13529-17-4Relevant articles and documents
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Nazorova et al.
, (1967)
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Mechanistic Studies on the Photooxidation of 5-Hydroxymethylfurfural by Polyoxometalate Catalysts and Atmospheric Oxygen
Li, Zheng,Zhang, Mo,Xin, Xing,Lv, Hongjin
, p. 1389 - 1395 (2021)
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.
Alkaline ionic liquid modified Pd/C catalyst as an efficient catalyst for oxidation of 5-hydroxymethylfurfural
Bin, Zou,Xueshan, Chen,Jiaojiao, Xia,Cunshan, Zhou
, (2018)
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.
Hybrid Conversion of 5-Hydroxymethylfurfural to 5-Aminomethyl-2-furancarboxylic acid: Toward New Bio-sourced Polymers
Lancien, Antoine,Wojcieszak, Robert,Cuvelier, Eric,Duban, Matthieu,Dhulster, Pascal,Paul, Sébastien,Dumeignil, Franck,Froidevaux, Renato,Heuson, Egon
, p. 247 - 259 (2021)
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.
Chloroperoxidase-catalyzed oxidation of 5-hydroxymethylfurfural
Van Deurzen,Van Rantwijk,Sheldon
, p. 299 - 309 (1997)
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.
Hydrotalcite-supported gold-nanoparticle-catalyzed highly efficient base-free aqueous oxidation of 5-hydroxymethylfurfural into 2,5- furandicarboxylic acid under atmospheric oxygen pressure
Gupta, Navneet Kumar,Nishimura, Shun,Takagaki, Atsushi,Ebitani, Kohki
, p. 824 - 827 (2011)
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.
Selective synthesis of 2-furoic acid and 5-hydroxymethyl-2-furancarboxylic acid from bio-based furans by recombinant Escherichia coli cells
Shi, Sai-Sai,Zhang, Xue-Ying,Zong, Min-Hua,Wang, Chuan-Fu,Li, Ning
, p. 68 - 74 (2019)
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%.
CeO2@N/C@TiO2 Core-shell Nanosphere Catalyst for the Aerobic Oxidation of 5-Hydroxymethylfurfural to 5-Hydroxymethyl-2-Furancarboxylic Acid
Song, Yong,Waterhouse, Geoffrey I. N.,Han, Feng,Li, Yan,Ai, Shiyun
, p. 2931 - 2941 (2021)
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.
Visible-Light-Driven Valorization of Biomass Intermediates Integrated with H2 Production Catalyzed by Ultrathin Ni/CdS Nanosheets
Han, Guanqun,Jin, Yan-Huan,Burgess, R. Alan,Dickenson, Nicholas E.,Cao, Xiao-Ming,Sun, Yujie
, p. 15584 - 15587 (2017)
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.
Enzyme-catalyzed selective oxidation of 5-hydroxymethylfurfural (HMF) and separation of HMF and 2,5-diformylfuran using deep eutectic solvents
Qin, Ye-Zhi,Li, Yan-Mei,Zong, Min-Hua,Wu, Hong,Li, Ning
, p. 3718 - 3722 (2015)
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.
Inexpensive but Highly Efficient Co–Mn Mixed-Oxide Catalysts for Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid
Rao, Kasanneni Tirumala Venkateswara,Rogers, Jennifer Lorraine,Souzanchi, Sadra,Dessbesell, Luana,Ray, Madhumita Bhowmick,Xu, Chunbao (Charles)
, p. 3323 - 3334 (2018)
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.
Highly Efficient Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid with Heteropoly Acids and Ionic Liquids
Chen, Ruru,Xin, Jiayu,Yan, Dongxia,Dong, Huixian,Lu, Xingmei,Zhang, Suojiang
, p. 2715 - 2724 (2019)
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.
Kinetics and mechanism of 5-hydroxymethylfurfural oxidation and their implications for catalyst development
Davis, Sara E.,Benavidez, Angelica D.,Gosselink, Robert W.,Bitter, Johannes H.,De Jong, Krijn P.,Datye, Abhaya K.,Davis, Robert J.
, p. 123 - 132 (2014)
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.
