Oxidation of 5-hydroxymethyl furfural to 2,5-diformylfuran in aqueous media over heterogeneous manganese based catalysts

Neaţu, Florentina; Petrea, Nicoleta; Petre, Răzvan; Şomoghi, Vasile; Florea, Mihaela; Pârvulescu, Vasile I.

doi:10.1016/j.cattod.2016.03.031

Cited by 64 publications

(37 citation statements)

References 34 publications

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“…In the series of Ru-(Mn-M)O X catalysts, the surface specific area varied as follows: Ru-(Mn-Al)O X < Ru-(Mn-Zn)O X -< Ru-Mn-Ti)O X -< Ru-(Mn-Zr)O X with 26, 37, 47 and 61 m 2 g −1 , respectively. These values are lower than those reported in the literature for dried or calcined Mn-Cu-Al layered double hydroxides [26]. The lowest specific area is associated with the lowest M content in the mixed oxide catalysts.…”

Section: Catalyst Characterizationcontrasting

confidence: 53%

“…The Ru-(Mn-Zr)O X and Ru-(Mn-Zn)O X catalysts were prepared analogously to this procedure. The Ru-(Mn-Ti)O X was prepared as previously, however, Mn(OAc) 2 was used as the precursor due to the use of Ti(OiPr) 4 [24,26]. The material was dried and calcined, as previously.…”

Section: Catalysts Preparationmentioning

confidence: 99%

“…The Ru-mixed oxide based catalysts were prepared by a standard co-precipitation method according to the literature [24,26]. In the synthesis of Ru-(Mn-Al)O X catalyst, an aqueous solution (330 mL) of Mn(NO 3 ) 2 ·4H 2 O (9.1 g), Al(NO 3 ) 3 ·9H 2 O (3.4 g) and Ru(NO)(NO 3 ) 3 ·xH 2 O (0.4 g) and an aqueous solution (264 mL) of NaOH (10.5 g) and Na 2 CO 3 (8.7 g) were added simultaneously dropwise under vigorous stirring at RT into a round-bottom 1 L flask and the pH was controlled at 12 ± 0.5.…”

Section: Catalysts Preparationmentioning

confidence: 99%

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Ru-(Mn-M)OX Solid Base Catalysts for the Upgrading of Xylitol to Glycols in Water

et al. 2018

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A series of Ru-(Mn-M)O X catalysts (M: Al, Ti, Zr, Zn) prepared by co-precipitation were investigated in the hydrogenolysis of xylitol in water to ethylene glycol, propylene glycol and glycerol at 200 • C and 60 bar of H 2 . The catalyst promoted with Al, Ru-(Mn-Al)O X , showed superior activity (57 h −1 ) and a high global selectivity to glycols and glycerol of 58% at 80% xylitol conversion. In comparison, the catalyst prepared by loading Ru on (Mn-Al)O X , Ru/(Mn-Al)O X was more active (111 h −1 ) but less selective (37%) than Ru-(Mn-Al)O X . Characterization of these catalysts by XRD, BET, CO 2 -TPD, NH 3 -TPD and TEM showed that Ru/(Mn-Al)O X contained highly dispersed and uniformly distributed Ru particles and fewer basic sites, which favored decarbonylation, epimerization and cascade decarbonylation reactions instead of retro-aldol reactions producing glycols. The hydrothermal stability of Ru-(Mn-Al)O X was improved by decreasing the xylitol/catalyst ratio, which decreased the formation of carboxylic acids and enabled recycling of the catalyst, with a very low deactivation.

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Section: Catalyst Characterizationcontrasting

confidence: 53%

Section: Catalysts Preparationmentioning

confidence: 99%

Section: Catalysts Preparationmentioning

confidence: 99%

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Ru-(Mn-M)OX Solid Base Catalysts for the Upgrading of Xylitol to Glycols in Water

et al. 2018

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“…From the thermodynamic point of view, the aldehyde group on HMF is more prone to be oxidized to carboxyl group . Therefore the selective oxidation of HMF to DFF remains a great challenge that requires the oxidation of its primary hydroxyl group while leaving the aldehyde group intact.…”

Section: Introductionmentioning

confidence: 99%

An efficient approach to produce 2,5‐diformylfuran from 5‐hydroxymethylfurfural using air as oxidant

