Realizing direct conversion of glucose to furfurals with tunable selectivity utilizing a carbon dot catalyst with dual acids controlled by a biphasic medium

Sharma, Raina; Selim, Abdul; Devi, Bhawana; Arumugam, Senthil Murugan; Sartaliya, Shaifali; Elumalai, Sasikumar; Jayamurugan, Govindasamy

doi:10.1007/s13399-022-03182-w

Cited by 11 publications

(13 citation statements)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The higher PMI value may be due to the reverse formation of fructose by consumption of the formed product(s). The lower CE estimation of the process (37.7%) is due to unwanted fructose degradations . Nevertheless, the process’s AE was estimated as 100%, indicating good conversion efficiency of the reactant (atom) into the product(s).…”

Section: Resultsmentioning

confidence: 94%

See 1 more Smart Citation

Fructose Epimerization to l-Sorbose in Water over Molybdenum Oxide: Reaction Kinetics and Mechanism Insights

Devi

Arumugam²,

Mahala

et al. 2023

Ind. Eng. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Herein, we report the significant production of l-sorbose via a chemical catalysis method over molybdenum oxide (MoO3) using fructose in a water medium. The heterogeneous catalytic setup could produce 32% l-sorbose and 55% selectivity via C5-fructose epimerization. However, the synthesis was accompanied by a minor formation of tagatose (∼4%) and allulose (∼1%) side products via 1,3-hydride shift and 1,2-hydride shift mechanisms, respectively, using the single fructose source. Moreover, the interconversion reaction (fructose–sorbose) exhibited temperature-dependent characteristics, with an activation barrier of 68.2 kJ/mol. Based on the kinetics, fructose is shown to have a preference for reaching equilibrium with sorbose, which forms through a single 1,4-hydride shift. Due to this, a delayed formation of side products was observed, which follows a series of hydride shifts between the intermediates. From the results, the catalyst is versatile for various epimerization reactions. Selective extraction of fructose from the postreaction medium for product enrichment via naphthalene-2-boronic acid liquid–liquid, however, resulted in the recovery of both fructose and sorbose (ketoses) because of identical characteristics. Thus, the catalytic setup represents an environmentally friendly and sustainable method for upscaling based on the process’s green matrices.

show abstract

Section: Resultsmentioning

confidence: 94%

“…The lower CE estimation of the process (37.7%) is due to unwanted fructose degradations. 57 Nevertheless, the process's AE was estimated as 100%, indicating good conversion efficiency of the reactant (atom) into the product(s).…”

Section: Plausible Reaction Mechanism Of D-fructose Conversion To Pro...mentioning

confidence: 99%

Fructose Epimerization to l-Sorbose in Water over Molybdenum Oxide: Reaction Kinetics and Mechanism Insights

Devi

Arumugam²,

Mahala

et al. 2023

Ind. Eng. Chem. Res.

Self Cite

View full text Add to dashboard Cite

show abstract

“…For a chemical process, the green metric parameters, mainly environmental factor (E-factor), process mass intensity (PMI), and reaction carbon efficiency (CE), are considered important to establish the process’s environmental impact, viability, and sustainability from up-scaling and commercialization perspectives. , The E -factor signifies the wastes generated in a chemical reaction; for bulk chemicals’ production, it lies in the <1–5 range . In this case, it was estimated to be 2.18 (Table S8); this mid-average value of the process is likely caused by the significant residual glucose (unreacted) accounted for by up to 58%, which was included as a waste in the calculation, but it would not affect the environment.…”

Section: Resultsmentioning

confidence: 99%

Thermodynamic Insights into MgBr₂-Mediated Glucose Interconversion to Fructose Undertaking Multiple Reaction Pathways by Applying the Macro- and Micro-Kinetic Principles

