- Mechanistic Studies on the Photooxidation of 5-Hydroxymethylfurfural by Polyoxometalate Catalysts and Atmospheric Oxygen
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Efficient oxidation of 5-hydroxymethylfurfural (HMF) to corresponding furanic products represents an important research focus of biomass valorization, recent research on polyoxometalates (POMs)-catalyzed aerobic oxidation of HMF usually requires high temperature and sometimes high O2/air pressure. In this work, we report a mild and green approach to photocatalytically transform HMF into various furanic products using atmospheric oxygen as oxidant and POMs as photocatalysts. The influence of different POMs, light sources, and additives were systematically investigated by various experimental and spectroscopic results. Under minimally optimized conditions, 88.0 % HMF can be efficiently photooxidized with as high as 70.2 % furanic yield by TBA-W10 catalyst after 2 h irradiation of 365 nm UV light when coupling with TEMPO and Na2CO3 as additives. Finally, detailed mechanistic pathways of HMF photooxidation have been proposed to illustrate the transformation of HMF to various furanic products. This work provides some insightful guidelines for photooxidation of biomass-derived platform chemicals to value-added products under efficient, mild, and green conditions, exhibiting potential practical applications in the future.
- Li, Zheng,Zhang, Mo,Xin, Xing,Lv, Hongjin
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- Paired electrocatalytic hydrogenation and oxidation of 5-(hydroxymethyl)furfural for efficient production of biomass-derived monomers
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Electrochemical conversion of biomass-derived compounds is a promising route for sustainable chemical production. Herein, we report unprecedentedly high efficiency for conversion of 5-(hydroxymethyl)furfural (HMF) to biobased monomers by pairing HMF reduction and oxidation half-reactions in one electrochemical cell. Electrocatalytic hydrogenation of HMF to 2,5-bis(hydroxymethyl)furan (BHMF) was achieved under mild conditions using carbon-supported Ag nanoparticles (Ag/C) as the cathode catalyst. The competition between Ag-catalyzed HMF hydrogenation to BHMF and undesired HMF hydrodimerization and hydrogen evolution reactions was sensitive to cathode potential. Also, the carbon support material in Ag/C was active for HMF reduction at strongly cathodic potentials, leading to additional hydrodimerization and low BHMF selectivity. Accordingly, precise control of the cathode potential was implemented to achieve high BHMF selectivity and efficiency. In contrast, the selectivity of HMF oxidation facilitated by a homogeneous electrocatalyst, 4-acetamido-TEMPO (ACT, TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl), together with an inexpensive carbon felt electrode, was insensitive to anode potential. Thus, it was feasible to conduct HMF hydrogenation to BHMF and oxidation to 2,5-furandicarboxylic acid (FDCA) in a single divided cell operated under cathode potential control. Electrocatalytic HMF conversion in the paired cell achieved high yields of BHMF and FDCA (85% and 98%, respectively) and a combined electron efficiency of 187%, corresponding to a nearly two-fold enhancement compared to the unpaired cells.
- Chadderdon, Xiaotong H.,Chadderdon, David J.,Pfennig, Toni,Shanks, Brent H.,Li, Wenzhen
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- Alkaline ionic liquid modified Pd/C catalyst as an efficient catalyst for oxidation of 5-hydroxymethylfurfural
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Conversion of HMF into FDCA was carried out by a simple and green process based on alkaline ionic liquid (IL) modified Pd/C catalyst (Pd/C-OH-). Alkaline ionic liquids were chosen to optimize Pd/C catalyst for special hydrophilicity and hydrophobicity, redox stability, and unique dissolving abilities for polar compounds. The Pd/C-OH- catalyst was successfully prepared and characterized by SEM, XRD, TG, FT-IR, and CO2-TPD technologies. Loading of alkaline ionic liquid on the surface of Pd/C was 2.54 mmol·g-1. The catalyst showed excellent catalytic activity in the HMF oxidation after optimization of reaction temperature, reaction time, catalyst amount, and solvent. Supported alkaline ionic liquid (IL) could be a substitute and promotion for homogeneous base (NaOH). Under optimal reaction conditions, high HMF conversion of 100% and FDCA yield of 82.39% were achieved over Pd/C-OH- catalyst in water at 373 K for 24 h.
- Bin, Zou,Xueshan, Chen,Jiaojiao, Xia,Cunshan, Zhou
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- Catalytic carbonylation of renewable furfural derived 5-bromofurfural to 5-formyl-2-furancarboxylic acid in oil/aqueous bi-phase system
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Utilizing sustainable biomass to partly replace the fossil feedstock as the carbon source of chemical industry has been well acknowledged because of the scarcity of the fossil resources. This work introduced a novel route for the synthesis of 5-formyl-2-furancarboxylic acid (FFA) from renewable furfural derived 5-bromofurfural, which achieves the transformation of furfural based platform molecule to the products having multifunctional groups, thus opens up its potential market in polymeric applications. Under the optimized conditions, this new catalysis provided up to 99% yield of FFA through oil/aqueous bi-phasic carbonylation. Remarkably, the FFA product could be feasibly separated from the remaining substrate and catalyst because of its aqueous solubility in the biphasic system, giving 95% isolated yield in gram scale synthesis. Currently, FFA is an unstable intermediate in hydroxymethylfurfural (HMF) oxidations; in viewing of that furfural is industrially produced from bulky agroforestrial byproducts, this furfural based route to FFA through catalytic carbonylation has offered an opportunity for its production in large scale.
- Shen, Guanfei,Zhang, Sicheng,Lei, Yu,Shi, Jiaqi,Xia, Yu,Mei, Fuming,Chen, Zhuqi,Yin, Guochuan
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- Hybrid Conversion of 5-Hydroxymethylfurfural to 5-Aminomethyl-2-furancarboxylic acid: Toward New Bio-sourced Polymers
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Hybrid catalysis, which combines chemo- and biocatalytic benefits, is an efficient way to address green chemistry principles. 5-Hydroxymethylfurfural (HMF) is a versatile building block in numerous industrial applications. To date, few studies have described the production of its amine derivatives and their polymers. Finding a good methodology to directly transform HMF to 5-aminomethyl-2-furancarboxylic acid (AMFC) therefore represents an important challenge. After selecting the best oxidation catalyst for HMF conversion to 5-aldehyde-2-furancarboxylic acid and immobilizing a transaminase onto a solid carrier, we implemented the first one-pot/two-steps hybrid catalytic process to produce AMFC (77 % yield); this is the most efficient AMFC catalytic production method from HMF reported to date. This process also produced 2,5-furandicarboxylic acid (21 % yield) as a major secondary product that can be applied to polymer syntheses such as polyethylene furanoate. Herein, we report a novel way to access new biosourced polymers based on HMF oxidized and aminated derivatives.
- Lancien, Antoine,Wojcieszak, Robert,Cuvelier, Eric,Duban, Matthieu,Dhulster, Pascal,Paul, Sébastien,Dumeignil, Franck,Froidevaux, Renato,Heuson, Egon
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- Oxidation of 5-hydroxymethyl furfural to 2,5-diformylfuran in aqueous media over heterogeneous manganese based catalysts
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Manganese-copper layered double hydroxides prepared following a conventional procedure were investigated for the selective oxidation of 5-hydroxymethyl-2-furfural into 2,5-diformylfuran. After checking the effect of the different parameters it has been found that a composition corresponding to Mn0.70Cu0.05Al0.25, of the catalyst already calcined, led to the highest conversion (90%) and selectivity (87% in DFF). Noteworthy, this has been achieved working under mild aqueous conditions (90?°C and 8?bars O2). The performances of the catalysts were closely associated to the strength of the basic sites.
- Nea?u,Petrea,Petre,Somoghi,Florea,Parvulescu
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- Chloroperoxidase-catalyzed oxidation of 5-hydroxymethylfurfural
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Chloroperoxidase (CPO) catalyzes the oxidation of 5-hydroxymethylfurfural (HMF) with hydrogen peroxide as the oxidant. The reaction proceeds with 60-74% selectivity to furan-2,5-dicarboxaldehyde (FDC). The main byproduct is 5-hydroxymethyl-2-furancarboxylic acid (HFCA); a minor amount of 5-formylfuran-2-carboxylic acid (FFCA) was also detected. When H218O2 was used a virtually quantitative incorporation of 18O was observed in the HFCA product, whereas no 18O was incorporated from H218O. Hence, the CPO-catalyzed oxidation of aldehydes to acids proceeds with direct oxygen transfer from the iron-oxo complex of CPO. Controlling the H2O2-addition with a H2O2-stat facilitated the reaction procedure and a conversion of 87% of HMF was reached within 21 min.
- Van Deurzen,Van Rantwijk,Sheldon
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- Influence of support on the aerobic oxidation of HMF into FDCA over preformed Pd nanoparticle based materials
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Here, the preparation and evaluation of supported nanoparticle based catalytic material is reported. Polyvinylpyrrolidone (PVP) stabilized palladium nanoparticles with a mean particle size of 1.8 nm were synthesized in ethylene glycol and subsequently deposited onto different metal oxide supports (TiO 2, γ-Al2O3, KF/Al2O 3, and ZrO2/La2O3). The prepared catalysts were applied to the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in aqueous solution at atmospheric pressure (T = 90 °C, pO2 = 1 bar) and compared regarding their catalytic performance and stability. The highest FDCA yield (>90%) was obtained for the Pd/ZrO2/La2O3 catalysts which additionally showed a relatively stable catalytic performance when the material was reused. Various characterization methods including XRD, TEM, XPS, and AAS were applied to obtain information about the Pd NP before and after utilization in HMF oxidation. For the Pd/TiO2 the least changes in Pd NP structure were observed after using the material in HMF oxidation. This was attributed to a stronger interaction between the Pd NP and the TiO2 support compared to other supports used in the studies.
- Siyo, Baraa,Schneider, Matthias,Radnik, J?rg,Pohl, Marga-Martina,Langer, Peter,Steinfeldt, Norbert
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- Hydrotalcite-supported gold-nanoparticle-catalyzed highly efficient base-free aqueous oxidation of 5-hydroxymethylfurfural into 2,5- furandicarboxylic acid under atmospheric oxygen pressure
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Green synthesis of 2,5-furandicarboxylic acid, one of the most important chemical building blocks from biomass, via oxidation of 5-hydroxymethylfurfural has been demonstrated using hydrotalcite-supported gold nanoparticle catalyst in water at 368 K under atmospheric oxygen pressure without addition of homogeneous base. The Royal Society of Chemistry.
