163857-09-8Relevant articles and documents
One-step approach to 2,5-diformylfuran from fructose by proton- and vanadium-containing graphitic carbon nitride
Chen, Jinzhu,Guo, Yuanyuan,Chen, Jiayi,Song, Lu,Chen, Limin
, p. 3174 - 3181 (2014)
5-Hydroxymethylfurfural (HMF) was selectively synthesized from fructose by using protonated graphitic carbon nitride [g-C3N4 (H+)] as a solid acid. With g-C3N4 as the same precursor material, 2,5-diformylfuran (DFF) was efficiently obtained from aerobic oxidation of HMF by using vanadium-doped g-C3N4 (V-g-C3N4) as an environmentally benign heterogeneous catalyst with atmospheric pressure of molecular oxygen as the oxidant. In addition, a combination of g-C3N4(H+) and V-g-C3N4 successfully afforded the direct synthesis of DFF from fructose through g-C3N4(H+)-promoted fructose dehydration and V-g-C3N4-catalyzed successively aerobic oxidation of HMF to DFF in a one-pot and two-step process. Moreover, a bifunctional catalyst made of protonated V-g-C3N4 [V-g-C3N4(H+)] allowed onepot as well as one-step direct transformation of fructose into DFF. Under optimized conditions, 80% yield of HMF and 82% yield of DFF were obtained from g-C3N4(H+)-promoted fructose dehydration and V-g-C3N4-catalyzed HMF oxidation, respectively. Stepwise addition of g-C3N4(H+) and V-g-C3N4 in the one-pot process improved the DFF yield up to 63% from fructose. In contrast, V-g-C3N4(H+)-catalyzed direct one-step transformation of fructose into DFF led to a DFF yield of 45 %. The research highlights a one-step approach to DFF from fructose with functional g-C3N4 catalyst.
AuPd-Fe3O4 Nanoparticle-Catalyzed Synthesis of Furan-2,5-dimethylcarboxylate from 5-Hydroxymethylfurfural under Mild Conditions
Cho, Ahra,Byun, Sangmoon,Cho, Jin Hee,Kim, Byeong Moon
, p. 2310 - 2317 (2019)
Efficient one-pot oxidative esterification of 5-hydroxymethylfurfural (HMF) to furan-2,5-dimethylcarboxylate (FDMC) was achieved under extremely mild reaction conditions by using AuPd alloy nanoparticles (NPs) supported on Fe3O4. A high yield of FDMC (92 %) was obtained at room temperature under atmospheric O2. The reaction proceeded through the synergistic effects of the AuPd heterobimetallic catalyst system. The most effective molar ratio of noble metal contents for HMF oxidation was 1.00:1.18. If Au-Fe3O4 NPs were used as the catalyst, selective synthesis of 5-hydroxymethylfuroic acid methyl ester (HMFE) was achieved. Additionally, the AuPd-Fe3O4 catalyst could be successfully reused.
Aerobic oxidation of biomass derived 5-hydroxymethylfurfural into 5-hydroxymethyl-2-furancarboxylic acid catalyzed by a montmorillonite K-10 clay immobilized molybdenum acetylacetonate complex
Zhang, Zehui,Liu, Bing,Lv, Kangle,Sun, Jie,Deng, Kejan
, p. 2762 - 2770 (2014)
In this study, we have successfully prepared a heterogeneous catalyst (K-10 clay-Mo) by the immobilization of bis(acetylacetonato) dioxo-molybdenum(vi) [MoO2(acac)2] on montmorillonite K-10 clay. The structure of the resultant catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electronic microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The catalytic activity of K-10 clay-Mo was tested in the aerobic oxidation of 5-hydroxymethylfurfural (HMF). Although a molecule of HMF contains one hydroxyl group and one aldehyde group, to our surprise, the catalyst showed high catalytic activity for the oxidation of the aldehyde group of HMF into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). A variety of important reaction parameters such as the reaction temperature, catalyst amount, and solvent were explored. HMFCA could be obtained in a high yield of 86.9% with a HMF conversion of 100% after a short reaction time of 3 h in toluene. More importantly, the catalyst K-10 clay-Mo could be reused several times without a significant loss of its catalytic activity. the Partner Organisations 2014.
