve along with the series, becoming more compact as the framework covalence and Lewis-basicity decrease upon Sb enrichment of the structure (for greater p values). The amount and lability of the H3O+ species also increase throughout the series, as wanted: a straightforward correlation of the catalytic activity in the fructose dehydration reaction to 5-hydroxymethylfurfural has been observed, reaching conversion rates up to 88.5% of concentrated fructose solution for the p = 0.25 catalyst. Moreover, a pseudo-first-order kinetic mechanism was simulated, and the kinetic constants obtained from diluted and concentrated enhanced reaction systems were determined and compared.

Topics: Antimony; Catalysis; Dehydration; Fructose; Furaldehyde; Hot Temperature; Isomerism; Molecular Conformation; Niobium; Onium Compounds; Oxides; Powder Diffraction; Tellurium; Time Factors; X-Ray Diffraction