- Gupta, Navneet Kumar,Nishimura, Shun,Takagaki, Atsushi,Ebitani, Kohki
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- Synthesis and characterization of an α-MoO3nanobelt catalyst and its application in one-step conversion of fructose to 2,5-diformylfuran
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In this study, α-MoO3nanobelts were successfully synthesized by a simple, green and economic hydrothermal method and applied as a bifunctional catalyst for one-step conversion of fructose to DFF under atmospheric air. The structure of the as-prepared α-MoO3catalyst was characterized in detail by SEM, TEM, EDS, XRD, XPS, H2-TPR and NH3-TPD to better understand the relationship between structure and performance. α-MoO3nanobelts exhibited high catalytic activities for production of DFF from HMF and fructose in atmospheric air. Under optimized reaction conditions, high DFF yields of 97.2% and 78.3% were obtained by using HMF and fructose as raw materials, respectively. Furthermore, a plausible reaction pathway was proposed for the selective oxidation of HMF to DFF according to the experimental and catalyst characterization results. Importantly, α-MoO3is a robust catalyst that can be used at least five times without obvious loss in its catalytic activity. In brief, α-MoO3is an easily-prepared, eco-friendly, low cost and highly effective catalyst which has potential application in one-step conversion of fructose to DFF under atmospheric air.
- Yang, Zhenzhen,Zhu, Bangchong,He, Yuhan,Zhang, Genlei,Cui, Peng,He, Jianbo
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- Selective synthesis of 2-furoic acid and 5-hydroxymethyl-2-furancarboxylic acid from bio-based furans by recombinant Escherichia coli cells
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Upgradation of bio-based furans into chemicals and biofuels has received great interest recently. In this work, we reported selective synthesis of furan carboxylic acids from the corresponding aldehydes by recombinant Escherichia coli cells expressing 3-succinoylsemialdehyde-pyridine dehydrogenase (SAPDH) from Comamonas testosteroni SC1588. The effects of induction and reaction conditions on whole-cell catalytic oxidation of furfural (FF) were studied. High temperature induction resulted in decreased activities of recombinant cells, likely due to improper protein folding. Nonetheless, recombinant cells induced under high temperature enable the byproduct furfuryl alcohol to be faster re-oxidized into 2-furoic acid (FCA) than those induced under low temperature. So the yield and selectivity of FCA were improved significantly by using high temperature induction, at expense of slightly longer reaction periods. The activities of recombinant cells highly depended on pH. The tolerant levels of this recombinant strain toward FF and 5-hydroxymethylfurfural (HMF) were approximately 100 mM. FCA and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) were obtained with the yields of 95–98%. FCA of up to 147 mM was produced by a fed-batch strategy, in a quantitative yield. In addition, most aromatic aldehydes tested were transformed into the target carboxylic acids by this biocatalytic method, with the yields up to 100%.
- Shi, Sai-Sai,Zhang, Xue-Ying,Zong, Min-Hua,Wang, Chuan-Fu,Li, Ning
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- Efficient Aerobic Oxidation of 5-Hydroxymethylfurfural in Aqueous Media with Au–Pd Supported on Zinc Hydroxycarbonate
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Bimetallic catalysts with Au–Pd supported on zinc hydroxycarbonate (ZOC) were synthesized by a simple deposition–precipitation method and analyzed by transmission electron microscopy to have a narrow-size distribution of predominantly 1–2 nm. The prepared Au–Pd/ZOC catalysts exhibited excellent activity towards 5-hydoxymethylfurfural (HMF) oxidation in water in the presence of the base NaHCO3 at benign conditions of 80 °C and 3 bar O2, resulting in quantitative yield of 2,5-furandicarboxylic acid (FDCA). The addition of base not only enhanced the yield of FDCA but also stabilized the support ZOC by preventing ZOC from the reaction with formed carboxylic acid intermediates/products, thus allowing Au–Pd/ZOC to be recycled for at least six times without significant loss of activity. The basicity of ZOC could play an important role in obtaining the improved yield of FDCA as compared to other supports.
- Gui, Zhenyou,Cao, Wenrong,Saravanamurugan, Shunmugavel,Riisager, Anders,Chen, Lifang,Qi, Zhiwen
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- CeO2@N/C@TiO2 Core-shell Nanosphere Catalyst for the Aerobic Oxidation of 5-Hydroxymethylfurfural to 5-Hydroxymethyl-2-Furancarboxylic Acid
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Defective D-CeO2@N/C@TiO2 nanospheres, each comprising a spherical CeO2 core coated with shells of N-doped carbon and TiO2, were successfully synthesized then evaluated for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Detailed catalyst characterization studies using XRD, SEM, TEM, TG-DTA, XPS, N2 physisorption confirmed the hierarchical core-shell structure of the D-CeO2@N/C@TiO2 nanospheres, with the defective surface structures created through a thermal hydrogenation process using NaBH4 promoting HMF conversion. The effect of various reaction parameters, including the reaction time, temperature, oxygen pressure, type of alkali co-reactant and the amount of catalyst, on HMF oxidation to HMFCA over the D-CeO2@N/C@TiO2 nanospheres were studied. Under the optimized reaction conditions (temperature 80 °C, reaction time 30 min, O2 pressure 1 MPa), a high HMF conversion of 87.8 % and a remarkable HMFCA selectivity of 100 % were obtained. In addition, the D-CeO2@N/C@TiO2 nanosphere catalyst showed great stability over four consecutive HMF oxidation tests, implying good catalyst stability. Experimental findings were used to develop a plausible reaction mechanism for the selective oxidation of HMF on the D-CeO2@N/C@TiO2 nanospheres.
- Song, Yong,Waterhouse, Geoffrey I. N.,Han, Feng,Li, Yan,Ai, Shiyun
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- Porphyrin-based porous organic polymer-supported iron(III) catalyst for efficient aerobic oxidation of 5-hydroxymethyl-furfural into 2,5-furandicarboxylic acid
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Environmentally friendly and efficient synthesis of 2,5-furandicarboxylic acid (FDCA), a polyester building block chemical from biomass, was carried out in water by aerobic oxidation of 5-hydroxymethylfurfural (HMF) with highly cross-linked, robust structured, and thermally stable FeIII-porous organic polymer (FeIII-POP-1) material containing basic porphyrin subunits and iron metal center. EPR analysis confirmed that the catalyst retained the oxidation state of Fe(III) after catalysis and can be reused.
- Saha, Basudeb,Gupta, Dinesh,Abu-Omar, Mahdi M.,Modak, Arindam,Bhaumik, Asim
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- Visible-Light-Driven Valorization of Biomass Intermediates Integrated with H2 Production Catalyzed by Ultrathin Ni/CdS Nanosheets
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Photocatalytic upgrading of crucial biomass-derived intermediate chemicals (i.e., furfural alcohol, 5-hydroxymethylfurfural (HMF)) to value-added products (aldehydes and acids) was carried out on ultrathin CdS nanosheets (thickness ~1 nm) decorated with nickel (Ni/CdS). More importantly, simultaneous H2 production was realized upon visible light irradiation under ambient conditions utilizing these biomass intermediates as proton sources. The remarkable difference in the rates of transformation of furfural alcohol and HMF to their corresponding aldehydes in neutral water was observed and investigated. Aided by theoretical computation, it was rationalized that the slightly stronger binding affinity of the aldehyde group in HMF to Ni/CdS resulted in the lower transformation of HMF to 2,5-diformylfuran compared to that of furfural alcohol to furfural. Nevertheless, photocatalytic oxidation of furfural alcohol and HMF under alkaline conditions led to complete transformation to the respective carboxylates with concomitant production of H2.
- Han, Guanqun,Jin, Yan-Huan,Burgess, R. Alan,Dickenson, Nicholas E.,Cao, Xiao-Ming,Sun, Yujie
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- Nitrogen doped carbon spheres with wrinkled cages for the selective oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furancarboxylic acid
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Nitrogen doped carbon spheres with wrinkled cages (NCSWCs), which were used for the first time as metal-free catalysts, exhibited high catalytic activity and selectivity in the oxidation of 5-hydroxymethylfurfural (HMF) to 5-formyl-2-furancarboxylic acid
- Zhu, Jiaping,Yao, Chaojian,Maity, Ayan,Xu, Jielai,Zhan, Tong,Liu, Weibing,Sun, Mingtai,Wang, Suhua,Polshettiwar, Vivek,Tan, Hua
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- Enzyme-catalyzed selective oxidation of 5-hydroxymethylfurfural (HMF) and separation of HMF and 2,5-diformylfuran using deep eutectic solvents
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An enzyme toolbox was developed for the synthesis of 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) with good yields from 5-hydroxymethylfurfural (HMF) via selective oxidation. In addition, a proof-of-concept based on deep eutectic solvents (DES) was provided for the efficient separation of HMF and DFF. The DFF purity was improved to 97% from 76% after extraction by choline-based DES.
- Qin, Ye-Zhi,Li, Yan-Mei,Zong, Min-Hua,Wu, Hong,Li, Ning
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- Pt Nanoparticles Supported on Nitrogen-Doped-Carbon-Decorated CeO2 for Base-Free Aerobic Oxidation of 5-Hydroxymethylfurfural
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Currently, the base-free aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to produce 2,5-furandicarboxylic acid (FDCA) is attracting intense interest due to its prospects for the green, sustainable, and promising production of biomass-based aromatic polymers. Herein, we have developed a new Pt catalyst supported on nitrogen-doped-carbon-decorated CeO2 (NC-CeO2) for the aerobic oxidation of HMF in water without the addition of any homogeneous base. It was demonstrated that the small-sized Pt particles could be well dispersed on the surface of the hybrid NC-CeO2 support, and the activity of the supported Pt catalyst depended strongly on the surface structure and properties of the catalysts. The as-fabricated Pt/NC-CeO2 catalyst, with abundant surface defects, enhanced basicity, and favorable electron-deficient metallic Pt species, enabled an almost 100 % yield of FDCA in water with molecular oxygen (0.4 MPa) at 110 °C for 8 h without the addition of any homogeneous base, which is indicative of exceptional catalytic performance. Furthermore, this Pt/NC-CeO2 catalyst also showed good stability and reusability owing to strong metal–support interactions. An understanding of the role of surface structural defects and basicity of the hybrid NC-CeO2 support provides a basis for the rational design of high-performance and stable supported metal catalysts with practical applications in various transformations of biomass-derived compounds.
- Ke, Changxuan,Li, Mengyuan,Fan, Guoli,Yang, Lan,Li, Feng
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- Inexpensive but Highly Efficient Co–Mn Mixed-Oxide Catalysts for Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid
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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 O2). 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.