Jia

Liu

et al. 2019

J of Chemical Tech & Biotech

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BACKGROUND 2,5‐Diformylfuran (DFF) is a versatile bio‐derived platform chemical. Multiple catalytic systems including homogeneous and heterogeneous catalysts have been studied for the oxidation of 5‐hydroxymethylfurfural (HMF) to DFF, but a more efficient and economical approach to produce DFF via HMF remains to be developed. RESULTS This study provides a practical approach to oxidizing HMF to DFF using Fe(NO3)3/Cu(NO3)2 as catalysts and air as oxidant with the assistance of K2S2O8. The typical oxidation of HMF to DFF was conducted under conditions of 4 wt% catalyst, 80 °C and 3 h, achieving an excellent DFF yield of over 99%. CONCLUSION In this oxidation reaction, Fe(NO3)3 played a crucial catalytic role by the redox cycle of Fe(III) and Fe(II), while Cu(NO3)2 functioned as a co‐catalyst to promote the redox cycle of Fe(II) and Fe(III) by the redox cycle of Cu(II) and Cu(I) with the assistance of oxygen. Meanwhile, NO2 released from the decomposition of Fe(NO3)3 during the redox cycle of Fe(II) and Fe(III) also participated in the oxidation of Fe(II) to Fe(III) by the redox cycle of NO2 and NO with the assistance of oxygen. Noteworthily, K2S2O8 provided an essential acidity to the oxidation of HMF to DFF through its decomposition product SO3. All these factors together ensured the efficient conversion of HMF and high selectivity of DFF. © 2019 Society of Chemical Industry

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“…[11] Recent studies have shown that DFF can be synthesized in water with good conversion and 87 %s electivity by using Mn 0.70 Cu 0.05 Al 0.25 OH as catalystu nder mild conditions in the absence of any additives. [12] To our knowledge, no other reported methods have attained comparables electivity towards DFF when using water as solvent and homogeneous or heterogeneous catalysts. [12] To our knowledge, no other reported methods have attained comparables electivity towards DFF when using water as solvent and homogeneous or heterogeneous catalysts.…”

Section: Introductionmentioning

confidence: 92%

Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran or 2‐Formyl‐5‐furancarboxylic Acid in Water by using MgO⋅CeO₂ Mixed Oxides as Catalysts

Ventura

Lobefaro²,

Giglio

et al. 2018

ChemSusChem

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Mixed oxides based on MgO⋅CeO were used as efficient catalysts in the aerobic oxidation of 5-hydroxymethylfurfural (5-HMF) to afford, with very high selectivity, either 2,5-diformylfuran (DFF, 99 %) or 2-formyl-5-furancarboxylic acid (FFCA, 90 %), depending on the reaction conditions. 5-Hydroxymethyl-2-furancarboxylic acid (HMFCA, 57-90 %) was formed only at low concentration of 5-HMF (<0.03 m) or in presence of external bases. The conversion of 5-HMF ranged from a few percent to 99 %, according to the reaction conditions. The oxidation was performed in water, with O as oxidant, without any additives. The surface characterization of the catalysts gave important information about their acid-base properties, which drive the selectivity of the reaction towards DFF. FFCA was formed from DFF at longer reaction times. Catalysts were studied by XPS and XRD before and after catalytic runs to identify the reason why they undergo reversible deactivation. XRD showed that MgO is hydrated to Mg(OH) , which, even if not leached out, changes the basic properties of the catalyst that becomes less active after some time. Calcination of the recovered catalyst allows recovery of its initial activity. The catalyst is thus recoverable (>99 %) and reusable. The use of mixed oxides allows tuning of the basicity of the catalysts, avoiding the need for external bases for efficient and selective conversion of 5-HMF and waste formation, resulting in an environmentally friendly, sustainable process.

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Oxidation of 5-hydroxymethyl furfural to 2,5-diformylfuran in aqueous media over heterogeneous manganese based catalysts

Cited by 64 publications

References 34 publications

Ru-(Mn-M)OX Solid Base Catalysts for the Upgrading of Xylitol to Glycols in Water

Ru-(Mn-M)OX Solid Base Catalysts for the Upgrading of Xylitol to Glycols in Water

An efficient approach to produce 2,5‐diformylfuran from 5‐hydroxymethylfurfural using air as oxidant

Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran or 2‐Formyl‐5‐furancarboxylic Acid in Water by using MgO⋅CeO₂ Mixed Oxides as Catalysts

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Oxidation of 5-hydroxymethyl furfural to 2,5-diformylfuran in aqueous media over heterogeneous manganese based catalysts

Cited by 64 publications

References 34 publications

Ru-(Mn-M)OX Solid Base Catalysts for the Upgrading of Xylitol to Glycols in Water

Ru-(Mn-M)OX Solid Base Catalysts for the Upgrading of Xylitol to Glycols in Water

An efficient approach to produce 2,5‐diformylfuran from 5‐hydroxymethylfurfural using air as oxidant

Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran or 2‐Formyl‐5‐furancarboxylic Acid in Water by using MgO⋅CeO2 Mixed Oxides as Catalysts

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Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran or 2‐Formyl‐5‐furancarboxylic Acid in Water by using MgO⋅CeO₂ Mixed Oxides as Catalysts