625-86-5Relevant articles and documents
Selective hydrogenation of bio-based 5-hydroxymethyl furfural to 2,5-dimethylfuran over magnetically separable Fe-Pd/C bimetallic nanocatalyst
Talpade, Abhijit D.,Tiwari, Manishkumar S.,Yadav, Ganapati D.
, p. 1 - 15 (2019)
There is an ever increasing need to innovate and provide alternative energy sources to reduce the overdependence on conventional fossil fuels. 2, 5-Dimethylfuran (DMF), a bio-based chemical, has gained a lot of attention due to its potential application as a biofuel additive and is synthesized through hydrogenation of 5-hydroxymethylfurfural (HMF). Bimetallic nano-catalysts have gained importance in recent years due to their excellent selectivity and activity. In this paper, a magnetically separable Fe-Pd/C bimetallic nano-catalyst was developed which not only showed excellent selectivity to DMF but also helped reduce the noble metal consumption, thereby making the catalyst cheaper. Using XPS, XRD and TPR characterizarion techniques, the Fe-Pd/C catalyst was found to exist as bimetallic containing a partially oxidized Fe and reduced Pd atoms. It exhibited 85% selectivity towards DMF with 100% conversion of HMF. The reaction was conducted in a liquid-acid-free environment, thus making the process environmental friendly. The oxidized Fe imparts magnetic properties to the catalyst making it easy to recover. The catalyst was found to be robust and showed excellent activity on repeated use. Overall a highly efficient, economic and green process for DMF synthesis was developed based on biomass as feedstock.
Synthesis and ring opening reactions of 2-glyco-1,4-dimethyl-3-nitro-7-oxabicyclo[2.2.1]hept-5-enes
Araújo, Noelia,Gil, María V.,Román, Emilio,Serrano, José A.
, p. 2664 - 2674 (2010)
The high-pressure asymmetric Diels-Alder reactions of d-galacto- (1a) and d-manno-3,4,5,6,7-penta-O-acetyl-1,2-dideoxy-1-nitrohept-1-enitol (1b) with 2,5-dimethylfuran (2) afforded mixtures of cycloadducts, from which the (2S,3R)-3-exo-nitro (3a and 3b), (2R,3S)-3-exo-nitro (4a and 4b), and (2R,3S)-1′,2′,3′,4′,5′-penta-O-acetyl-1′-C-(1,4-dimethyl-3-endo-nitro-7-oxabicyclo[2.2.1]hept-5-en-2-exo-yl)-d-galacto-pentitol (5b) were isolated pure. Deacetylation of these compounds led to new chiral mono-, bi-, and tricyclic ethers, being their asymmetric centers arising from the chiral inductor used in the cycloaddition reaction. A ring opening mechanism through a 1-nitro-1,3-cyclohexadiene intermediate has been proposed.
Studies of synergy between metal-support interfaces and selective hydrogenation of HMF to DMF in water
Goyal, Reena,Sarkar, Bipul,Bag, Arijit,Siddiqui, Nazia,Dumbre, Deepa,Lucas, Nishita,Bhargava, Suresh Kumar,Bordoloi, Ankur
, p. 248 - 260 (2016)
Metal-support interfaces play a very important role in heterogeneous catalysis. The interfacial interactions not only are responsible for stabilizing the necessary oxidation state to facilitate the reaction but also enhance the stability of the catalyst system. Nano dispersion of Ni on mesoporous nitrogen-rich carbon material has been achieved using two different synthesis methods. It was observed that nickel (0) gets stabilized by strong interfacial interaction with the nitrogen atoms of the support material, and the material was found to be very economic and efficient for the conversion of HMF to DMF in aqueous medium. The material shows ≥99% conversion to 5-(hydroxymethyl) furfural (HMF) within 6 h of reaction with 98.7% DMF selectivity. A unique correlation between synthesis methods and particle sizes with catalytic performance has been observed for these newly developed materials. Furthermore, a DFT calculation has been performed to predict the reaction mechanism.