- Rao, Kasanneni Tirumala Venkateswara,Rogers, Jennifer Lorraine,Souzanchi, Sadra,Dessbesell, Luana,Ray, Madhumita Bhowmick,Xu, Chunbao (Charles)
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- Selective aqueous phase oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over Pt/C catalysts: Influence of the base and effect of bismuth promotion
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5-Hydroxymethylfurfural (HMF) was quantitatively oxidized to 2,5-furandicarboxylic acid (FDCA) at 100 °C under 40 bar air in moderately basic aqueous solution in the presence of active carbon supported platinum and bismuth-platinum catalysts. The transformation of HMF into FDCA proceeded via the 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) and 2,5-diformylfuran (DFF) intermediates; both of these were very reactive and rapidly oxidized to 5-formylfurancarboxylic acid (FFCA), the subsequent oxidation of which was found to be the rate-limiting step. The preparation method of the platinum catalysts influenced the particle size of metallic platinum and modified the surface of the support, therefore determining the activity. The addition of a carbonate base (Na2CO3/HMF molar ratio = 2) led to faster overall conversion than bicarbonate (NaHCO3/HMF = 4) by maintaining an appropriate pH for the oxidation reaction. The ex situ or in situ addition of a bismuth promoter still accelerated the reaction; the highest activity was observed for a Bi/Pt molar ratio of ca. 0.2. Furthermore, the promoter helped to prevent some deactivation of the Pt catalyst upon recycling experiments. Quantitative conversion of HMF (0.1 M) and >99% yield of FDCA were achieved using a molar ratio of HMF to Pt of 100 and Na2CO3 as the homogeneous base in less than 2 h.
- Ait Rass, Hicham,Essayem, Nadine,Besson, Michele
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- Highly Efficient Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid with Heteropoly Acids and Ionic Liquids
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2,5-Furandicarboxylic acid (FDCA) is regarded as an important bioderived substitute for petrochemically derived terephthalic acid (PTA), which is widely applied in the polymer industry. This work delineates the base-free oxidation of 5-hydroxymethylfurfural (HMF) to FDCA in an ionic liquid/heteropoly acid (IL–HPA) catalytic system. HPAs displayed high activity for selective oxidation; their active center (Mo/V) was activated by O2 and transformed from oxygen single and double bonds to epoxy groups, resulting in an FDCA yield of 89 % for HPMV6 (HPM=H3PMo12O40) in the presence of [Bmim]Cl (1-butyl-3-methylimidazolium chloride) under optimized reaction conditions. The high solubility of imidazole ILs for FDCA improved the affinity of HMF and the active centers of the catalyst and protected the furan ring from oxidative cleavage. Furthermore, multiple hydrogen bonds simultaneously formed between the electronegative anions and hydroxy protons of HMF, as well as the hydrogen atoms of the imidazole rings and hydroxy groups, promoting the transformation to aldehyde groups. Various starting materials were studied, and a moderate FDCA yield was obtained from glucose. This work provides an interesting IL–HPA catalytic system for the base-free synthesis of FDCA from accessible monosaccharides and illustrates the great potential of FDCA production from renewable carbohydrates.
- Chen, Ruru,Xin, Jiayu,Yan, Dongxia,Dong, Huixian,Lu, Xingmei,Zhang, Suojiang
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- Lipase-mediated selective oxidation of furfural and 5-hydroxymethylfurfural
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Furfural and 5-hydroxymethylfurfural (HMF) are important biomass-derived platform chemicals that can be obtained from the dehydration of lignocellulosic sugars. A possible route for the derivatization of furanics is their oxidation to afford a broad range of chemicals with promising applications (e.g., diacids, hydroxyl acids, aldehyde acids, monomers for novel polymers). Herein we explore the organic peracid-assisted oxidation of furanics under mild reaction conditions. Using lipases as biocatalysts, alkyl esters as acyl donors, and aqueous solutions of hydrogen peroxide (30% v/v) added stepwise, peracids are formed in situ, which subsequently oxidize the aldehyde groups to afford carboxylic acids with high yields and excellent selectivities. Furthermore, the use of an immobilized silicabased 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) affords the selective oxidation of the hydroxymethyl group of HMF to afford 2,5-diformylfuran. That product can be subsequently oxidized using again lipases for the in situ peracid formation to yield 2,5-furandicarboxylic acid, which is considered to be a key building block for biorefineries. These lipase-mediated reactions proceeded efficiently even with high substrate loadings under still non-optimized conditions. Overall, a proof-of-concept for the oxidation of furanics (based on in situ formed organic peracids as oxidants) is provided.
- Krystof, Monika,Pérez-Sánchez, María,De María, Pablo Domínguez
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- Kinetics and mechanism of 5-hydroxymethylfurfural oxidation and their implications for catalyst development
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The reaction mechanism of 5-hydroxymethylfurfural (HMF) oxidation in neutral aqueous solution with O2 to 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-furandicarboxylic acid (FDCA) was evaluated over a 3 wt% Pt/activated carbon catalyst in a semibatch reactor and confirmed that the mechanism was the same as that determined at high pH. In addition, the reaction kinetics of intermediate HFCA oxidation to FDCA over supported Pt at high pH were investigated. The combination of reaction kinetics and isotopic labeling studies using 18O-labeled H2O and O2 was used to suggest a reaction mechanism in which H2O inserts oxygen into the product and O2 scavenges electrons from the metal catalyst. Carbon nanofibers (CNF) containing excess acid or base groups were also used as supports for Pt and Au nanoparticles and evaluated as catalysts in HMF oxidation. Although the CNF-supported samples catalyzed HMF oxidation at rates similar to other carbon-supported Pt and Au catalysts, the CNF support with basic groups improved the ability of supported Au to form FDCA from HMF under mild conditions.
- Davis, Sara E.,Benavidez, Angelica D.,Gosselink, Robert W.,Bitter, Johannes H.,De Jong, Krijn P.,Datye, Abhaya K.,Davis, Robert J.
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- Selective oxidation of 5-hydroxymethylfurfural with H2O2 catalyzed by a molybdenum complex
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Organic solvent free 5-hydroxymethylfurfural (HMF) oxidation into 2,5-furandicarboxylic acid (FDCA) with hydrogen peroxide using quaternary ammonium octamolybdate and quaternary ammonium dectungstate was studied. Tetra-1-ethyl-3-methylimidazolium octamolybdate ([EMIM]4Mo8O26), tetra-hexadecyltrimethyl ammonium octamolybdate ([CTAB]4Mo8O26) and tetra-ethylpyridinium octamolybdate ([EPy]4Mo8O26) displayed high activity for the selective oxidation of HMF to FDCA, and the selectivity of FDCA could reach 100% with a 99.5% conversion of HMF in the presence of [EMIM]4Mo8O26. The byproduct formed in competition with FDCA was identified as the intermediate 5-hydroxymethyl-2-furan carboxylic acid (HMFCA) and 5-formyl-2-furan carboxylic acid (FFCA), and neither 2,5-diformyl furan (DFF) nor any other byproducts from the oxidative cleavage of the HMF furan ring were detected during the oxidation process, which indicated that the aldehyde group of HMF oxidizes first, followed by the oxidation of the hydroxymethyl group in this reaction system. Although the quaternary ammonium salts, such as [EMIM]Br, EPyBr and CTAB, prevented FDCA formation from the HMFCA advanced oxidation, they could eliminate the oxidative cleavage of the furan ring and improve the affinity of HMF and catalysts, to make the catalytic active centers readily accessible to HMF molecules. However, tetra-1-ethyl-3-methylimidazolium dectungstate ([EMIM]4W10O32), tetra-hexadecyltrimethyl ammonium dectungstate ([CTAB]4W10O32) and tetra-ethylpyridinium dectungstate ([EPy]4W10O32) were unfavorable for FDCA formation. The great difference in performance of quaternary ammonium octamolybdate and quaternary ammonium dectungstate in HMF oxidation with H2O2 was attributed to their different structure.
- Li, Shuang,Su, Kunmei,Li, Zhenhuan,Cheng, Bowen
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- Fe-Zr-O catalyzed base-free aerobic oxidation of 5-HMF to 2,5-FDCA as a bio-based polyester monomer
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An environment-friendly and economical route for 5-hydroxymethylfurfural (HMF) aerobic oxidation to 2,5-furandicarboxylic acid (FDCA) in an ionic liquid (IL)-promoted base-free reaction system was reported using Fe-Zr-O as a catalyst. A series of FexZr1-xO2 catalysts were synthesized by a hydrothermal method and the catalytic performance was investigated. Among these catalysts, Fe0.6Zr0.4O2 exhibited excellent catalytic activity in the HMF oxidation. A 60.6% FDCA yield and 99.9% HMF conversion could be obtained after 24 h under 2 MPa O2 pressure and base-free conditions. The good performance could be attributed to the large amount of acidic and basic sites on the surface of the catalyst and its high reducibility and oxygen mobility. In addition, the formation of humins and the reaction pathways in the ILs were also investigated, which revealed parallel reactions between FDCA and humin formation. A plausible reaction mechanism was proposed based on the results of a series of designed experiments. Finally, the catalyst was used five times without obvious loss of activity. To the best of our knowledge, this is the best result for a non-noble metal catalyzed base-free oxidation of HMF to FDCA using molecular oxygen as an oxidant.
- Yan, Dongxia,Xin, Jiayu,Zhao, Qiu,Gao, Kai,Lu, Xingmei,Wang, Gongying,Zhang, Suojiang
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- Two-dimensional metal-organic framework nanosheets for highly efficient electrocatalytic biomass 5-(hydroxymethyl)furfural (HMF) valorization
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To construct a green chemical synthesis system for a better future of human beings, the utilization of water as an oxygen source and electricity as the driving force for the oxygenation of biomass valorization is of great significance and essential. Here, we first investigated the possibility for 5-hydroxymethylfurfural (HMF) electrooxidation into 2,5-furandicarboxylic acid (FDCA) by Ni-based two-dimensional metal-organic frameworks (2D MOFs) as electrocatalysts. FDCA is a desirable alternative to fossil-based terephthalic acids for the production of environmentally friendly polymers. The as-prepared Co-doped 2D MOFs NiCoBDC (Ni2+, BDC = terephthalic acid) have a high FDCA yield of 99%, an excellent yield rate of 20.1 μmol cm-2 h-1 and a faradaic efficiency of 78.8% at 1.55 V vs. RHE, as performed in an electrolyte at pH 13, where the degradation of HMF was ignored. Benefitting from the accessible pores of HMF molecules, abundant exposed active sites and coupling effects between Ni and Co atoms, 2D NiCo-MOFs realized a high catalytic activity and a robust electrochemical durability. This work demonstrates 2D MOFs as promising electrocatalysts for highly efficient biomass valorization because of their porosity and rich active sites.
- Cai, Mengke,Li, Guangqin,Li, Yinle,Liu, Qinglin,Zhang, Yawei,Zhao, Yiyue
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- The continuous oxidation of HMF to FDCA and the immobilisation and stabilisation of periplasmic aldehyde oxidase (PaoABC)
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By manipulating the reaction conditions, furandicarboxylic acid (FDCA) was prepared by the biooxidation of hydroxymethyl furfural (HMF) in a continuous one-pot reaction using galactose oxidase M3-5, periplasmic aldehyde oxidase (PaoABC), catalase and horseradish peroxidase. In addition, PaoABC was successfully entrapped in a SiO2 hydrogel and recycled 14 times without loss of activity. The catalyst was able to tolerate up to 200 mM DFF concentration giving FDCA in full conversion with very promising TOF and TON values.