Devi

Arumugam²,

Kumar³

et al. 2023

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

While many reports on the kinetics and mechanism of glucose isomerization to fructose via a chemical pathway have been published, thermodynamic insights into the interconversion reaction are rarely reported. Here, we report the temperature-dependent characteristics of the cation- and anion-mediated glucose conversion to fructose. The counter ions of MgBr2 enabled the reaction via different pathways in water; e.g., Mg2+ influenced the reaction by undertaking the 1,2-hydride shift mechanism and accounted for up to 50% of the conversion. However, the counter ion (Br–) promoted the conversion via the proton transfer mechanism, which contributed to the remaining 50%, based on the results of the isotopic labeling experiments. This selective transformation (32% wt fructose yield and 76% selectivity) aided by MgBr2 is attributed to the formation of a weak water shell around Mg2+ (due to a lower ratio of MgBr2 to water), which permitted the cation to expose its catalytic activity and affected the administering activity by Br–, which induces maximum side reactions. By applying the principles of transition-state Eyring and Marcus theories to the elementary steps involving a proton transfer and electron transfer, respectively, the temperature-dependent characteristics of the corresponding pathways were determined. The Eyring model exhibited a linear trend in the ln(k/T) vs 1/T plot with an activation energy barrier of 70.25 kJ/mol (comparable to the value of the collision-based Arrhenius model). The semi-classical Marcus model disclosed that the hydride shift is a normal electron transfer rate based on the localization of k ET in the λ< -ΔG o >0 region.

show abstract

“…From an upscaling perspective, the green metric parameters (such as environmental factor (E-factor), process mass intensity (PMI), atom economy (AE), and carbon efficiency (CE%)) of the glucose interconversion to fructose process were calculated. 48,49 These parameters normally determine a chemical process's feasibility and sustainability. For example, the E-factor signifying the process's environmental impact by accounting for the waste disposal should range between 1 and 5 for a chemical process.…”

Section: Green Matrices Of the Glucose Interconversion Processmentioning

confidence: 99%

Tuning of MgO's base characteristics by blending it with amphoteric ZnO facilitating the selective glucose isomerization to fructose for bioenergy development

Mahala

Arumugam²,

Kumar³

et al. 2023

Nanoscale Adv.

Self Cite

View full text Add to dashboard Cite

show abstract

Realizing direct conversion of glucose to furfurals with tunable selectivity utilizing a carbon dot catalyst with dual acids controlled by a biphasic medium

Cited by 11 publications

References 68 publications

Fructose Epimerization to l-Sorbose in Water over Molybdenum Oxide: Reaction Kinetics and Mechanism Insights

Fructose Epimerization to l-Sorbose in Water over Molybdenum Oxide: Reaction Kinetics and Mechanism Insights

Thermodynamic Insights into MgBr₂-Mediated Glucose Interconversion to Fructose Undertaking Multiple Reaction Pathways by Applying the Macro- and Micro-Kinetic Principles

Tuning of MgO's base characteristics by blending it with amphoteric ZnO facilitating the selective glucose isomerization to fructose for bioenergy development

Contact Info

Product

Resources

About

Realizing direct conversion of glucose to furfurals with tunable selectivity utilizing a carbon dot catalyst with dual acids controlled by a biphasic medium

Cited by 11 publications

References 68 publications

Fructose Epimerization to l-Sorbose in Water over Molybdenum Oxide: Reaction Kinetics and Mechanism Insights

Fructose Epimerization to l-Sorbose in Water over Molybdenum Oxide: Reaction Kinetics and Mechanism Insights

Thermodynamic Insights into MgBr2-Mediated Glucose Interconversion to Fructose Undertaking Multiple Reaction Pathways by Applying the Macro- and Micro-Kinetic Principles

Tuning of MgO's base characteristics by blending it with amphoteric ZnO facilitating the selective glucose isomerization to fructose for bioenergy development

Contact Info

Product

Resources

About

Thermodynamic Insights into MgBr₂-Mediated Glucose Interconversion to Fructose Undertaking Multiple Reaction Pathways by Applying the Macro- and Micro-Kinetic Principles