Heterogeneously‐Catalyzed Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid with MnO₂

Abstract

A simple non-precious-metal catalyst system based on costeffective and ubiquitously available MnO , NaHCO , and molecular oxygen was used to convert 5-hydroxymethylfurfural (HMF) to 2,5-difurandicarboxylic acid (FDCA) as a bioplastics precursor in 91 % yield. The MnO catalyst could be recovered by simple filtration and reused several times. The present system was also applicable to the aerobic oxidation of other biomass-derived substrates and the gram-scale oxidation of HMF to FDCA, in which 2.36 g (86 % yield) of the analytically pure FDCA could be isolated.

Inexpensive but Highly Efficient Co–Mn Mixed‐Oxide Catalysts for Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid

“…[16] Weak bases such as NaHCO 3 and KHCO 3 were more effective for obtaining ah igh FDCA yield (95-96%). [4,16] As shown in Figure S2, the HMF conversion and FDCA yield increasedw ith increasing amounto fb ase and the maximum values ( % 100 %a nd 95 %, respectively) were obtained at a base/HMF molar ratio of 2. [16] Conversely,b icarbonate (HCO 3 À )b ases (irrespective of the cation, Na + or K + )w ere the most effectivea dditive for the transformation of HMF to FDCA.…”

“…[4] In the presenti nvestigation, we examined the effects of different base compounds of varying strengths on the selectiveo xida-tion of HMFi nto FDCA over the Co-Mn-0.25 catalysta t1 20 8C for 5h.A ss hown in Figure 2b,t he FDCA yield gradually decreasedw ith increasing base strength,a sr eported previously. [16] Conversely,b icarbonate (HCO 3 À )b ases (irrespective of the cation, Na + or K + )w ere the most effectivea dditive for the transformation of HMF to FDCA. In contrast, strong and mediums trength bases such as NaOH, KOH, Na 2 CO 3 and K 2 CO 3 were less effective fors elective oxidation of HMF to FDCA, although almost1 00 %H MF conversion was achieved in all experiments irrespectiveo ft he type of base used, suggesting that the presence of as trongb ase in the reaction medium promoted the formationo fm ore byproducts that were undetectable by HPLC.…”

“…[4] Both homogeneousand heterogeneous noble-metal (Au, Pd, Pt and Ru) catalysts have been investigated for the oxidation of HMF to FDCA. [11][12][13][14][15][16][17] Among them, Mn-based catalysts have been found to be highly active owing to their different oxidations tates and high oxygen storage capacity,a sw ell as faster oxygen absorption and oxide reduction. Alternatively,inexpensive heterogeneousC o-, Fe-, and Mn-based catalysts have provedt ob ee ffective for this reaction.…”

Furfural Oxidation on Gold Supported on MnO2: Influence of the Support Structure on the Catalytic Performances

“…Indeed, 2-furoic acid can undergo a C-H carboxylation with CO 2 to form 2,5-furanodicarboxylic acid (FDCA) [19]. Secondly, MnO 2 is one of the most attractive materials because of its technological importance and possible application in different catalytic and electrochemical processes [20]. Moreover, the properties of MnO 2 are significantly influenced by its structure and morphology, which permits the study of the effect of the support structure on the catalytic activity.…”

Aerobic Oxidation of 5‐(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan‐2,5‐dicarboxylic Acid Formation with CeO2‐Supported Gold Catalyst

“…[13][14][15][16][17][18][19] HMF is one of the key intermediates derived from biobased glucose through acid-catalyzed dehydration [20][21][22][23] and can be converted into useful furans, including FDCA. [13][14][15][16][17][18][19] HMF is one of the key intermediates derived from biobased glucose through acid-catalyzed dehydration [20][21][22][23] and can be converted into useful furans, including FDCA.…”