Organic radical functionalized SBA-15 as a heterogeneous catalyst for facile oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran
Mittal, Neha,Nisola, Grace M.,Seo, Jeong Gil,Lee, Seong-Poong,Chung, Wook-Jin
, p. 106 - 114 (2015)
Organic radical functionalized mesoporous silica was prepared by the immobilization of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) on ordered mesoporous silica (SBA-15) and applied as a heterogeneous catalyst (TEMPO-SBA-15) for the synthesis of 2,5-diformylfuran (2,5-DFF) from 5-hydroxymethylfurfural (5-HMF). A 73 % 2,5-DFF yield was obtained from 5-HMF oxidation under mild reaction conditions in ethyl acetate with the addition of [bis(acetoxy) iodo]benzene (BAIB) and acetic acid as co-oxidants in an oxygen-rich environment. The presence of BAIB and oxygen facilitated the in-situ regeneration of TEMPO (the hydroxylamine form) whereas acetic acid addition aided in the initial formation of oxoammonium form of TEMPO, which was responsible for facile 5-HMF oxidation. All reaction components were found critical in maximizing the 2,5-DFF yield. The pore size distribution and architecture of SBA-15 played essential roles for the diffusive transport of reactants and products and resulted in improved reaction selectivity. Aside from these advantages, TEMPO-SBA-15 catalyst was easily separated and re-used several times with negligible loss in its catalytic activity. The prepared heterogeneous TEMPO-SBA-15 is an efficient catalyst that offers a sustainable route for 2,5-DFF production.
Efficient one-pot fructose to DFF conversion using sulfonated magnetically separable MOF-derived Fe3O4 (111) catalysts
Fang, Ruiqi,Luque, Rafael,Li, Yingwei
, p. 647 - 655 (2017)
Aerobic oxidation of carbohydrate-derived 5-hydroxymethylfurfural (HMF) into high added-value 2,5-diformylfuran (DFF) has attracted much attention in recent years. However, the direct synthesis of DFF from cheap and abundant carbohydrates via HMF as an intermediate through a one-pot process is highly desirable but challenging. In this work, we have developed a highly efficient and recyclable non-noble heterogeneous catalyst for one-pot conversion of fructose into DFF with extremely high yields (>99%). The catalyst was prepared by a simple pyrolysis method using Fe-based metal-organic frameworks (MOF) as a template and sulfur powder as a dopant. The pyrolysis of the MOF template under interactions of Ostwald ripening and Kirkendall effects led to the formation of uniform octahedral Fe3O4 nanoparticles with exposed (111) crystal facets highly dispersed on sulfur doped carbon. The superior selectivity to DFF over the designed Fe-based catalyst is related to the low adsorption energy of DFF on the support as well as the existence of non-oxidized sulfur that makes the catalytic system less oxidative.
Heterostructured manganese catalysts for the selective oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran
Pal, Priyanka,Saravanamurugan, Shunmugavel
, (2020)
A series of manganese oxide catalysts were synthesised in the presence of various precipitants using hydrothermal approach. The manganese oxide synthesised (MnOx?A?U) using manganese acetate tetrahydrate and urea as precursor and precipitant, respectively, was found to be composed of heterostructures of manganese, that is, MnCO3, ?-MnO2 and Mn2O3, and their presence were confirmed by XRD, FTIR and XPS analyses. The catalytic activity of MnOx?A?U towards selective oxidation of HMF to DFF in ethanol afforded 92.0 % conversion along with 88.0 % DFF yield at 120 °C, 30 bar O2, after 4 h of reaction time. Performing HMF oxidation under N2 atmosphere with MnOx?A?U yielded only 15.0 % DFF, revealing that lattice oxygen played a crucial role in the oxidation process, which was confirmed by subjecting the spent catalyst to XPS analysis. Based on the results obtained from XPS analysis, it was speculated that ?-MnO2 and MnCO3 could be the active species which could selectively catalyse the reaction. The MnOx?A?U catalyst was able to recycle for at least three runs with a small loss of activity due to ?-MnO2 content decreased.