Fe-Zr-O catalyzed base-free aerobic oxidation of 5-HMF to 2,5-FDCA as a bio-based polyester monomer
Yan, Dongxia,Xin, Jiayu,Zhao, Qiu,Gao, Kai,Lu, Xingmei,Wang, Gongying,Zhang, Suojiang
, p. 164 - 175 (2018)
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.
The continuous oxidation of HMF to FDCA and the immobilisation and stabilisation of periplasmic aldehyde oxidase (PaoABC)
McKenna,Mines,Law,Kovacs-Schreiner,Birmingham,Turner,Leimkühler,Carnell
, p. 4660 - 4665 (2017)
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.
Ruthenium(iii) polyethyleneimine complexes for bifunctional ammonia production and biomass upgrading
Xu, Guang-Rui,Batmunkh, Munkhbayar,Donne, Scott,Jin, Hongni,Jiang, Jia-Xing,Chen, Yu,Ma, Tianyi
, p. 25433 - 25440 (2019)
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.
Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites: fact or fiction?
Ardemani, Leandro,Cibin, Giannantonio,Dent, Andrew J.,Isaacs, Mark A.,Kyriakou, Georgios,Lee, Adam F.,Parlett, Christopher M. A.,Parry, Stephen A.,Wilson, Karen
, p. 4940 - 4945 (2015)
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.
Base-free atmospheric O2-mediated oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic acid triggered by Mg-bearing MTW zeolite supported Au nanoparticles
Chen, Lei,Zhuang, Wenxia,Lan, Jingmin,Liu, Xiaoling,Jiang, Shi,Wang, Lei,Zhou, Yu,Wang, Jun
, (2021)
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.
Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid
Chen, Lei,Jiang, Shi,Liu, Xiaoling,Wang, Jun,Xu, Hongzhong,Zhou, Yu
, p. 994 - 1003 (2021)
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.
Metal-functionalized carbon nanotubes for biomass conversion: Base-free highly efficient and recyclable catalysts for aerobic oxidation of 5-hydroxymethylfurfural
Sharma, Poonam,Solanki, Mohit,Sharma, Rakesh K.
, p. 10601 - 10609 (2019)
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.
Pt and Pt/Sn carbonyl clusters as precursors for the synthesis of supported metal catalysts for the base-free oxidation of HMF
Bonincontro, Danilo,Lolli, Alice,Storione, Alba,Gasparotto, Alberto,Berti, Beatrice,Zacchini, Stefano,Dimitratos, Nikolaos,Albonetti, Stefania
, (2019)
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.
Synthesis of 2,5-furandicarboxylic acid by a TEMPO/laccase system coupled withPseudomonas putidaKT2440
Ouyang, Jia,Tan, Huanghong,Xu, Qianqian,Zheng, Zhaojuan,Zou, Lihua
, p. 21781 - 21788 (2020)
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.
Effect of Gold Particles Size over Au/C Catalyst Selectivity in HMF Oxidation Reaction
Megías-Sayago, Cristina,Lolli, Alice,Bonincontro, Danilo,Penkova, Anna,Albonetti, Stefania,Cavani, Fabrizio,Odriozola, José Antonio,Ivanova, Svetlana
, p. 1177 - 1183 (2020)
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.
Efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran on manganese oxide catalysts
Nie, Junfang,Liu, Haichao
, p. 57 - 66 (2014)
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.
Defect-Rich High-Entropy Oxide Nanosheets for Efficient 5-Hydroxymethylfurfural Electrooxidation
Gu, Kaizhi,Huang, Gen,Liu, Yanbo,Tao, Li,Wang, Dongdong,Wang, Shuangyin,Wang, Tehua,Xie, Chao,Zou, Yuqin
, p. 20253 - 20258 (2021)
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.
Efficient synthesis of 2,5-furandicarboxylic acid from biomass-derived 5-hydroxymethylfurfural in 1,4-dioxane/H2O mixture
Fang, Huayu,Ke, Xixian,Li, Tianyuan,Lin, Lu,Liu, Huai,Sun, Yong,Tang, Xing,Xie, Weizhen,Zeng, Xianhai
, (2021/12/17)
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.
A PROCESS FOR THE SYNTHESIS OF FURANDICARBOXYLIC ACID
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Paragraph 00049; 00056, (2021/06/26)
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%.
