Base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over a Pt/C–O–Mg catalyst

Han, Xuewang; Geng, Li; Guo, Yong; Jia, Ru; Liu, Xiaohui; Zhang, Yongguang; Wang, Yanqin

doi:10.1039/c5gc02114f

Cited by 140 publications

(88 citation statements)

References 40 publications

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“…The XPS spectrum of Pt@Dowex‐Na in the Pt 4 f region, in which the usual asymmetric doublet of Pt was observed, is shown in Figure . The peaks were deconvoluted in one component only, the binding energies of which are in agreement with those previously reported for metallic Pt [Pt 0 4 f 7/2 (71.1±0.1) eV, spin‐orbit coupling 4.0 eV] . No peaks attributable to other oxidation states were detected.…”

Section: Methodssupporting

confidence: 86%

Continuous‐Flow Oxidation of HMF to FDCA by Resin‐Supported Platinum Catalysts in Neat Water

2019

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The oxidation reaction of 5‐hydroxymethylfurfural to the bioplastic monomer 2,5‐furandicarboxylic acid over heterogenous resin‐supported Pt catalysts was investigated in detail, under continuous flow, base‐free conditions, and in neat water. The product was continuously obtained in 99 % yield by running the reaction at 120 °C, 303 s residence time, 1.2 mL min−1 O2 flow rate, and 7.7 bar O2 pressure. The product was isolated with a high space‐time‐yield of 46.0 g L−1 h−1 without purifications or acid/base treatments.

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Section: Methodssupporting

confidence: 86%

Continuous‐Flow Oxidation of HMF to FDCA by Resin‐Supported Platinum Catalysts in Neat Water

2019

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“…The carbonyl/quinone and/or phenol groups on CNT surfaces are crucial in the enhancement of HMF adsorption as well as reaction intermediates from the water phase which might facilitate hydrogen transfer. Han et al also realized basefree aerobic oxidation of HMF to FDCA using a novel Pt/C _ O _ Mg catalyst for ten cycles with little loss of activity 50) . .…”

Section: Oxidative Transformations Of Hmfmentioning

confidence: 99%

金属担持触媒を用いたバイオマス由来アルコールの選択的酸化反応

Nishimura

Ebitani

2017

J. Jpn. Petrol. Inst.

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Simple transformation of sustainable biomass-resources to value-added chemicals and fuels has become important to diminish our heavy reliance on decreasing petroleum resources. Biomass-derived materials with hydroxyl groups such as 5-hydroxymethylfurfural (HMF) and glycerol can be obtained from sugars directly and transesterification of triglycerides with methanol as by-products, respectively. These chemicals are versatile starting materials because hydroxyl groups can be easily converted to afford value-added chemicals and fuels under oxidative/reductive conditions using supported metal catalysts. This review overviews recent studies on supported metal catalyzed oxidation reactions of HMF, glycerol and biomass-derived aliphatic a,w-diols together with our research to develop highly efficient catalytic systems for bio-refining, based on petroleum conversion and nanotechnologies. Especially, role of external bases in the selective oxidation of biomass-derived alcohols will be discussed. We found that external base-free oxidation of HMF and glycerol is possible if basic supports are used. The activity of alloyed metal nanoparticles for selective oxidation of aliphatic a,w-diols to w-hydroxycarboxylic acids in basic aqueous media at high-pH value is also demonstrated. Keywords5-Hydroxymethylfurfural, Glycerol, Aliphatic a,w-diols, Selective oxidation, Supported metal catalyst, Bimetallic nanoparticle DOI: doi.org/10.1627/jpi.60.72 To whom correspondence should be addressed. E-mail: ebitani@jaist.ac.jp using molecular oxygen as the oxidant 18) . For example, Sahu and Dhepe compared the catalytic performance of various metal-oxide supported Pt catalysts with 0.1 MPa O2 in the presence of NaOH (1 equiv.) at 348 K for 12 h 19) . Under the same reaction conditions, Pt/ γ-A12O3, Pt/ZrO2, and Pt/C showed high catalytic activity with FDCA yields of 96, 94, and 89 %, respectively. In contrast, Pt supported on reducible TiO2 and CeO2 produced little FDCA (2 % and 8 % yields) even with ca. 100 % HMF conversion. Cai et al. reported superior catalytic performance of Au nanoparticles (1 nm size) encapsulated in the supercage of HY zeolite for selective HMF oxidation into FDCA with 99 % FDCA yield in water under 0.3 MPa O2 in the presence of NaOH at 333 K 20) . It has been reported the structures of Au nanoparticles and HY zeolite are stable under these conditions, and the Au/HY catalyst is reusable for several catalytic cycles. Negatively-charged Au nanoparticles may be responsible for this excellent catalytic performance.Pasini et al. reported AuCu bimetallic alloy catalyst (4.4 nm diameter) supported on TiO2 for HMF oxidation to FDCA under 1 MPa O2 in the presence of NaOH at 368 K to afford 99 % FDCA yield with complete HMF conversion 21) . A strong synergistic effect is evident with the addition of Cu to Au, especially for catalyst reusability without significant leaching of metal nanoparticles. However, stability test experiments showed the final product is mainly 5-hydroxymethyl-2-furancaoboxylic acid (HMFCA) instead...