- McKenna,Mines,Law,Kovacs-Schreiner,Birmingham,Turner,Leimkühler,Carnell
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- Efficient and Selective Oxidation of 5-Hydroxymethylfurfural into 2, 5-Diformylfuran Catalyzed by Magnetic Vanadium-Based Catalysts with Air as Oxidant
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Abstract: In this study, a new kind of magnetic vanadium-based catalyst was successfully prepared and employed to produce 2, 5-diformylfuran (DFF) in the liquid phase through selective oxidation of biomass-derived 5-hydroxymethylfurfur (HMF) with air as oxidant. It was found that magnetic Fe3O4 nanoparticles supported NH4·V3O8 showed excellent catalytic performance with the achievement of 95.5% HMF conversion along with 82.9% selectivity to DFF under optimal reaction conditions. More importantly, the catalyst could be readily separated from the reaction mixture by a permanent magnet, and recycled several times without the loss of its catalytic activity. Graphic Abstract: The NH4·V3O8/Fe3O4 catalyst showed high activity for selective oxidation of 5-hydroxymethylfurfural into 2, 5-diformylfuran.[Figure not available: see fulltext.]
- Lai, Jinhua,Zhou, Shuolin,Cheng, Feng,Guo, Dongwen,Liu, Xianxiang,Xu, Qiong,Yin, Dulin
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- Ruthenium(iii) polyethyleneimine complexes for bifunctional ammonia production and biomass upgrading
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As an effective strategic approach to produce ammonia (NH3), electrocatalytic nitrogen reduction reactions (NRRs) under ambient conditions using renewable energy sources (e.g. solar) have attracted significant attention; however, the design of an efficient electrocatalyst for the NRR is a challenging task and has been of central research interest. Herein, we report the synthesis of ruthenium(iii) polyethyleneimine (Ru(iii)-PEI) catalysts supported on carboxyl-modified carbon nanotubes (Ru(iii)-PEI?MWCNTs) by a self-assembly process driven by electrostatic forces at room temperature. Our newly designed Ru(iii)-PEI?MWCNTs were employed as bifunctional catalysts for the NRR and 5-hydroxymethylfurfural (HMF) oxidation. At -0.10 V vs. the reversible hydrogen electrode (RHE), our Ru(iii)-PEI?MWCNTs exhibited the high NH3 yield rate of 188.90 μgNH3 mgcat.-1 h-1 and the faradaic efficiency (FE) of 30.93% at room temperature. Furthermore, owing to its favorable thermodynamics for HMF oxidation, the Ru(iii)-PEI?MWCNT electrode demonstrated an impressive electrocatalytic HMF oxidation at 1.24 V, 220 mV lower than that for oxygen evolution. The two-electrode electrolyzer employing Ru(iii)-PEI?MWCNTs as a bifunctional catalyst for both the cathode and the anode showed the current density of 0.50 mA cm-2 with the cell voltage of only 1.34 V over 27 hours of stable electrolysis with a 94% FE for 2,5-furandicarboxylic acid (FDCA) production; this suggested an outstanding performance of this electrolyzer for the coupling of NRR with HMF oxidation. This study represents the first attempt at the ground demonstration of combining NH3 production with biomass upgrading.
- Xu, Guang-Rui,Batmunkh, Munkhbayar,Donne, Scott,Jin, Hongni,Jiang, Jia-Xing,Chen, Yu,Ma, Tianyi
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- Continuous-Flow Oxidation of HMF to FDCA by Resin-Supported Platinum Catalysts in Neat Water
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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.
- Liguori, Francesca,Barbaro, Pierluigi,Calisi, Nicola
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- Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites: fact or fiction?
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Nanoparticulate gold has emerged as a promising catalyst for diverse mild and efficient selective aerobic oxidations. However, the mechanism of such atom-economical transformations, and synergy with functional supports, remains poorly understood. Alkali-free Mg-Al hydrotalcites are excellent solid base catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA), but only in concert with high concentrations of metallic gold nanoparticles. In the absence of soluble base, competitive adsorption between strongly-bound HMF and reactively-formed oxidation intermediates site-blocks gold. Aqueous NaOH dramatically promotes solution phase HMF activation, liberating free gold sites able to activate the alcohol function within the metastable 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) reactive intermediate. Synergistic effects between moderate strength base sites within alkali-free hydrotalcites and high gold surface concentrations can afford highly selective and entirely heterogeneous catalysts for aqueous phase aldehyde and alcohol cascade oxidations pertinent to biomass transformation.
- Ardemani, Leandro,Cibin, Giannantonio,Dent, Andrew J.,Isaacs, Mark A.,Kyriakou, Georgios,Lee, Adam F.,Parlett, Christopher M. A.,Parry, Stephen A.,Wilson, Karen
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- Enzymatic versatility and thermostability of a new aryl-alcohol oxidase from Thermothelomyces thermophilus M77
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Background Fungal aryl-alcohol oxidases (AAOx) are extracellular flavoenzymes that belong to glucose-methanol-choline oxidoreductase family and are responsible for the selective conversion of primary aromatic alcohols into aldehydes and aromatic aldehydes to their corresponding acids, with concomitant production of hydrogen peroxide (H2O2) as by-product. The H2O2 can be provided to lignin degradation pathway, a biotechnological property explored in biofuel production. In the thermophilic fungus Thermothelomyces thermophilus (formerly Myceliophthora thermophila), just one AAOx was identified in the exo-proteome. Methods The glycosylated and non-refolded crystal structure of an AAOx from T. thermophilus at 2.6 ? resolution was elucidated by X-ray crystallography combined with small-angle X-ray scattering (SAXS) studies. Moreover, biochemical analyses were carried out to shed light on enzyme substrate specificity and thermostability. Results This flavoenzyme harbors a flavin adenine dinucleotide as a cofactor and is able to oxidize aromatic substrates and 5-HMF. Our results also show that the enzyme has similar oxidation rates for bulky or simple aromatic substrates such as cinnamyl and veratryl alcohols. Moreover, the crystal structure of MtAAOx reveals an open active site, which might explain observed specificity of the enzyme. Conclusions MtAAOx shows previously undescribed structural differences such as a fully accessible catalytic tunnel, heavy glycosylation and Ca2+ binding site providing evidences for thermostability and activity of the enzymes from AA3_2 subfamily. General significance Structural and biochemical analyses of MtAAOx could be important for comprehension of aryl-alcohol oxidases structure-function relationships and provide additional molecular tools to be used in future biotechnological applications.
- Godoy, Andre Schutzer,Higasi, Paula Miwa Rabelo,Kadowaki, Marco Antonio Seiki,Polikarpov, Igor,Prade, Rolf Alexander,de Araújo, Evandro Ares,de Godoy, Mariana Ortiz
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- Base-free atmospheric O2-mediated oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic acid triggered by Mg-bearing MTW zeolite supported Au nanoparticles
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Mg-bearing MTW silicalite zeolite, MgSi-ZSM-12, was straightforwardly synthesized by involving an unusual acidic pre-gelation system and engaged as the task-specific support for loading the Au nanoparticles (NPs). The resulting Au/MgSi-ZSM-12 catalyst showed stably excellent activity for the oxidation of HMF into FDCA in the presence of atmospheric dioxygen (O2) without externally adding any liquid base, affording a yield of 87 % and turnover number (TON) of 331 based on the surface Au sites. Superior basicity was evidenced by embedding Mg species into the all-silica zeolitic skeleton, which enables strong, weak, and near-zero affinity towards aldehyde, alcohol, and carboxyl groups, respectively, thus, allows rapid and high-uptake adsorption of HMF, but negligible adsorption of FDCA. This unique feature of the Mg-bearing all-silica zeolite support together with its synergy with the active sites of Au NPs is revealed to accelerate the production of FDCA under the base-free mild condition.
- Chen, Lei,Zhuang, Wenxia,Lan, Jingmin,Liu, Xiaoling,Jiang, Shi,Wang, Lei,Zhou, Yu,Wang, Jun
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- Heterogeneously-Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid with MnO2
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A simple non-precious-metal catalyst system based on costeffective and ubiquitously available MnO2, NaHCO3, and molecular oxygen was used to convert 5-hydroxymethylfurfural (HMF) to 2,5-difurandicarboxylic acid (FDCA) as a bioplastics precursor in 91 % yield. The MnO2catalyst could be recovered by simple filtration and reused several times. The present system was also applicable to the aerobic oxidation of other biomass-derived substrates and the gram-scale oxidation of HMF to FDCA, in which 2.36 g (86 % yield) of the analytically pure FDCA could be isolated.
- Hayashi, Eri,Komanoya, Tasuku,Kamata, Keigo,Hara, Michikazu
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- Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid
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Encapsulating noble metal nanoparticles (NPs) within the zeolite framework enhances the stability and accessibility of active sites; however, direct synthesis remains a challenge because of the easy precipitation of noble metal species under strong alkali crystallization conditions. Herein, beta zeolite-encapsulated Pt NPs (Pt?Beta) were synthesized via a hydrothermal approach involving an unusual acid hydrolysis preaging step. The ligand—(3-mercaptopropyl)trimethoxysilane—and Pt precursor were cohydrolyzed and cocondensed with a silica source in an initially weak acidic environment to prevent colloidal precipitation by enhancing the interaction between the Pt and silica species. Thus, the resultant 0.2%Pt?Beta was highly active in the transformation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid (FDCA) under atmospheric O2 conditions by using water as the solvent while stably evincing a high yield (90%) associated with a large turnover number of 176. The excellent catalysis behavior is attributable to the enhanced stability that inhibits Pt leaching and strengthens the intermediates that accelerate the rate-determining step for the oxidation of 5-formyl-2-furan carboxylic acid into FDCA.
- Chen, Lei,Jiang, Shi,Liu, Xiaoling,Wang, Jun,Xu, Hongzhong,Zhou, Yu
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- Electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid on supported Au and Pd bimetallic nanoparticles
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This work explores the potential-dependent electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) in alkaline media over supported Au and Pd nanoparticles and demonstrates the synergistic effects of bimetallic Pd-Au catalysts for the selective formation of 2,5-furandicarboxylic acid (FDCA). Results from electrolysis product analysis at various electrode potentials, along with cyclic voltammetry of HMF and its oxidation intermediates, revealed the unique catalytic properties of Pd and Au for competitive oxidation of alcohol and aldehyde side-groups present in HMF. Aldehyde oxidation was greatly favored over alcohol oxidation on the Au/C catalyst, which was very active for HMF oxidation to 5-hydroxymethyl-2-furancarboxylic acid (HFCA), however high electrode potentials were required for further oxidation of the alcohol group to FDCA. HMF oxidation on Pd/C followed two competitive routes to FDCA and the pathway was dependent on the electrode potential. Oxidation of aldehyde groups occurred much slower on Pd/C than on Au/C at low potentials, but was greatly enhanced at increased potentials or by alloying with Au. It was found that Pd-Au bimetallic catalysts achieved deeply oxidized products (FFCA and FDCA) at lower potentials than monometallic catalysts and the product distribution was dependent on the electrode potential and surface alloy composition. Bimetallic catalysts with 2: 1 and 1 : 2 Pd-Au molar ratios (Pd2Au1/C and Pd1Au2/C) exhibited advantages of both single components with facile alcohol and aldehyde group oxidation, resulting in greatly improved HMF conversion rate and selectivity to fully oxidized FDCA. This journal is the Partner Organisations 2014.
