Selective oxidation of 5-hydroxymethyl furfural over non-precious metal heterogeneous catalysts

Neaţu, Florentina; Marin, Roxana Simona; Florea, Mihaela; Petrea, Nicoleta; Pavel, Octavian Dumitru; Pârvulescu, Vasile I.

doi:10.1016/j.apcatb.2015.07.043

Cited by 123 publications

(76 citation statements)

References 47 publications

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“…Therefore, in this study, we propose to clarify some mechanistic aspects for the selective oxidation of p ‐cymene with O 2 in the presence of a Mn–Fe mixed‐oxide heterogeneous catalyst. This catalyst was chosen because Mn 2+ ions are one of the main components of the industrial catalyst for the oxidation of p ‐xylene to TA and because the incorporation of Fe 3+ ions in manganese oxide enhances its redox properties . The role of Mn in Co/Fe/O spinel‐type oxides as an electron/O 2− ion carrier in the chemical‐loop reforming of ethanol was also recently investigated, and Mn affects the redox properties of the spinel…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Terephthalic Acid by p‐Cymene Oxidation using Oxygen: Toward a More Sustainable Production of Bio‐Polyethylene Terephthalate

et al. 2016

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The synthesis of terephthalic acid from biomass remains an unsolved challenge. In this study, we conducted the selective oxidation of p-cymene (synthesized from biodegradable terpenes, limonene, or eucalyptol) into terephthalic acid over a Mn-Fe mixed-oxide heterogeneous catalyst. The impact of various process parameters (oxidant, temperature, reaction time, catalyst amount, oxygen pressure) on the selectivity to terephthalic acid was evaluated, and some mechanistic aspects were elucidated. An unprecedented synthesis of biobased terephthalic acid (51 % yield) in the presence of O is reported.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Terephthalic Acid by p‐Cymene Oxidation using Oxygen: Toward a More Sustainable Production of Bio‐Polyethylene Terephthalate

et al. 2016

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“…7 Among the studied heterogeneous catalysts are noteworthy those based on noble metals such as Pt, 8,9 Au, 10,11 and Ru. 12 However, it should be underlined that in most of the reported reaction procedures a base additive, essentially NaOH, KOH or Na 2 CO 3 , is required, [13][14][15] so only very few works applying base-free catalysts have been reported.…”

Section: Introductionmentioning

confidence: 99%

Direct catalytic effect of nitrogen functional groups exposed on graphenic materials when acting cooperatively with Ru nanoparticles

et al. 2017

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A number of inorganic carbonaceous materials (activated carbon, high surface area graphite and graphenic materials) have been used as supports of Ru nanoparticles in order to determine their catalytic properties in the base-free aqueous-phase oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). In particular, we have studied in detail reduced graphene oxide (rGO) and nitrogen doped reduced graphene oxide (NrGO), which are the support materials that produce more selective ruthenium catalysts. Also the effects of different metal precursors used in the preparation of the Ru nanocrystallites have been evaluated. Both support materials and Ru catalysts were characterized by elemental analysis, nitrogen physisorption (BET), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The point of zero charge (PZC) for the graphenic materials was also determined. Interestingly the different supports significantly modify the catalytic performances, the graphenic materials being those that under our experimental reaction conditions produce the highest selectivity to FDCA. On these supports (rGO and NrGO) the highest HMF conversion was achieved by using triruthenium dodecacarbonyl as the ruthenium precursor. For the improved catalyst, Ru supported on NrGO, the yield of FDCA becomes close to 80%. This catalyst has been reused several times with neither loss of activity nor modification in selectivity values. Characterization data indicate these catalytic results can be correlated to the basic properties of the NrGO support as well as to the surface properties of Ru nanoparticles. These findings indicated that the metal precursor and the surface functional groups exposed on the support can modulate the catalytic properties, in particular amending the selectivity towards FDCA production.

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“…The average particle size of the Co-Mn-0.25 catalyst was approximately 6.5 nm (measured throughi maging software),w hichw as in ag ood agreement with ar ecent literature reporto faM n-modifiedc obalt oxide catalystp repared through solid-state grinding. [40] Thes urface base concentration of the Co-Mn-0.25 catalyst wase stimated to be 0.97 mmol g À1 , which was the highest among the other catalysts analyzed. Both techniques revealed that thesec atalysts contained both acidic and basic sites, as well as the same acid andb ase type.…”

Section: Characterization Of the Fresh And Spent Catalystsmentioning

confidence: 89%

“…[39] The acid-base properties of the catalyst were investigated by ammonia temperature programmed desorption (NH 3 -TPD) and CO 2 -TPD, and the results are presentedi nF igures S6 and S7. [40,15] This variation in the catalytic selectivity with calcination temperature( as shown in Figure 1) could be attributedt ot he variation in the structuralp roperties of the catalysts during thermal treatment (calcination). The total acidity and basicity of the catalysts were measured from the peak areas of the TPD profile and presented in Ta ble S3.A ll catalysts contained both weak and strong acid sites and the Co-Mn-0.25 catalyste xhibited al ower acidity than the others.C onversely,t he CO 2 -TPD profile of the MnO x catalysts howed as harpC O 2 desorption peak in the high-temperatureregion,whereas the Co-Mn catalysts exhibited adistribution of basic sites in the low-and high-temperature regions, indicating the presence of strong basic sites on the catalyst surface.…”

Section: Characterization Of the Fresh And Spent Catalystsmentioning

confidence: 93%

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

et al. 2018

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A highly active and inexpensive Co-Mn mixed-oxide catalyst was prepared and used for selective oxidation of 5-hydroxymethylfurfural (HMF) into 2, 5-furandicarboxylic acid (FDCA). Co-Mn mixed-oxide catalysts with different Co/Mn molar ratios were prepared through a simple solid-state grinding method-a low-cost and green catalyst preparation method. The activity of these catalysts was evaluated for selective aerobic oxidation of HMF into FDCA in water. Excellent HMF conversion (99 %) and FDCA yield (95 % ) were obtained under the best reaction conditions (i.e., 120 °C, 5 h, Co-Mn mixed-oxide catalyst with a Co/Mn molar ratio of 0.25 calcined at 300 °C (Co-Mn-0.25) and 1 MPa O ). The catalyst could be reused five times without a significant decrease in activity. The results demonstrated that the catalytic activity and selectivity of the Co-Mn mixed-oxide catalysts prepared through solid-state grinding were superior to the same Co-Mn catalyst prepared through a conventional coprecipitation method. The high catalytic activity of the Co-Mn-0.25 catalyst was attributed to its high lattice oxygen mobility and the presence of different valence states of manganese. The high activity and low cost of the Co-Mn mixed-oxide catalysts prepared by solid-state grinding make it promising for industrial application for the manufacturing of polyethylene furanoate, a bioreplacement for polyethylene terephthalate, from sustainable bioresources.

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Selective oxidation of 5-hydroxymethyl furfural over non-precious metal heterogeneous catalysts

Cited by 123 publications

References 47 publications

Synthesis of Terephthalic Acid by p‐Cymene Oxidation using Oxygen: Toward a More Sustainable Production of Bio‐Polyethylene Terephthalate

Synthesis of Terephthalic Acid by p‐Cymene Oxidation using Oxygen: Toward a More Sustainable Production of Bio‐Polyethylene Terephthalate

Direct catalytic effect of nitrogen functional groups exposed on graphenic materials when acting cooperatively with Ru nanoparticles

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

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