One-Step Approach to 2,5-Diformylfuran from Fructose over Molybdenum Oxides Supported on Carbon Spheres

Abstract

An effective one-pot process of synthesizing 2,5-diformylfuran (DFF) directly from fructose was accomplished over carbon sphere (CS)-supported molybdenum oxides (MoO x /CS) catalysts. The MoO x /CS catalyst was first prepared by a glucose hydrothermal carbonization method and subsequently annealed under different atmospheres. The annealing treatment under air at 275 °C afforded abundant mesopores over the CS and exposed more active sites. Kinetics studies suggested that 5-hydroxymethylfurfural (HMF) was the key intermediate; acid and oxide sites were active toward the dehydration of fructose and aerobic oxidation of HMF to DFF, respectively. A relatively faster dehydration rate compared to oxidation rate was critical for the dehydration of fructose to HMF instead of decomposing fructose under oxidative conditions. Under the optimized reaction conditions, nearly 78% yield of DFF at 100% conversion of fructose was obtained in dimethyl sulfoxide under atmospheric pressure of oxygen at 160 °C within 2 h.

Nanoengineering Carbon Spheres as Nanoreactors for Sustainable Energy Applications

“…Coville and co‐workers also reported the boron‐doped hollow carbon spheres encapsulating Pd nanoparticles, which showed excellent catalytic oxidation of alcohols into aldehydes; it was found that boron atoms can stabilize the Pd nanoparticles on the carbon support . Recently, due to the high cost and scarcity of noble metal, transitional‐based carbon sphere catalysts such as Mn‐and Mo‐related catalysts have been obtained and proved to be highly efficient, selective and recyclable . Yang and co‐workers prepared carbon spheres with decorated molybdenum oxides (MoO x /CS), which showed high catalytic activity in aerobic oxidation of fructose (nearly 78% yield of 2,5‐diformylfuran at 100% conversion) .…”

“…Recently, due to the high cost and scarcity of noble metal, transitional‐based carbon sphere catalysts such as Mn‐and Mo‐related catalysts have been obtained and proved to be highly efficient, selective and recyclable . Yang and co‐workers prepared carbon spheres with decorated molybdenum oxides (MoO x /CS), which showed high catalytic activity in aerobic oxidation of fructose (nearly 78% yield of 2,5‐diformylfuran at 100% conversion) . The acid and oxide sites in the MoO x /CS catalysts played an important role for dehydration of fructose and aerobic oxidation…”

Upgrading the chemistry of π-conjugated polymers toward more sustainable materials

“…115 2,5-diformylfuran can be obtained by selective oxidation of 5-HMF, but also in one step by derivatizing fructose. 116,117 Finally, difurfural can be obtained by dimerization of bromofurfural under photoirradiation. The latter experimental protocol was improved by using bromofurfural as a photosensitive initiator, and furfural as the main reagent.…”

Hydroxyapatite‐Supported Polyoxometalates for the Highly Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural or Glucose to 2,5‐Diformylfuran under Atmospheric Pressure

“…Additionally, the one-pot conversion of monosaccharides (such as fructose and glucose) into DFF is of greater value and lower cost in comparison to production of DFF from 5-HMF. [45,57,58] About 85 1.2 % yield of DFF was achieved directly from glucose in the presence of multi-site catalysts under oxygen pressure. By contrast, it is difficult to achieve a higher yield of DFF production from monosaccharides under atmospheric pressure, even thought this condition meets the safety and economical requirements [45,57,59] Using PMo 4 V 8 /HAP as a catalyst, the multifunctional sites could be more suitable for directly producing DFF from glucose.…”

“…Thus, a new catalytic system is required to be developed to achieve 5‐HMF oxidation to DFF under atmospheric pressure with high efficiency. Additionally, the one‐pot conversion of monosaccharides (such as fructose and glucose) into DFF is of greater value and lower cost in comparison to production of DFF from 5‐HMF [45,57,58] . About 8∼51.2 % yield of DFF was achieved directly from glucose in the presence of multi‐site catalysts under oxygen pressure.…”