- Chadderdon, David J.,Xin, Le,Qi, Ji,Qiu, Yang,Krishna, Phani,More, Karren L.,Li, Wenzhen
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- Metal-functionalized carbon nanotubes for biomass conversion: Base-free highly efficient and recyclable catalysts for aerobic oxidation of 5-hydroxymethylfurfural
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In this study, the oxidative conversion of 5-hydroxymethylfurfural into essential chemicals on recyclable metal (Pt, Pd, Ru, Co, & Ni)- supported catalysts is reported. While most of the catalytic reactions require a base as an additive, this current study provided a base-free environmentally benign heterogeneous catalytic system. The reactions were performed on various M/CNT catalysts. As a support, CNT played an important role in the reaction mechanism. These catalysts showed a high activity for the base free oxidation of HMF under air in aqueous media. The CNT-supported Pt, Pd, and Ru catalysts were found to be more selective towards FDCA (>97%) compared to Ni and Co for DFF (>96%). The conversion and selectivity of the products were determined using NMR and HPLC. The (1 wt%) M/CNT catalysts were prepared via solution processing and were characterized using BET, XRD, TEM, TGA, FTIR, and XPS.
- Sharma, Poonam,Solanki, Mohit,Sharma, Rakesh K.
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- Experimental and DFT Study of Metal-Free Catalyst for Selective Oxidation of Biomass-Derived Molecule (HMF)
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Catalytic conversion of biomass or biomass-derived intermediate to value-added chemicals is important for both biomass waste management and production of industrially important chemicals. Oxidation of 5-hydroximethyl furfural (HMF) is considered one of th
- Afroz, Khurshida,Ntambwe, Mike,Nuraje, Nurxat
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- Pt and Pt/Sn carbonyl clusters as precursors for the synthesis of supported metal catalysts for the base-free oxidation of HMF
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In the present work, Pt and Pt/Sn nanoparticles (NPs), synthesized from carbonyl cluster precursors were deposited on TiO2 and the resulting materials were tested as catalysts in selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). The work was mainly focused on the study of the formation of bimetallic or mixed oxide-metal nanoparticles on TiO2 starting with Pt/Sn carbonyl clusters and on the structure-activity relationship in the reaction of HMF oxidation in base-free conditions. The developed synthesis procedure allowed to obtain very small mono and bimetallic particles characterized by a narrow particle size distribution. Promising results in base-free FDCA production have been achieved using the prepared samples. In particular, the introduction of Sn in an equimolar amount with Pt improved the catalyst activity as well as its time stability upon operation, demonstrating that the modification of Pt electronic configuration by Sn is a key factor for the mastering of functional performances.
- Bonincontro, Danilo,Lolli, Alice,Storione, Alba,Gasparotto, Alberto,Berti, Beatrice,Zacchini, Stefano,Dimitratos, Nikolaos,Albonetti, Stefania
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- Base-free aerobic oxidation of 5-hydroxymethyl-furfural to 2,5-furandicarboxylic acid in water catalyzed by functionalized carbon nanotube-supported au-pd alloy nanoparticles
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The aerobic oxidation of 5-hydroxymethylfurfural (HMF), a key platform compound in cellulose transformation, into 2,5-furandicarboxylic acid (FDCA), a promising renewable alternative to petroleum-derived terephthalic acid, is one of the most attractive reactions for establishing biomass-based sustainable chemical processes. Supported Au catalysts have shown encouraging performance for this reaction, but the need of an excess amount of base additives makes the process less green and less cost-effective. Here, we report a stable and efficient carbon nanotube (CNT)-supported Au-Pd alloy catalyst for the aerobic oxidation of HMF to FDCA in water without any bases. The functionalization of CNT surfaces is crucial for FDCA formation. We have clarified that the CNT containing more carbonyl/quinone and less carboxyl groups favors FDCA formation by enhancing the adsorption of the reactant and reaction intermediates. Significant synergistic effects exist between Au and Pd in the alloy for the base-free oxidation of HMF to FDCA through three tandem steps. The present work provides understanding of the support-enhanced adsorption effect and the alloying effect for supported Au-based bimetallic catalysts, and this knowledge may help develop efficient catalysts for the aerobic oxidation of relatively complicated organic compounds with different functional groups in water.
- Wan, Xiaoyue,Zhou, Chunmei,Chen, Jiashu,Deng, Weiping,Zhang, Qinghong,Yang, Yanhui,Wang, Ye
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- Synthesis of 2,5-furandicarboxylic acid by a TEMPO/laccase system coupled withPseudomonas putidaKT2440
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As a useful and renewable chemical building block from biomass, 2,5-furandicarboxylic acid (FDCA) has become an increasingly desirable platform chemical as a terephthalic acid replacement for polymerization. In this work, an efficient and highly selective biocatalytic approach for the synthesis of FDCA from 5-hydroxymethylfurfural (HMF) was successfully developed using a TEMPO/laccase system coupled withPseudomonas putidaKT2440. TEMPO/laccase afforded the selective oxidation of the hydroxymethyl group of HMF to form 5-formyl-2-furancarboxylic acid as a major product, which was subsequently oxidized to FDCA byP. putidaKT2440. Manipulating the reaction conditions resulted in a good conversion of HMF (100percent) and an excellent selectivity of FDCA (100percent) at substrate concentrations up to 150 mM within 50 h. The cascade catalytic process established in this work offers a promising approach for the green production of FDCA.
- Ouyang, Jia,Tan, Huanghong,Xu, Qianqian,Zheng, Zhaojuan,Zou, Lihua
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- Selective photoelectrocatalytic oxidation of 5-(hydroxymethyl)-2-furaldehyde in water by using Pt loaded nanotube structure of TiO2 on Ti photoanodes
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Photoelectrocatalytic (PEC) synthesis of 2,5-furandicarbaldehyde (FDC) from 5-(hydroxymethyl)-2-furaldehyde (HMF) has been performed in water by using TiO2 films on Ti layer prepared by thermal annealing of Ti (Ti/TiO2) and TiO2
- ?zcan, Levent,Yal??n, P?nar,Alag?z, O?uzhan,Yurdakal, Sedat
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- Effect of Gold Particles Size over Au/C Catalyst Selectivity in HMF Oxidation Reaction
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A series of gold nanoparticles in the 4–40 nm range were prepared, immobilized on activated carbon and further tested, at low base concentration, in the catalytic oxidation of 5-hydroxymethyl furfural (HMF) to 2,5-furandicarboxylic acid (FDCA). Gold particles size variation has no influence on HMF conversion but significantly affects product selectivity and carbon balance. This behavior is ascribed to the thermodynamically favorable oxygen reduction reaction on Au(100) faces. As the gold particle size decreases the Au(100)/Au(111) exposure ratio, estimated by using the van Hardeveld-Hartog model, increases as well as the FDCA selectivity. The smaller the gold particle size the smaller the 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) to FDCA ratio pointing to the gold size dependent behavior of the oxidation of the alcohol function of the HMF molecule.
- Megías-Sayago, Cristina,Lolli, Alice,Bonincontro, Danilo,Penkova, Anna,Albonetti, Stefania,Cavani, Fabrizio,Odriozola, José Antonio,Ivanova, Svetlana
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- Fabrication of spinel CoMn2O4 hollow spheres for highly selective aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran
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Spinel CoMn2O4 hollow spheres were prepared by a solvothermal method, where uniform cobalt-manganese glycerate spheres as the precursor were self-assembled and converted into hollow spheres by calcination. The as-prepared catalysts were characterized by field emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and desorption isotherms, thermogravimetric analysis, and H2 temperature programmed reduction (H2-TPR). The results show that body-centered tetragonal and face-centered cubic spinel structures of CoMn2O4 hollow spheres can be tuned by different Co/Mn molar ratios. Moreover, the spinel CoMn2O4 hollow spheres exhibit high catalytic activity for the selective oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-diformyfuran (DFF). Importantly, the spinel CoMn2O4 hollow spheres with Co/Mn molar ratio of 2/3 shows the highest catalytic performance with a 41.6percent HMF conversion and a 100percent selectivity to DFF. On one hand, the spinel CoMn2O4 hollow spheres with large surface area have sufficient exposed active sites for the oxidation of HMF and oxidized product DFF can fast leave the catalyst surface leading to high selectivity, avoiding further oxidation. On the other hand, the synergistic effect between Co and Mn species in the binary oxides by the formation of heteronuclear cluster complexes CoMn2O4, which affects and promotes the electron-transfer process, results in significant improvement in catalyst performance. Additionally, the effects of different Co/Mn molar ratios, catalyst amounts, reaction time and temperatures of the catalyst for HMF oxidation were also investigated. Furthermore, the spinel CoMn2O4 hollow spheres can be used for six consecutive runs without significant loss of its catalytic activity.
- Chen, Lifang,Cheng, Hongye,Ding, Lei,Qi, Zhiwen,Yang, Wenyu
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- Efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran on manganese oxide catalysts
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A cryptomelane-type manganese oxide octahedral molecular sieve with a (2 × 2, 4.6 A × 4.6 A) tunnel size (OMS-2) efficiently catalyzed aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) with a high yield of 97.2% at 383 K and 0.5 MPa O 2 in N,N-dimethylformamide. OMS-2 was superior to other MnO 2 catalysts with different morphologies, including OMS-1, OMS-6, and OMS-7 with various tunnel sizes, amorphous MnO2 and birnessite-type MnO2, apparently due to its (2 × 2) tunnel structure and consequently high reducibility and oxidizability. Kinetic and isotopic studies on OMS-2 showed near half-order dependence of the activities on HMF and O 2 concentrations and marked kinetic isotope effects for deuterated HMF at its methylene group. These results, together with the similar initial rates under aerobic and anaerobic conditions, suggest that HMF oxidation to DFF on OMS-2 proceeds via a redox mechanism involving kinetically-relevant steps of C-H bond cleavage in adsorbed alcoholate intermediate, derived from quasi-equilibrated dissociation of HMF, using lattice oxygen and reoxidation of Mn3+ to Mn4+ by dissociative chemisorption of O 2.
- Nie, Junfang,Liu, Haichao
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- NaBr/DMSO-induced synthesis of 2,5-diformylfuran from fructose or 5-(hydroxymethyl)furfural
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2,5-Diformylfuran (DFF) was obtained by heating a solution of 5-(hydroxymethyl)furfural in DMSO. The addition of acids or salts improved the selectivity, especially if bromides were employed. Good yields of DFF were obtained with HBr or NaBr as the catalyst. One-pot procedures were developed from fructose, which led to DFF in medium yields. This transformation occurs through the formation of 5-(bromomethyl)furan-2-carbaldehyde followed by a Kornblum-type reaction. In the presence of bromide salts, the in situ formation of the catalyst involves the thermolysis of DMSO and the association of the resulting strong acids with the bromides. With a pinch of salt: The association of NaBr as a catalyst and DMSO as a solvent allows the synthesis of 2,5-diformylfuran from 5-(hydroxymethyl)furfural (HMF) or fructose in 75 or 50 % yield, respectively. This transformation occurs through the formation of 5-(bromomethyl)furan-2-carbaldehyde followed by a Kornblum-type reaction.
