Boosting the activity of catalytic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over nitrogen-doped manganese oxide catalysts

Abstract

Doping of nitrogen into MnO2 is employed as an efficient catalyst for the catalytic oxidation of HMF to DFF under an oxygen atmosphere.

Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid

“…Additionally, the synthesis of DFF from HMF commonly requires molecular oxygen or expensive transition metal (co)-catalyst (e. g. Ru) which further reduces the applicability of DFF-derived reaction at a higher scale. [26][27][28][29] We conducted the oxidation of HMF in a semi-continuous manner using a column packed with commercial electrolytically precipitated 88 % MnO 2 (Supporting Information, Figure S1) and the toluene alternative 2,2,5,5-tetramethyloxolane (TMO, Figure 1, 14) as the solvent. [30] The non-peroxide forming TMO used in this reaction was recovered and reused after distillation.…”

“…In addition, this system did not require the use of inert atmosphere, molecular oxygen or co-catalyst as previously reported. [26,31,32] The solution collected after one passage through the column was analysed by GC-FID to assess the conversion of HMF. If the conversion was not complete, the solution was recirculated through the column.…”

“…This loss of activity was initially thought to be owing to the formation of the inactive species MnOOH as suggested previously. [26,31] Hence, another system was designed where pure O 2 was bubbled continuously in the HMF solution before the column to favor the re-oxidation of the partially reduced MnO 2-d to MnO 2 and avoid the formation of the red-ox Figure 1. a) Synthetic route to unsaturated monomer 1 a. MnO2 (excess; e. g., 7.73 g), 1 % HMF solution in TMO (e. g., 1 g in 100 mL), 75°C semi-continuous 1 mL/min, residence time~3 min, total reaction time 100 min.…”

Polymethylaminosiloxane Grafted Transition Metal Catalyst DICAT‐V for Chemoselective Aerobic Oxidation of 5‐HMF into 2,5‐Diformyl Furan

“…Yang et al [21] have reported iron-based Fe 3 O 4 -SBA-SO 3 H and K-OMS-2 catalysts to obtain a 99 % yield of DFF with 100 % selectivity of 5-HMF in DMSO. Ke et al [22] have reported Nitrogen-doped manganese oxide (N-MnO 2 ) catalysts and showed > 99.9 % selectivity of DFF with a 100 % conversion of 5-HMF. Moreau et al [23] have reported V 2 O 5 /TiO 2 catalysts with 91 % 5-HMF conversion and 93 % selectivity of DFF.…”

“…have reported iron‐based Fe 3 O 4 ‐SBA‐SO 3 H and K‐OMS‐2 catalysts to obtain a 99 % yield of DFF with 100 % selectivity of 5‐HMF in DMSO. Ke et al . have reported Nitrogen‐doped manganese oxide (N‐MnO 2 ) catalysts and showed >99.9 % selectivity of DFF with a 100 % conversion of 5‐HMF.…”