While chromium trichloride hydrate (CrCl 3 ·6H 2 O) effectively catalyzed the isomerization of glucose into fructose in aqueous solution, a general product selectivity behavior was observed independent of reaction variables such as reaction time, temperature, catalyst loading, halide ion, and initial glucose concentration. By studying the mixed solution of dimethylsulfoxide (DMSO) and water at varied DMSO/H 2 O ratios, it was found that deviation from the general water-phase fructose yield curve, with concomitant 5-hydroxymethylfurfral (HMF) formation, occurred when the fructose concentration in available water became sufficiently high in DMSO rich solvent mix. Therefore, tuning the solvent system was the most effective approach to change the product distribution from CrCl 3 ·6H 2 O catalyzed glucose conversion. The apparent activation energy of glucose conversion in the studied system was estimated to be 58.6 kJ mol −1 . Special attention was also given to gain some mechanistic insights by control experiments with simple model compounds and additives, 13 C NMR and UV–vis spectroscopic analyses.
In order to ameliorate the issues of corrosion and high regeneration energy associated with traditional biphasic solvents, a nonaqueous biphasic solvent has been proposed as a potential alternative. This study introduces Tetramethylethylenediamine (TMEDA) as a phase splitter within the Ethanolamine (MEA)/Dimethyl sulfoxide (DMSO) system, resulting in a novel nonaqueous biphasic solvent, TMEDA/MEA/DMSO. Compared with other screened phase splitters, the appropriate polar size and intermolecular interaction force of TMEDA are the key factors that make it comply with the screening of nonaqueous biphasic solvent. When the mass ratio of TMEDA/MEA/DMSO is maintained at 3:3:4, the CO 2 loading attains 0.54 mol (CO 2 )/mol (MEA), with the rich phase comprising 75 % of the total. 13 C NMR and FT-IR characteristics showed that the absorbent product is mainly in the form of MEACOO − /MEAH + . Absorption and phase separation mechanisms of absorbent elucidated by DFT calculations and molecular dynamics simulations. The limited opportunity for TMEDA to interact with MEA molecules emerges as the primary reason for its reduced involvement in the reaction, with the inclusion of TMEDA intensifying the aggregation of MEACOO − /MEAH + and triggering phase transition. In comparison to a 30 wt% MEA water-based absorbent, TMEDA/MEA/DMSO exhibits a 40 % reduction in regeneration energy (estimate) and possesses energy-saving attributes, rendering it a promising candidate for CO 2 capture.
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