- Laugel, Caroline,Estrine, Boris,Le Bras, Jean,Hoffmann, Norbert,Marinkovic, Sinisa,Muzart, Jacques
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- Defect-Rich High-Entropy Oxide Nanosheets for Efficient 5-Hydroxymethylfurfural Electrooxidation
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High-entropy oxides (HEOs), a new concept of entropy stabilization, exhibit unique structures and fascinating properties, and are thus important class of materials with significant technological potential. However, the conventional high-temperature synthesis techniques tend to afford micron-scale HEOs with low surface area, and the catalytic activity of available HEOs is still far from satisfactory because of their limited exposed active sites and poor intrinsic activity. Here we report a low-temperature plasma strategy for preparing defect-rich HEOs nanosheets with high surface area, and for the first time employ them for 5-hydroxymethylfurfural (HMF) electrooxidation. Owing to the nanosheets structure, abundant oxygen vacancies, and high surface area, the quinary (FeCrCoNiCu)3O4 nanosheets deliver improved activity for HMF oxidation with lower onset potential and faster kinetics, outperforming that of HEOs prepared by high-temperature method. Our method opens new opportunities for synthesizing nanostructured HEOs with great potential applications.
- Gu, Kaizhi,Huang, Gen,Liu, Yanbo,Tao, Li,Wang, Dongdong,Wang, Shuangyin,Wang, Tehua,Xie, Chao,Zou, Yuqin
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- Oxidation of 5-hydroxymethylfurfural over supported Pt, Pd and Au catalysts
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Supported Pt, Pd, and Au catalysts were evaluated in the aqueous-phase oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) at 295 K and high pH in a semibatch reactor. The intermediate reaction product 5-hydroxymethyl-2-furancarboxylic acid (HFCA) was formed in high yield over Au/C and Au/TiO2 at 690 kPa O2, 0.15 M HMF and 0.3 M NaOH, but did not continue to react substantially to FDCA at the specified O2 pressure and base concentration. In contrast, the final reaction product FDCA was formed over Pt/C and Pd/C under identical conditions. The initial turnover frequency of HMF conversion was an order of magnitude greater on Au catalysts compared to either Pt or Pd. Increasing the O2 pressure and NaOH concentration facilitated the conversion of HFCA to FDCA over the supported Au. The significant influence of base concentration on the product distribution indicates an important role of OH- in the activation, oxidation and degradation of HMF.
- Davis, Sara E.,Houk, Levi R.,Tamargo, Erin C.,Datye, Abhaya K.,Davis, Robert J.
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- Efficient synthesis of 2,5-furandicarboxylic acid from biomass-derived 5-hydroxymethylfurfural in 1,4-dioxane/H2O mixture
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The catalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a renewably sourced substitution for petroleum-derived terephthalic acid, at a high concentration is highly demanding but challenging. Herein, the efficient conversion of HMF (10–25 wt%) in 1,4-dioxane/H2O was achieved, and a desirable FDCA yield of 98% was obtained from HMF (10 wt%) over commercial Ru/C (2 Equiv. NaHCO3, 4 MPa O2, 3 h, and 140 ℃). In addition, a two-step cascade reaction was developed for FDCA production, in which FDCA was employed as the acid catalyst to promote the dehydration of fructose (10 wt%) to HMF, followed by oxidation in 1,4-dioxane/H2O to FDCA over Ru/C. As compared to pure water or 1,4-dioxane, the better stability of HMF in 1,4-dioxane/H2O with a weak alkaline environment and the enhancement of superoxide radicals (·O2-) in 1,4-dioxane/H2O could ensure high FDCA yield at high HMF concentration.
- Fang, Huayu,Ke, Xixian,Li, Tianyuan,Lin, Lu,Liu, Huai,Sun, Yong,Tang, Xing,Xie, Weizhen,Zeng, Xianhai
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- A CuMn2O4spinel oxide as a superior catalyst for the aerobic oxidation of 5-hydroxymethylfurfural toward 2,5-furandicarboxylic acid in aqueous solvent
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A CuMn2O4spinel oxide was preparedviaa freezing-assisted sol-gel method and used in the aerobic oxidation of 5-hydroxylmethylfurfural (HMF) toward 2,5-furandicarboxylic acid (FDCA) in aqueous solvent. A highest FDCA yield of 92.1% over the CuMn2O4spinel oxide was achieved and the catalyst could be regenerated by calcination in air after the sixth consecutive run, outperforming several other Mn-based spinel and single oxide catalysts. Kinetic studies reveal that HMF → 2,5-diformylfuran → 5-formylfuran-2-carboxylic acid (FFCA) → FDCA is the primary reaction route of the reaction and that the oxidation of FFCA is the rate-determining step over the CuMn2O4spinel. Characterization measurements show that Mn species enrichment and proper Mn4+/Mn3+, Cu2+/Cu+and Cu/Mn ratios on the surface of the catalyst led to an appropriate Olatt./Oads.ratio, which facilitated oxygen mobility between the Olatt.consumption and the Olatt.generationviathe refilling of oxygen vacancies. Synergistic effects between Mn and Cu in the CuMn2O4spinel inhibit the secondary reaction and accelerate the rate-determining step rate to enhance FDCA formation.
- Wan, Xiaoyue,Tang, Nannan,Xie, Qi,Zhao, Shuangyan,Zhou, Chunmei,Dai, Yihu,Yang, Yanhui
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p. 1497 - 1509
(2021/03/14)
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- A PROCESS FOR THE SYNTHESIS OF FURANDICARBOXYLIC ACID
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The present invention provides a process for the synthesis of FDC A comprising heating a mixture of fructose, aqueous NaCl or KC1, solvent, methyl isobutyl ketone (MIBK) and a catalyst at a temperature in the range of 150 to 200°C in a sealed vessel for a time period in the range of 2 to 5 hours to yield crude 5-HMF. The crude HMF further reacts with a biocatalyst at a temperature in a range of 20 to 50°C for a period at a range of 24 to 96 hours to yield Furandicarboxylic acid (FDCA) ), wherein the conversion of 5- HMF to FDCA is in the range of 90 to 100%.
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Paragraph 00049; 00056
(2021/06/26)
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- Electro-catalytic oxidation of HMF to FDCA over RuO2/MnO2/CNT catalysts in base-free solution
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The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one of the most attractive reactions to establish a sustainable chemical process based on biomass resources. In this work, a CNT-supported ruthenium-manganese oxide nano-catalyst (RuO2/MnO2/CNT) was employed for the electro-catalytic oxidation of HMF in base-free aqueous solution. The activity test showed that α-MnO2 can effectively promote the activity of RuO2 in the oxidation of HMF. In comparison with RuO2/CNT, RuO2/MnO2/CNT possessed a lower activation energy and more than twice the FDCA formation rate. Under the optimized reaction conditions, the RuO2/MnO2/CNT catalyst afforded a FDCA yield of 72.1% in a 0.1 M K2SO4 aqueous solution at a 0.9 V (vs. Ag/AgCl) applied potential. To our knowledge, this is the first demonstration of FDCA formation as the primary product with high yield in an initially neutral electrolyte. The product FDCA can be easily separated after cooling the reaction solution to room temperature. This journal is
- Dai, Yihu,Jin, Yuguang,Song, Yu,Wan, Xiaoyue,Wang, Tianci,Yang, Yanhui,Zhao, Wanna,Zhou, Chunmei
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p. 21285 - 21292
(2021/12/09)
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- Selective Oxidation of 5-Hydroxymethylfurfural to 2, 5-Diformylfuran Over a Vanadium Manganese Oxide Catalyst
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5-Hydroxymethylfurfural (HMF) is a major feedstock derived from biomass which could be converted to various high-value-added chemicals. However, it is a challenge to obtain a target product with high selectivity under mild conditions using a heterogeneous non-noble catalyst. In this study, a vanadium manganese oxide catalyst was prepared by a simple chemical synthesis method. Detailed characterization was performed to reveal that the catalyst phase composition is V2O5 and Mn(VO3)2. The catalyst showed good catalytic activity in the selective oxidation of HMF to produce 2,5-diformylfuran (DFF) at atmospheric oxygen pressure. Under optimal conditions, DFF selectivity of 97.8% was obtained at 80?°C with acetonitrile as the solvent. Furthermore, the catalyst could be recovered conveniently and reused for several runs without significant loss of the catalytic activity. Graphic Abstract: The vanadium manganese oxide catalyst was developed for the selective oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran under atmospheric pressure of molecular oxygen. [Figure not available: see fulltext.].
- Cheng, Feng,Liu, Xianxiang,Wang, Fei,Wen, Sha,Zhu, Jie
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- Understanding the Roles of Electrogenerated Co3+ and Co4+ in Selectivity-Tuned 5-Hydroxymethylfurfural Oxidation
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The Co-based electrocatalyst is among the most promising candidates for electrochemical oxidation of 5-hydroxymethylfurfural (HMF). However, the intrinsic active sites and detailed mechanism of this catalyst remains unclear. We combine experimental evidence and a theoretical study to show that electrogenerated Co3+ and Co4+ species act as chemical oxidants but with distinct roles in selective HMF oxidation. It is found that Co3+ is only capable of oxidizing formyl group to produce carboxylate while Co4+ is required for the initial oxidation of hydroxyl group with significantly faster kinetics. As a result, the product distribution shows explicit dependence on the Co oxidation states and selective production of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) and 2,5-furandicarboxylic acid (FDCA) are achieved by tuning the applied potential. This work offers essential mechanistic insight on Co-catalyzed organic oxidation reactions and might guide the design of more efficient electrocatalysts.
- Deng, Xiaohui,Fu, Xian-Zhu,Li, Jian-Feng,Luo, Jing-Li,Wang, Lei,Xu, Ge-Yang,Zhang, Jiujun,Zhang, Yue-Jiao
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supporting information
p. 20535 - 20542
(2021/08/12)
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- Facile Production of 2,5-Furandicarboxylic Acid via Oxidation of Industrially Sourced Crude 5-Hydroxymethylfurfural
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The oxidation of 5-hydroxymethylfurfural (HMF) produces value-added chemicals such as 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). In this work, FDCA production was achieved by oxidation of crude HMF solution containing around 45 % HMF a
- Martin, Kevin J.,Subramaniam, Bala,Venkitasubramanian, Padmesh,Zuo, Xiaobin
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- Synergistic chemo/biocatalytic synthesis of 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural
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2,5-Furandicarboxylic acid (FDCA) is a promising bio-based chemical in polymer industry. In this work, we constructed an oxidative cascade for one-pot synthesis of FDCA from 5-hydroxymethylfurfural (HMF) by exploiting Comamonas testosteroni SC1588 cells and laccase-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) system. HMF was oxidized to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) by the cells at neutral pH. The HMFCA formation shifted pH of the reaction mixture to acidic range, which favored laccase-TEMPO catalytic oxidation. 5-Formyl-2-furancarboxylic acid derived from HMFCA via laccase-TEMPO catalysis was converted to FDCA by the cells. FDCA was obtained in an 87% yield within 36 h, providing a productivity of around 0.4 g/L h.