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“…Other than Au catalysts, Pt‐, Ru‐ and Pd‐based catalysts were also reported in the oxidation of 5‐HMF. In this direction, Pt‐based catalysts have exhibited high efficiency for the complete oxidation of 5‐HMF to FDCA, however, in the presence of a strong base and high pressure of O 2 or air . For example, recently Han et al.…”

Section: Introductionmentioning

confidence: 99%

“…For example, recently Han et al. explored the oxidation of 5‐HMF to FDCA over Pt/C− O −Mg catalyst at 110 °C and 1.0 MPa O 2 gas . On the other side, Ru catalyst showed only partial oxidation of 5‐HMF to DFF at 110 °C with high pressure of O 2 , 2.0 MPa, using organic solvents .…”

Section: Introductionmentioning

confidence: 99%

“…also reported in the oxidation of 5-HMF.I nt his direction, Ptbased catalysts have exhibited high efficiency for the complete oxidation of 5-HMF to FDCA, however,i nt he presenceo f as trong base and high pressure of O 2 or air. [39,[48][49][50][51][52][53][54][55] [55] On the other side, Ru catalysts howed only partial oxidation of 5-HMF to DFF at 110 8Cw ith high pressure of O 2 , 2.0 MPa, using organic solvents. [56,57] Similarly to Au, Pd catalysts also showed high activity towards the oxidation of alcohols and carbonyl compounds.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Aerial Oxidation of Biomass‐Derived Furans to Furan Carboxylic Acids in Water over Bimetallic Nickel–Palladium Alloy Nanoparticles

et al. 2016

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Bimetallic Ni1−xPdx (0.10≤x≤0.75) alloy nanoparticle catalysts were synthesised and successfully employed for the catalytic aerial oxidation of biomass‐derived furans, such as 2‐furfuraldehyde (furfural), 2‐furfuryl alcohol (furfuryl alcohol), 5‐hydroxymethyl‐2‐furfural (5‐HMF), 5‐methyl‐2‐furfural (MF) and 5‐methyl‐2‐furfuryl alcohol (MFA), to selectively afford the corresponding furan carboxylic acids (2‐furoic acid, furan‐2,5‐dicarboxylic acid (FDCA) and 5‐methyl‐2‐furoic acid (MFCA)) in water at 80 °C. Among the studied Ni1−xPdx nanoparticle catalysts, Ni0.90Pd0.10 nanoparticle catalyst outperformed the others, achieving high yields of the corresponding furan carboxylic acid products. The presence of Ni in the Ni1−xPdx nanoparticle catalysts was advantageous, because it not only enhanced the catalytic activity for the facile oxidation of biomass‐derived furans using aerial oxygen to achieve high catalytic turnover, but also provided excellent stability to the Ni0.90Pd0.10 nanoparticle catalyst towards air and water and thus significantly enhanced its recyclability (up to 10 catalytic runs). The experiments revealed that the catalytic oxidation of 5‐HMF proceeded by the initial oxidation of the formyl group to carboxylic acid, and, subsequently, the conversion of alcohol to carboxylic acid via the formyl group to form FDCA. Moreover, the one‐pot direct transformation of fructose to furan carboxylic acid products (such as FDCA) was also achieved by using the Ni0.90Pd0.10 nanoparticle catalyst.

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Base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over a Pt/C–O–Mg catalyst

Abstract: Base-free aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) was realized successfully based on the design of a novel Pt/C–O–Mg catalyst.

Cited by 140 publications

References 40 publications

Continuous‐Flow Oxidation of HMF to FDCA by Resin‐Supported Platinum Catalysts in Neat Water

Continuous‐Flow Oxidation of HMF to FDCA by Resin‐Supported Platinum Catalysts in Neat Water

金属担持触媒を用いたバイオマス由来アルコールの選択的酸化反応

Catalytic Aerial Oxidation of Biomass‐Derived Furans to Furan Carboxylic Acids in Water over Bimetallic Nickel–Palladium Alloy Nanoparticles

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