Effects of Water on the Copper‐Catalyzed Conversion of Hydroxymethylfurfural in Tetrahydrofuran

Liu, Yifei; Mellmer, Max A.; Alonso, David Martín; Dumesic, James A.

doi:10.1002/cssc.201501122

Cited by 48 publications

(32 citation statements)

References 25 publications

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“…To wards the upgradationoffurans, monometallic and bimetallic Ru based catalysts have also shown high efficacy towards the hydrogenation of furans. [113,[115][116][117][118][119][120][121][122][123] Nagpuree tal. explored hydrogenolysis of HMF to DMFo ver Ru containing hydrotalcite(HT) catalysts and achieved complete conversion of HMF to DMF at 220 8Ci n4h.…”

Section: Catalytic Hydrogenation And/or Hydrogenolysis Of Biomass-dermentioning

confidence: 99%

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

2018

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Catalytic transformation of biomass‐derived compounds to different platform chemicals and liquid fuel is a prominent way to reduce the global dependence on fossil resources. In past few decades, biomass‐derived furans such as 2‐furfuraldehyde (furfural) and 5‐hydroxymethyl‐2‐furfural (HMF) have received outstanding attention because of their wide applications in the production of various industrially important value‐added chemicals and fuel components. Various catalytic systems and methodologies have been extensively explored for the transformation of these furans to a wide range of products including open ring diketones, ketoacids, alcohols and long chain alkanes. This Review is aimed to provide an extensive overview of the recent developments of several high‐performing heterogeneous catalysts for the catalytic upgradation of the key biomass‐derived furans (furfural and HMF) to value‐added chemicals. Moreover, the role of these catalysts in the catalytic transformations including hydrogenation, decarbonylation, oxidation, hydrogenolysis and ring opening reactions, and the mechanistic pathways are also highlighted in this Review.

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Section: Catalytic Hydrogenation And/or Hydrogenolysis Of Biomass-dermentioning

confidence: 99%

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

2018

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“…A fitting of the apparent rate constants was performed by least‐square minimization, according to a mechanism based on the following steps:…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, as DMTHF appears in the last stage, once DMF has been produced and accumulated, and other hydrogenation products have not been detected, we will suppose that the hydrogenation of the furan ring does not take place to a large extent on the minor intermediate products. [31] A fitting of the apparent rate constants was performed by least-square minimization, according to a mechanism based on the following steps: [31,32] -HMF being consumed by paths 1 and 2, its consumption was fitted using a first-rate law of rate constant (k 1,app + k 2,app ):…”

Section: Kinetics Of the Reactionmentioning

confidence: 99%

Hydroconversion of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran and 2,5‐Dimethyltetrahydrofuran over Non‐promoted Ni/SBA‐15

et al. 2020

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The selective hydroconversion of 5‐hydroxymethylfurfural (HMF) to biofuels is currently highly sought‐for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non‐promoted Ni/SBA‐15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5‐dimethylfuran (DMF) and to 2,5‐dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5‐methylfurfural (MFFR) as intermediate, though the route via 2,5‐bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates.

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“…Therefore, selective transformations of these two functional groups with conventional reactions such as oxidation, reduction, hydrogenolysis and condensation have been widely investigated to produce chemicals and fuels 13) . For example, HMFbased diols of 2,5-bis(hydroxymethyl)furan (BHMF) 14), 15) a n d 2,5-b i s ( h y d r o x y m e t h y l ) t e t r a h y d r o f u r a n (BHMTHF) 16), 17) are candidates for biomass-derived monomer sources. HMF can also be oxidized into 2,5-diformylfuran (DFF) and/or 2,5-furandicarboxylic acid (FDCA) (Scheme 1).…”

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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Effects of Water on the Copper‐Catalyzed Conversion of Hydroxymethylfurfural in Tetrahydrofuran

Cited by 48 publications

References 25 publications

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

Hydroconversion of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran and 2,5‐Dimethyltetrahydrofuran over Non‐promoted Ni/SBA‐15

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

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