- Yang, Zi-Yue,Wen, Mao,Zong, Min-Hua,Li, Ning
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- Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid over Holey 2 D Mn2O3 Nanoflakes from a Mn-based MOF
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The aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a promising renewable monomer to produce bio-based polymers such as polyethylene furanoate (PEF), has recently emerged as the subject of increasing interest. Here, holey 2 D Mn2O3 nanoflakes were obtained by a facile thermal treatment of a Mn-based metal–organic framework (MOF) precursor. The structural and morphological properties of the nanoflakes were characterized by powder XRD, FTIR, SEM and TEM to explore the formation process. It was inferred that the linker loss in the MOF precursor and the oxidation of the Mn cation induced by the heat-treatment in air were responsible for the formation of holey 2 D Mn2O3 nanoflakes. The specific morphology and redox cycle of the Mn cation on the surface endowed the synthesized nanoflakes with promising performance on the selective oxidation. The obtained nanoflakes calcined at 400 °C (M400) afforded over 99.5 % yield of FDCA at complete conversion of HMF, which is superior to the catalytic activity of commercial Mn2O3 and activated MnO2. To our knowledge, Mn2O3 exhibiting such a high performance on the aerobic oxidation of HMF to FDCA has not yet been reported. Based on the investigation of the experimental parameters, a plausible reaction mechanism was proposed.
- Bao, Liwei,Sun, Fang-Zhou,Zhang, Guo-Ying,Hu, Tong-Liang
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p. 548 - 555
(2019/12/27)
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- One-pot hydrothermal synthesis of ultrafine Pd clusters within Beta zeolite for selective oxidation of alcohols
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Highly dispersive and ultrafine Pd clusters were straightforwardly encapsulated within the crystals of Beta zeolite. This series of Pd&at;Beta material was hydrothermally synthesized by performing a unique acid co-hydrolysis of silica and Pd salt precursors in the early gelation stage, by virtue of which the interaction between Si and Pd species was strengthened to inhibit the potential phase separation in the following high pH alkali crystallization. The ultrafine Pd clusters within the wall of the zeolite framework enabled the catalysis to occur in the microchannels, resulting in a high and recyclable yield of above 95percent and a large turnover number of ~50?000 in the oxidation of benzyl alcohol under an O2 atmosphere in water, which can be extended to other microchannel-diffusive aromatic alcohols. Moreover, the catalyst also showed high activity in the aerobic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). The excellent activity is attributable to the synergistic effect of Pd clusters and preferential substrate adsorption behavior. Shape-selective catalysis and stable reusability were achieved. This result provides a novel straightforward synthesis route for fabricating zeolite encapsulated noble metal clusters that effectively and stably catalyze aerobic organic oxidation reactions with shape-selectivity.
- Chen, Lei,Liu, Peiwen,Liu, Xiaoling,Wang, Jun,Wen, Haimeng,Zhou, Yu,Zhuang, Wenxia
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supporting information
p. 4199 - 4209
(2020/07/14)
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- Deep eutectic solvent stabilised Co-P films for electrocatalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid
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The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) has been studied extensively. However, the short lifetime of catalytic electrodes remains a challenge for the electrocatalytic HMF oxidation reaction, and the high pH of the electrolyte causes denaturation of HMF during the reaction. Herein, deep eutectic solvents (DES) are employed for the preparation of efficient and durable catalytic electrodes for HMF oxidation. The catalytic electrode made up of DES avoided the complexity of multiple alkylations leading to 99% HMF conversion affording FDCA in 85.3% yield with high durability, due in part to the lower pH of the electrolyte.
- Kang, Myung Jong,Yu, Hye Jin,Kim, Hyun Sung,Cha, Hyun Gil
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p. 14239 - 14245
(2020/09/04)
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- Aerobic oxidation of 5-(hydroxymethyl)furfural into 2,5-diformylfuran catalyzed by starch supported aluminum nitrate
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Al(NO3)3 immobilized on expanded corn starch catalyst (ECS-IL-Al(NO3)3) was prepared by silane-modified imidazolium ionic liquid reacting with expanded corn starch (ECS) and coordination of Al(NO3)3 with the imidazolium chloride grafted on the surface, as proved by FT-IR, NMR, SEM/EDS, and XPS. The catalytic activity of ECS-IL-Al(NO3)3 was evaluated in the 5-hydroxymethylfurfural (HMF) oxidation under mild conditions with 98% of 2,5-diformylfuran (DFF) production at 99% HMF conversion after 5 h at 50 °C, using molecular oxygen as the oxidant. Furthermore, this catalyst was found to exhibit excellent recyclability, making it an attractive catalytic system from economic and environmental points of view.
- Hong, Mei,Wu, Shuangyan,Li, Jiatong,Wang, Jing,Wei, Lifen,Li, Kun
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- Non-metallic Aerobic Oxidation of Alcohols over Anthraquinone Based Compounds
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The catalytic performances of substituted anthraquinones were investigated in catalytic oxidation of alcohols like cyclohexanol, benzyl alcohol and 5-hydroxymethylfurfural (HMF) to carbonyl compounds (cyclohexanone, benzyl aldehyde and diformylfuran). The reduction potential of anthraquinone plays the key role in the oxidation reactions. TOF numbers and selectivities to carbonyl compounds pass through the maximum with increase of the reduction potential. The maximum activity and selectivity (>80 %) is observed for sulfonated and carboxylated anthraquinones having intermediate reduction potentials (≈ 0.1-0.2 V vs SHE). Grafted 2-carboxyanthraquinone catalyst has demonstrated comparable catalytic performance to the parent molecule and might be used as heterogeneous catalyst. The oxidation reaction was found to have radical character with transfer of hydrogen from alcohol to anthraquinone and subsequent oxidation of hydrogenated anthraquinone by oxygen.
- Zhao, Jingpeng,Wu, Dan,Hernández, Willinton Yesid,Zhou, Wen-Juan,Capron, Mickael,Ordomsky, Vitaly V.
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- PRODUCTION OF PURIFIED DIALKYL-FURAN-2,5-DICARBOXYLATE (DAFD) IN A RETROFITTED DMT PLANT
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Disclosed is a process to produce a purified vapor comprising dialkyl- furan-2,5-dicarboxylate (DAFD). Furan-2,5-dicarboxylic acid (FDCA) and an alcohol in an esterification zone to generate a crude diester stream containing dialkyi furan dicarboxylate (DAFD), unreacted alcohol, 5-(alkoxycarbonyl)furan-2- carboxylic acid (ACFC), and alkyl furan-2-carboxylate (AFC). The esterification zone comprises at least one reactor that has been previously used in an DMT process.
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Paragraph 0085
(2020/03/23)
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- A 5 - formyl of furoic preparation method (by machine translation)
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The invention discloses a 5 - formyl furoic (FFCA) of the preparation method. The method comprises: 5 - hydroxymethyl furfural in the supported metal catalyst, cocatalyst, oxygen and organic solvent under the action of the, through the one-step oxidation reaction to obtain the product 5 - formyl furoic acid. The invention high selectivity, few by-products, high yield, purity is good, it is convenient to separate the product, the process is simple. (by machine translation)
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Paragraph 0072-0077; 0084-0085; 0100-0101; 0110-0111; 0116-
(2019/02/13)
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- A 2, 5 - furan dicarboxylic acid preparation method (by machine translation)
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The invention discloses a 2, 5 - furan dicarboxylic acid of preparation method, comprises the following steps: (1) the reaction substrate, oxidizing agent and water after the mixing, then adding catalyst, airtight reaction, to obtain 2, 5 - furan-phthalic acid salt; (2) adjusting step (1) of material that has to be pH to 1, to get the 2, 5 - furan-phthalic acid. The invention uses a readily available and inexpensive oxidizing agent as an oxygen source, in particular the action of a catalyst, under mild reaction conditions, high-efficiency for preparing high-purity of 2, 5 - furan-phthalic acid, solved in the prior art of low reaction efficiency, low product yield, high cost and the like, it has very good application prospect. (by machine translation)
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Paragraph 0023-0026; 0034
(2019/05/15)
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- PURIFIED 2,5-FURANDICARBOXYLIC ACID PATHWAY PRODUCTS
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The present disclosure provides processes for the purification of 2,5-furandicarboxylic acid (FDCA). The present disclosure further provides crystalline preparations of purified FDCA, as well as processes for making the same. In addition, the present disclosure provides mixtures used in processes for the purification of FDCA.
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Paragraph 0235
(2019/02/02)
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- Biomimetic oxidase based on functionalized mesoporous SiO2 and metalloporphyrin for 5-hydroxymethylfurfural conversion
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2,5-Furandicarboxylic acid (FDCA) has the potential to replace terephthalic acid (TPA) as a building block in the preparation of bio-based and degradable polyester materials. However, the lack of efficient and stable catalysts limits the commercial viability of FDCA production. In this work, metalloporphyrins were immobilized on mesoporous SiO2 and used as a novel oxidase to convert 5-hydroxymethylfurfural (HMF) to FDCA. As the catalytic active center of P450 monooxygenases and horseradish peroxidase, supported palladium, manganese, ferri, and cobalt porphyrins via ionic-liquid-functionalized SiO2 (PdPOP-SiO2, MgPOP-SiO2, FePOP-SiO2 and CoPOP-SiO2) were able to simulate oxidase alone under mild conditions. 100% HMF (0.02 M) conversion and 94.94% FDCA yield were achieved using PdPOP-SiO2 as a biomimetic oxidase after a 12 h reaction at 373 K in water at atmospheric pressure. This type of mimetic oxidase is stable, inexpensive, and readily available, and the method developed in this work can potentially be used to oxidize HMF to FDCA in an industrial setting.