The role of Ru and RuO2 in the catalytic transfer hydrogenation of 5-hydroxymethylfurfural for the production of 2,5-dimethylfuran
Jae, Jungho,Zheng, Weiqing,Karim, Ayman M.,Guo, Wei,Lobo, Raul F.,Vlachos, Dionisios G.
, p. 848 - 856 (2014)
We have previously shown that 2,5-dimethylfuran (DMF) can be produced selectively from 5-hydroxymethylfurfural in up to 80 % yield via catalytic transfer hydrogenation with 2-propanol as a hydrogen donor and Ru/C as a catalyst. Herein, we investigate the active phase of the Ru/C catalyst by using extended X-ray absorption fine structure, X-ray photoelectron spectroscopy, and high-resolution TEM analyses. The results reveal that RuO2 is the dominant phase in the fresh (active) catalyst and is reduced to metallic Ru during the reaction with the hydrogen produced insitu from 2-propanol. The deactivation of the catalyst is correlated with the reduction of the surface of RuO2. Reactivity studies of individual phases (bulk RuO2 and reduced Ru/C catalysts) indicate that RuO2 mainly catalyzes the Meerwein-Ponndorf-Verley reaction of 5-hydroxymethylfurfural that produces 2,5-bis(hydroxymethyl)furan and the etherification of 2,5-bis(hydroxymethyl) furan or other intermediates with 2-propanol and that the reduced Ru/C catalyst has moderate hydrogenolysis activity for the production of DMF (30 % selectivity) and other intermediates (20 %). In contrast, a physical mixture of the two phases increases the DMF selectivity up to 70 %, which suggests that both metallic Ru and RuO2 are active phases for the selective production of DMF. The oxidation of the reduced Ru/C catalyst at different temperatures and the insitu hydrogen titration of the oxidized Ru/C catalysts were performed to quantify the bifunctional role of Ru and RuO2 phases. The mild oxidation treatment of the Ru/C catalyst at 403K could activate the catalyst for the selective production of DMF in up to 72 % yield by generating a partially oxidized Ru catalyst. Double trouble: A selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran is achieved with a partially oxidized Ru/C as a catalyst and 2-propanol as a hydrogen donor. The oxidized Ru/C catalyst demonstrates bifunctional behavior, in which Ru catalyzes the dehydrogenation of 2-propanol and the hydrogenation-hydrogenolysis of 5-hydroxymethylfurfural and RuO2 promotes dimethylfuran production via hydrogenolysis.
Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals
Binder, Joseph B.,Raines, Ronald T.
, p. 1979 - 1985 (2009)
Lignocellulosic biomass is a plentiful and renewable resource for fuels and chemicals. Despite this potential, nearly all renewable fuels and chemicals are now produced from edible resources, such as starch, sugars, and oils; the challenges imposed by notoriously recalcitrant and heterogeneous lignocellulosic feedstocks have made their production from nonfood biomass inefficient and uneconomical. Here, we report that N,N-dimethylacetamide (DMA) containing lithium chloride (LiCl) is a privileged solvent that enables the synthesis of the renewable platform chemical 5-hydroxymethylfurfural (HMF) in a single step and unprecedented yield from untreated lignocellulosic biomass, as well as from purified cellulose, glucose, and fructose. The conversion of cellulose into HMF is unabated by the presence of other biomass components, such as lignin and protein. Mechanistic analyses reveal that loosely ion-paired halide ions in DMA-LiCl are critical for the remarkable rapidity (1-5 h) and yield (up to 92%) of this low-temperature (≤140 °C) process. The simplicity of this chemical transformation of lignocellulose contrasts markedly with the complexity of extant bioprocesses and provides a new paradigm for the use of biomass as a raw material for a renewable energy and chemical industries.
