Selective Hydrodeoxygenation of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Heterogeneous Iron Catalysts

Abstract

This work provided the first example of selective hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) over heterogeneous Fe catalysts. A catalyst prepared by the pyrolysis of an Fe-phenanthroline complex on activated carbon at 800 °C was demonstrated to be the most active heterogeneous Fe catalyst. Under the optimal reaction conditions, complete conversion of HMF was achieved with 86.2 % selectivity to DMF. The reaction pathway was investigated thoroughly, and the hydrogenation of the C=O bond in HMF was demonstrated to be the rate-determining step during the hydrodeoxygenation, which could be accelerated greatly by using alcohol solvents as additional H-donors. The excellent stability of the Fe catalyst, which was probably a result of the well-preserved active species and the pore structure of the Fe catalyst in the presence of H , was demonstrated in batch and continuous flow fixed-bed reactors.

The effect of me‐substituents of 1,4‐butanediol analogues on the thermal properties of biobased polyesters

“…With the development of improved routes from C5‐ and C6‐sugars to furans, methyl‐substituted furans are becoming more available. For example, C5‐sugar‐derived furfural is selectively converted into both furan and 2‐methylfuran, while C6‐sugar‐derived 5‐(hydroxymethyl)furan‐2‐carbaldehyde (HMF) is converted selectively into 2,5‐dimethylfuran . Similar to the conversion of furan to 1,4‐butanediol, aqueous hydrogenation of 2‐methylfuran gives 1,4‐pentanediol and 2,5‐dimethylfuran gives 2,5‐hexanediol …”

Homogenous Meets Heterogenous and Electro‐Catalysis: Iron‐Nitrogen Molecular Complexes within Carbon Materials for Catalytic Applications

“…Using sec ‐butanol as a reductant and solvent, their optimised conditions (160 °C, 15 h) gave 83 % selectivity and 92 % conversion of the starting material. Then, they explored 5‐HMF deoxygenation into dimethylfuran (DMF), using both H 2 and n ‐butanol as reductants (Scheme A) . In both cases catalyst recyclability was excellent (5 cycles) and 5‐HMF deoxygenation could be transposed to continuous‐flow synthesis, with a consistent DMF yield above 80 % over 72 hours.…”

“…The Fu group contributed further to the study by performing temperature‐programmed reduction (TPR) analysis on Fe‐phen/C‐800. Upon adsorbing H 2 on the material and studying its desorption pattern under a heating ramp, they correlated the presence of FeN x sites with a characteristic peak at 620 °C . However, NH 3 and CO 2 TPR analysis proved inconclusive to detect Lewis acidic and basic sites on the material …”

Hydrogenolysis of Biomass‐Derived 5‐Hydroxymethylfurfural to Produce 2,5‐Dimethylfuran Over Ru‐ZrO2‐MCM‐41 Catalyst

“…Li et al . demonstrated the selective hydrogenation of HMF to DMF using iron‐phenanthroline complex as a heterogeneous catalyst in n ‐butanol at 40 bar hydrogen pressure and 240 °C for 12 h . Yang et al .…”