Imidazole-Functionalized Polyoxometalate Catalysts for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran Using Atmospheric O2
Liu, Dan,Chen, Baokuan,Li, Jie,Lin, Zhengguo,Li, Peihe,Zhen, Ni,Chi, Yingnan,Hu, Changwen
, p. 3909 - 3916 (2021)
Biomass as a sustainable and abundant carbon source has attracted considerable attention as a potential alternative to petroleum resources. The selective oxidation of 5-hydroxymethylfurfural (HMF), a versatile platform molecule, to value-added 2,5-diformylfuran (DFF) provides an efficient pathway for biomass valorization. Herein, three discrete imidazole-functionalized polyoxometalates (POMs), HPMo8VVI4O40(VVO)2[(VIVO)(IM)4]2·nH2O·(IM)m (IM = 1-methylimidazole, n = 4, m = 8 for 1; IM = 1-ethylimidazole, n = 4, m = 9 for 2; IM = 1-propylimidazole, n = 0, m = 4 for 3), have been successfully synthesized by a facile solvothermal method and thoroughly characterized by routine techniques. Compounds 1-3 contain a bi-capped pseudo-Keggin {HPMo8V4O40(VO)2} and two imidazole-functionalized {(VO)(IM)4} groups, which, to our knowledge, represent the first examples of organic-functionalized Mo-V clusters. Compounds 1-3 as heterogeneous catalysts can effectively promote the transformation of HMF to DFF using atmospheric O2 as oxidant. Under minimally optimized conditions, 95% of HMF was converted by 1 with 95% selectivity for DFF and its catalytic activity was basically maintained after five cycles. Moreover, the important roles of the bi-capped pseudo-Keggin cluster and the functionalized V groups in the selective oxidation of HMF have been explored. According to experimental and spectroscopic results, a three-step oxidation mechanism of HMF to DFF has been proposed.
Polyaniline-grafted VO(acac)2: An effective catalyst for the synthesis of 2,5-diformylfuran from 5-hydroxymethylfurfural and fructose
Xu, Fenghua,Zhang, Zehui
, p. 1470 - 1477 (2015)
Herein, polyaniline-grafted vanadyl acetylacetonate [VO(acac)2] was prepared and used as an effective catalyst for the oxidation of 5-hydroxymethylfurfural (HMF) under atmospheric oxygen pressure. A high HMF conversion of 99.2 % was obtained after 12 h at 110 C, and 2,5-diformylfuran (DFF) was obtained in 86.2 % yield. More importantly, the one-pot conversion of fructose into DFF was also realized with two binary catalysts: Amberlyst-15 and polyaniline-VO(acac)2. Amberlyst-15 was used for the acid-catalyzed dehydration of fructose into HMF, followed by the in situ oxidation of HMF catalyzed by polyaniline-VO(acac)2. DFF could be obtained in a yield of 42.1 % from fructose by using the one-pot reaction, whereas two consecutive steps gave a higher DFF yield of 71.1 %. Owing to the facile catalyst preparation and low cost, this method showed a promising potential for the synthesis of DFF from abundant carbohydrates.
One-step synthesis of 2,5-diformylfuran from monosaccharides by using lanthanum(iii) triflate, sulfur, and DMSO
Nguyen, Quynh Nhu Ba,Le, Hao Anh Nguyen,Ly, Phat Duc,Phan, Ha Bich,Tran, Phuong Hoang
, p. 13005 - 13008 (2020)
The combination of lanthanum(iii) triflate, sulfur, and dimethyl sulfoxide prompted a facile, direct preparation of 2,5-diformylfuran from glucose and fructose. The one-step dehydration/oxidation of fructose afforded 2,5-diformylfuran in an excellent yield with high selectivity. The proposed mechanism, large-scale synthesis, and product separation were presented. This approach represents a straightforward and eco-friendly pathway, which can be applied in the large-scale production of 2,5-diformylfuran from fructose. This journal is
A one-pot two-step approach for the catalytic conversion of glucose into 2,5-diformylfuran
Xiang, Xi,He, Ling,Yang, Yu,Guo, Bin,Tong, Dongmei,Hu, Changwei
, p. 735 - 741 (2011)
One-pot two-step synthesis of DFF was achieved by catalytic conversion of glucose over CrCl3?6H2O/NaBr//NaVO 3?2H2O catalysts, and a DFF yield of 55% based on glucose was obtained. This glucose conversion process is characterized by the abundance and low cost of starting material and no need for HMF separation or purification. Graphical Abstract: An alternative one-pot one-step approach for the catalytic conversion of glucose into DFF with a yield of 18% in the CrCl3?6H2O/NaBr//NaVO3?2H 2O system has been reported for the first time. Two-step process can give higher DFF yield than one-step, and the best DFF yield of 55% can be obtained under mild reaction conditions.