Supported Pd-Au bimetallic nanoparticles as an efficient catalyst for the hydrodeoxygenation of vanillin with formic acid at room temperature
Cai, Chun,Lu, Guoping,Wu, Pengyu,Zhao, Danxia
, p. 1096 - 1102 (2022/02/17)
Hydrodeoxygenation (HDO) for upgrading biomass usually requires high temperature and high H2 pressure. Herein, g-C3N4-supported Pd-Au bimetallic nanoparticles are reported as an efficient catalyst for the HDO of vanillin, a typical biomass-derived compound, and some other aromatic aldehydes. With the catalyst and formic acid as the hydrogen donor, the reaction occurs at room temperature and under atmospheric air, and a satisfactory yield of the desired product was achieved within 1 h. A two-phase solvent of H2O and EA was used, and the catalyst could be reused at least 5 times. The superior performance of PdAu/g-C3N4 compared to monometallic catalysts could be mainly ascribed to the synergistic catalysis inside the catalyst, which was explored via characterization analysis. This journal is
Pt-Carbon interaction-determined reaction pathway and selectivity for hydrogenation of 5-hydroxymethylfurfural over carbon supported Pt catalysts
Wang, Xiaofeng,Zhang, Chengcheng,Jin, Baitang,Liang, Xinhua,Wang, Qingfa,Zhao, Zhe,Li, Qingbo
, p. 1298 - 1310 (2021/03/14)
In this study, a series of Pt catalysts supported on carbon materials, including multi-walled carbon nanotubes (CNTs), reduced graphene oxide (rGO), graphitic carbon nitride (g-C3N4), and biochar (BC), were prepared by impregnation or atomic layer deposition (ALD) methods. The Pt content was around 2.5 wt% in all the Pt catalysts, and the average Pt particle size was 1.6-1.9 nm for the catalysts prepared by impregnation (IM), which was slightly larger than that for the Pt catalyst (～1.4 nm) synthesized by ALD (Pt/CNTs-ALD). All the catalysts were used in the HMF hydrogenation reaction to investigate the effects of different carbon materials and Pt-carbon interactions on the catalytic performance of catalysts. The main product was DHMF over all the Pt catalysts prepared by impregnation, and Pt/BC-IM showed the highest turnover frequency and the highest selectivity to DHMF (95.3%) with an HMF conversion of 94.6% after 10 h of reaction time, which could be due to the abundant functional groups on the surface of BC. Compared with the Pt/CNTs-IM catalyst, the main product over the Pt/CNTs-ALD catalyst was DMF with a yield of 47% due to the relatively strong Pt-CNT interaction. The interaction between Pt and CNTs is the dominant factor in determining the main product in the selective HMF hydrogenation reaction. After introducing Ni nanoparticles to Pt/CNTs-ALD, the yield of DMF reached 93.4% over the PtNi/CNTs-ALD bimetallic catalyst owing to the synergistic effect between Pt and Ni.
Ni-Al/CoOx-catalyzed hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran at low temperatures without external hydrogen
An, Yadan,Bai, Guoyi,Bian, Gang,Li, Tianming,Niu, Libo,Xia, Zhanghui
, p. 7763 - 7772 (2021/10/12)
Catalytic hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran has received great interest in recent years. In this work, a ternary Ni-Al/CoOx-1 catalyst was fabricated, which provided 96% yield of DMF from in situ hydrodeoxygenation of HMF under mild reaction conditions. XRD, TEM and TPR revealed that the addition of Al to the Ni-Co bimetallic system could make the structure more stable and improve the dispersion of Ni and Co species. XPS, CO-DRIFTS and EPR verified that an enhanced electron transfer from Co species to Ni occurred on Ni-Al/CoOx-1. Reaction mechanism studies unraveled that the Al addition results in promoting in situ H2 production from 2-propanol and accelerating the aldehyde group hydrogenation to a hydroxymethyl group and the subsequent hydrogenolysis into a methyl group, due to the formation of a charge separated metal-couple-site (Niδ-Coδ+) and stronger Lewis acid sites in Ni-Al/CoOx-1. In addition, this ternary Ni-Al/CoOx-1 catalyst exhibits superior recyclability without significant loss of activity for 7 cycles.