- Zou, Bin,Wang, Pengyun,Liu, Zhenjiang,Xia, Jiaojiao,Chen, baihan,Tan, Zhiyuan
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- A Comparative Study of Nickel, Cobalt, and Iron Oxyhydroxide Anodes for the Electrochemical Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid
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2,5-Furandicarboxylic acid (FDCA) has received increasing attention as a near-market platform chemical that can potentially replace terephthalic acid in the production of commercial and high-performance polymers, such as polyethylene terephthalate. FDCA can be obtained from the oxidation of 5-hydroxymethylfurfural (HMF), which is produced from the dehydration of C-6 monosaccharides obtained from cellulosic biomass. Recently, various heterogeneous Ni- and Co-based electrocatalysts were reported that can efficiently oxidize HMF to FDCA. The actual catalytically active species of these catalysts are most likely NiOOH and CoOOH or species related to NiOOH and CoOOH. However, the intrinsic catalytic properties of NiOOH and CoOOH for HMF oxidation have yet to be carefully and systematically investigated. In this study, we prepared thin and thick sets of NiOOH, CoOOH, and FeOOH films having comparable numbers of metal sites to systematically and methodically compare the intrinsic catalytic activity of these materials for HMF oxidation in a 0.1 M KOH (pH 13) solution. Our investigation revealed that they have distinctively different catalytic abilities for HMF oxidation. The use of extremely thin MOOH films containing limited numbers of catalytic sites allowed us to resolve anodic currents that were generated from HMF oxidation by different oxidation pathways. By comparing the voltammetric results of thin and thick films, the effect of the film thickness on the current generated by different oxidation pathways could be observed. The thick set of MOOH films was also used to compare the performances of these films for constant potential HMF oxidation and product analysis. The work herein contributes to a better understanding of the mechanisms of HMF oxidation on Ni-, Co-, and Fe-containing heterogeneous electrocatalysts whose surfaces are covered by their hydroxide and oxyhydroxide phases.
- Taitt, Brandon J.,Nam, Do-Hwan,Choi, Kyoung-Shin
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p. 660 - 670
(2019/01/08)
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- Effect of MnO2 Crystal Structure on Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid
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Aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) as a bioplastics monomer is efficiently promoted by a simple system based on a nonprecious-metal catalyst of MnO2 and NaHCO3. Kinetic studies indicate that the oxidation of 5-formyl-2-furancarboxylic acid (FFCA) to FDCA is the slowest step for the aerobic oxidation of HMF to FDCA over activated MnO2. We demonstrate through combined computational and experimental studies that HMF oxidation to FDCA is largely dependent on the MnO2 crystal structure. Density functional theory (DFT) calculations reveal that vacancy formation energies at the planar oxygen sites in α- and γ-MnO2 are higher than those at the bent oxygen sites. β- and λ-MnO2 consist of only planar and bent oxygen sites, respectively, with lower vacancy formation energies. Consequently, β- and λ-MnO2 are likely to be good candidates as oxidation catalysts. On the other hand, experimental studies reveal that the reaction rates per surface area for the slowest step (FFCA oxidation to FDCA) decrease in the order of β-MnO2 > λ-MnO2 > γ-MnO2 ≈ α-MnO2 > δ-MnO2 > ?-MnO2; the catalytic activity of β-MnO2 exceeds that of the previously reported activated MnO2 by three times. The order is in good agreement not only with the DFT calculation results, but also with the reduction rates per surface area determined by the H2-temperature-programmed reduction measurements for MnO2 catalysts. The successful synthesis of high-surface-area β-MnO2 significantly improves the catalytic activity for the aerobic oxidation of HMF to FDCA.
- Hayashi, Eri,Yamaguchi, Yui,Kamata, Keigo,Tsunoda, Naoki,Kumagai, Yu,Oba, Fumiyasu,Hara, Michikazu
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p. 899 - 900
(2019/01/14)
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- AuPd-nNiO as an effective catalyst for the base-free oxidation of HMF under mild reaction conditions
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Au-Based catalysts supported on nanosized NiO (nNiO) were synthesized and were investigated in the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) under base-free conditions using molecular oxygen as the oxidant, at 90 °C. By choosing the optimal composition of Au-Pd nanoparticles (6:4 Au/Pd atomic ratio), we report an efficient and stable nNiO-supported Au-Pd alloy catalyst. The presence of nNiO and Au-Pd nanoparticles on the surface was essential to achieve high conversion (95%) and high activity, high yield of FDCA (70%) and good level of stability. Significant synergistic effects were observed between Au and Pd in the alloy as well as on NiO. The present work provides mechanistic insights into the alloying effect and support-metal interaction in terms of understanding better the role of the alloy and support in affecting specific reaction pathways. Finally, the outcome of this knowledge can help develop efficient catalysts for the aerobic oxidation of biomass-derived molecules under base-free conditions in water and under mild reaction conditions.
- Bonincontro, Danilo,Lolli, Alice,Villa, Alberto,Prati, Laura,Dimitratos, Nikolaos,Veith, Gabriel M.,Chinchilla, Lidia E.,Botton, Gianlugi A.,Cavani, Fabrizio,Albonetti, Stefania
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p. 4090 - 4099
(2019/08/12)
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- Catalytic Synthesis of 2,5-Furandicarboxylic Acid from Concentrated 2,5-Diformylfuran Mediated by N-hydroxyimides under Mild Conditions
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Producing polyester monomer 2,5-furandicarboxylic acid (FDCA) from biomass as an alternative to fossil-derived terephthalic acid has drawn much attention from both academy and industry. In this work, an efficient FDCA synthesis was proposed from 10.6 wt % 2,5-diformylfuran (DFF) in acetic acid using a combined catalytic system of Co/Mn acetate and N-hydroxyimides. The intermediate product of 5-formyl-2-furandicarboxylic acid (FFCA) possesses the least reactive formyl group. N-hydroxysuccinimide was found to be superior to N-hydroxyphthalimide in catalyzing the oxidation of the formyl group in FFCA intermediate, affording a near 95 % yield of FDCA under mild conditions of 100 °C. Trace maleic anhydride was detected as by-product, which mainly came from the oxidative cleavage of DFF via furfural, furoic acid and 5-acetoxyl-2(5H)-furanone as intermediates.
- Xia, Fei,Ma, Jiping,Jia, Xiuquan,Guo, Meiling,Liu, Xuebin,Ma, Hong,Gao, Jin,Xu, Jie
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p. 3329 - 3334
(2019/09/03)
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- One-Pot Enzyme Cascade for Controlled Synthesis of Furancarboxylic Acids from 5-Hydroxymethylfurfural by H2O2 Internal Recycling
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Furancarboxylic acids are promising biobased building blocks in pharmaceutical and polymer industries. In this work, dual-enzyme cascade systems composed of galactose oxidase (GOase) and alcohol dehydrogenases (ADHs) are constructed for controlled synthesis of 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF), based on the catalytic promiscuity of ADHs. The byproduct H2O2, which is produced in GOase-catalyzed oxidation of HMF to 2,5-diformylfuran (DFF), is used for horseradish peroxidase (HRP)-mediated regeneration of the oxidized nicotinamide cofactors for subsequent oxidation of DFF promoted by an ADH, thus implementing H2O2 internal recycling. The desired products FFCA and FDCA are obtained with yields of more than 95 %.
- Jia, Hao-Yu,Zong, Min-Hua,Zheng, Gao-Wei,Li, Ning
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p. 4764 - 4768
(2019/11/05)
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- PROCESS FOR OXIDISING A SUBSTRATE
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A process for oxidising a substrate selected from hydroxymethylfurfural (HMF), diformylfuran (DFF), hydroxymethylfurancarboxylic acid (HMFCA) and formylfurancarboxylic acid (FFCA). Said process comprises mixing said substrate with catalase, one or more further enzymes and hydrogen peroxide to form a reaction mixture. Said one or more further enzymes have the ability to catalyse oxidation of said substrate. Said hydrogen peroxide is provided at a total molar ratio of at least about 0.1:1 hydrogen peroxide to substrate.
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Page/Page column 53-54
(2019/10/23)
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- Active Oxygen Species Promoted Catalytic Oxidation of 5-Hydroxymethyl-2-furfural on Facet-Specific Pt Nanocrystals
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The aerobic oxidation of alcohols and aldehydes over noble metal catalysts is a critical reaction for the catalytic conversion of carbohydrates into value-added chemicals from biomass. However, to fully understand the reaction mechanism, in particular, the role of O2 and the generated active oxygen species in these reactions is still a challenging target. In the present work, the sub-10 nm Pt nanocrystals with cubic (Pt-NCs), octahedral (Pt-NOs), and spherical (Pt-NSs) morphologies were synthesized and used as catalysts in aerobic oxidation of 5-hydroxymethyl-2-furfural (HMF). Through experimental and computational investigations, the facet-dependent O2 conversion pathway and catalytic oxidation performance were discussed. The molecular O2 tends to be dissociated to generate a€¢OH on a Pt(100) surface but prefers to be reduced to a€¢O2 - on a Pt(111) surface. Moreover, Pt-NCs enclosed by the {100} facets exhibited significantly enhanced catalytic activity compared to Pt-NOs enclosed by the {111} facets and Pt-NSs, in particular, for the alcohol oxidation step. On the basis of the experimental data and density functional theory (DFT) calculations, an active oxygen species promoted dehydrogenation mechanism for aerobic oxidation of HMF was proposed. The dehydrogenation of the alcohol group is more favorable on the Pt(100) surface with assistance of a€¢OH, which is the dominant active oxygen species on the Pt(100) surface. We anticipate that this work would provide new insight into the role of active oxygen species in aerobic oxidation of alcohols and aldehydes over noble metal catalysts.
- Liu, Yaqi,Ma, Hong-Yan,Lei, Da,Lou, Lan-Lan,Liu, Shuangxi,Zhou, Wuzong,Wang, Gui-Chang,Yu, Kai
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p. 8306 - 8315
(2019/08/26)
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- Preparation method of 5-formyl-2-furancarboxylic acid
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The invention provides a preparation method of 5-formyl-2-furancarboxylic acid. The preparation method comprises the steps that 5-hydroxymethylfurfural (HMF) is taken as a raw material, water is takenas a solvent, 0.2-0.6 mmol of Na2CO3 is added, g-C3N4/NaNbO3-X is taken as a catalyst, X is the molar ratio of NaNbO3 to g-C3N4 and is equal to 0.4-0.75, oxygen is continuously introduced, a xenon lamp with the power being 300 W is used as a radiation source, meanwhile, an optical fiber is added to enable incident light gamma to be greater than 400 nm, and reaction is conducted for 4-10 h. The preparation method is mild in reaction condition, low in cost, environmentally friendly and good in selectivity, and the HMF can be subjected to catalytic oxidation in a high selectivity mode.
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Paragraph 0014-0030
(2019/11/21)
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- Selective oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran over VPO catalysts under atmospheric pressure
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Vanadium phosphate oxide (VPO) heterogeneous catalysts with different V/P molar ratios were prepared and used for selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to produce 2,5-diformylfuran (DFF) in the liquid phase. It was found that the VPO catalyst with V/P molar ratio 0.25 exhibited the best catalytic performance. Then the VPO catalyst was utilized to catalyze the oxidation of HMF in a batch reactor under different conditions, in terms of type of solvent (water and organic), reaction time and temperature. A high DFF yield of 83.6% with HMF conversion of 100% was obtained under atmospheric pressure.
- Lai, Jinhua,Liu, Kai,Zhou, Shuolin,Zhang, Du,Liu, Xianxiang,Xu, Qiong,Yin, Dulin
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p. 14242 - 14246
(2019/05/21)
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