Multifunctional nanocomposites with non-precious metals and magnetic core for 5-HMF oxidation to FDCA

Tîrşoaga, Alina; Fergani, Magdi El; Nuns, Nicolás; Simon, Pardis; Granger, Pascal; Pârvulescu, Vasile I.; Coman, Simona M.

doi:10.1016/j.apcatb.2020.119309

Cited by 57 publications

(26 citation statements)

References 76 publications

(90 reference statements)

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“…The failure of the above attempts for the production of FDCA made us move from the WO conditions to a catalytic oxygen transfer methodology, which requires oxygen donors such as H 2 O 2 or RO 2 H. Although more benign and, therefore, a preferable oxygen donor, H 2 O 2 , in combination with acetonitrile as a solvent, led to no oxidation products. A similar behavior has recently been reported by some of us in the HMF oxidation [ 60 ] and by Choudhary et al [ 61 ] in the solvent-free oxidation of benzyl alcohol to benzaldehyde. Therefore, all reactions were made by using t -butyl hydroperoxyde (t-BOOH) as an oxygen transfer agent and the main obtained results are presented in Table 5 .…”

Section: Resultssupporting

confidence: 87%

“…Among the investigated catalysts, these displayed the highest base/acid sites ratio, with a domination of the basic sites ( Table 3 ). These high basic OH − ions catalyze the formation of geminal diols from aldehyde and water, while the Nb + species catalyze the dehydrogenation steps, in accordance with a mechanism proposed by Donoeva et al [ 63 ] for the HMF oxidation on gold nanoparticles supported on basic carbon materials and recently confirmed in our group for 10M@xNb@MNP (where M=Co, Mn, and Fe) catalysts [ 60 ].…”

Section: Resultssupporting

confidence: 85%

“…Interestingly enough, the DFF intermediate was identified as only aleatory and in very low amounts. Accordingly, the reasonable reaction pathway for the HMF oxidation over these catalysts should follow the HMF → HMFCA → FFCA → FDCA sequence that is similar to that for supported Au and Pd catalysts [ 62 ] and for recently reported 10M@xNb@MNP (where M = Co, Mn and Fe) catalysts [ 60 ]. This route indicates a preferential adsorption of −CHO side chain of HMF, which requires the presence of basic sites and positive surface of the catalyst [ 63 ].…”

Section: Resultsmentioning

confidence: 63%

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Optimized Nb-Based Zeolites as Catalysts for the Synthesis of Succinic Acid and FDCA

et al. 2020

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Nb(0.05 moles%)-zeolites prepared via a post synthesis methodology (BEA, Y, ZSM-5), or a direct sol-gel method (Silicalite-1) were investigated in the hydroxymethylfurfural (HMF) oxidation by both molecular oxygen, in aqueous phase, and organic peroxides, in acetonitrile. The catalysts prepared through the post synthesis methodology (i.e., Nb-Y5, Nb-ZSM25, Nb-Y30, Nb-BEA12, and Nb-BEA18) displayed a mono-modal mesoporosity and contain residual framework Al-acid sites, extra framework isolated Nb(V)O-H and Nb2O5 pore-encapsulated clusters, while Nb-Sil-1, prepared through a direct synthesis procedure, displayed a bimodal micro-mesoporosity and contains only –Nb = O species. These modified zeolites behave as efficient catalysts in both HMF/glucose wet oxidation to succinic acid (SA) and HMF oxidation with organic peroxides to the 2, 5-furandicarboxylic acid (FDCA). The catalytic behavior of these catalysts, in terms of conversion and especially the selectivity, mainly depended on the base/acid sites ratio. Thus, the HMF/glucose wet oxidation occurred with a total conversion and a selectivity to SA of 37.7% (from HMF) or 69.1% (from glucose) on the Nb-Y5 catalyst, i.e., the one with the lowest base/acid sites ratio. On the contrary, the catalysts with the highest base/acid sites ratio, i.e., Nb-ZSM25 and Nb-Sil-1, afforded a high catalytic efficiency in HMF oxidation with organic peroxides, in which FDCA was produced with selectivities of 61.3–63.8% for an HMF conversion of 96.7–99.0%.

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Section: Resultssupporting

confidence: 87%

Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 63%

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Optimized Nb-Based Zeolites as Catalysts for the Synthesis of Succinic Acid and FDCA

et al. 2020

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“…More specifically, the oxidative transformations of HMF are key routes toward a wide variety of chemicals and biofuels ( Gao et al, 2020 ; Hong et al, 2021 ). In particular, FDCA, which is derived from the successive oxidation of HMF, is a substitute for petroleum-derived terephthalic acid, which can be employed in the preparation of polyethylene furanoate (PEF) to ultimately alleviate the shortage of resources and relieve environmental stress ( Tirsoaga et al, 2020 ).…”

Section: Introductionmentioning

confidence: 99%

Production of the 2,5-Furandicarboxylic Acid Bio-Monomer From 5-Hydroxymethylfurfural Over a Molybdenum-Vanadium Oxide Catalyst

et al. 2022

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2, 5-Furandicarboxylic acid (FDCA) is an important bio-monomer that can potentially replace terephthalic acid to synthesize degradable polyesters. Efficient selective oxidation of biomass-based 5-hydroxymethylfurfural (HMF) to FDCA has been a significant but challenging work in the past decades. In this study, a novel molybdenum-vanadium oxide (Mo-V-O) catalyst was prepared by a simple method and showed excellent catalytic activity for converting HMF to FDCA. A high FDCA selectivity of 94.5 and 98.2% conversion of HMF were achieved under the optimal conditions with tert-butyl hydroperoxide as the oxidant. FT-IR, SEM, XRD and TG were applied to investigate the properties of Mo-V-O catalyst. After fitting experimental data with the first-order kinetics equation, the evaluated apparent activation energies of HMF oxidation were obtained. The experimental design and study were carried out by response surface methodology (RSM) to test the effects of reaction conditions on the catalytic process.

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“…[1][2][3][4][5][6][7] Among a broad spectrum of biomassderived molecules, 5-hydroxymethylfurfural (HMF) obtained from acid-catalyzed hydrolysis of cellulose, has attracted the significant attention of researchers due to its versatile applications in fuel [8] pharmaceutical [9] and polymer [10] industries. Selective oxidation of HMF affords 2,5-furandicarboxylic acid [11][12][13][14][15][16] (FDCA) which is an important raw material used for the synthesis of polyethylene furanoate (PEF), a bio-based renewable polymer, through a simple polymerization with ethylene glycol. [17] PEF is identified as a suitable replacement for the petroleum-derived polyethylene terephthalate (PET).…”

Section: Introductionmentioning

confidence: 99%

Ultrafine Copper Oxide Particles Dispersed on Nitrogen‐Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass‐Derived 5‐Hydroxymethylfurfural

2021

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One-pot synthesis of furan-2,5-dimethylcarboxylate (FDMC) from 5-hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres (CuO/NÀ CÀ HNSs) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/NÀ CÀ HNSs was prepared through a template protection-sacrifice strategy using SiO 2 as a sacrificial template and histidine as the precursor for N and C. N-doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m 2 /g, the CuO/ NÀ CÀ HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP 3 CÀ H bond functionalization is also demonstrated using the same catalyst.

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Multifunctional nanocomposites with non-precious metals and magnetic core for 5-HMF oxidation to FDCA

Cited by 57 publications

References 76 publications

Optimized Nb-Based Zeolites as Catalysts for the Synthesis of Succinic Acid and FDCA

Optimized Nb-Based Zeolites as Catalysts for the Synthesis of Succinic Acid and FDCA

Production of the 2,5-Furandicarboxylic Acid Bio-Monomer From 5-Hydroxymethylfurfural Over a Molybdenum-Vanadium Oxide Catalyst

Ultrafine Copper Oxide Particles Dispersed on Nitrogen‐Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass‐Derived 5‐Hydroxymethylfurfural

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