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.
2,5-DMF production through hydrogenation of real and synthetic 5-HMF over transition metal catalysts supported on carriers with different nature
Iriondo,Mendiguren,Güemez,Requies,Cambra
, p. 286 - 295 (2017)
Catalytic hydrogenolysis reaction of 5-hydroxymethylfurfural platform molecule to produce 2,5-dimethylfuran conversion was studied. For that purpose noble (Pt and Ru) and non-noble (Ni and Cu) metal catalysts supported on acid (HYAl2O3 and Al2O3) and basic (ZrO2 and TiO2) supports were used. All of the tested catalysts were able to convert completely HMF. However, among the mentioned catalysts, the Cu catalyst supported on ZrO2 showed the best behavior in terms of DMF selectivity, probably due to the neutral nature associated to ZrO2 support. Moreover, this catalyst was studied in order to know the influence of some reaction parameters on DMF selectivity. As results obtained with CuZr catalyst concluded, a temperature increase had not influence on the aforementioned parameter because the reaction is exothermic. However, the type of feed, the increment of the pressure and the space velocity decrease improved the DMF selectivity.
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.
A High-Throughput Composite Catalyst based on Nickel Carbon Cubes for the Hydrogenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran
Mani, Christian Mbaya,Braun, Max,Molinari, Valerio,Antonietti, Markus,Fechler, Nina
, p. 3388 - 3394 (2017)
A high-throughput composite catalyst is prepared from porous carbon with an unconventional nanocube morphology decorated with nickel nanoparticles. Owing to the advantageous properties of the designed carbon support, the composite combines a high surface area and a hierarchical pore structure with high functionality. Furthermore, the regularly shaped nanocubes allow for a good packing of a fixed-bed flow reactor, in which the internal transport pores cannot be blocked and stay open for efficient column performance. The composite is employed as a catalyst in the hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF), showing good catalytic performance and overcoming the conventional problem of column blocking.
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.
One-pot production of 2,5-dimethylfuran from fructose over Ru/C and a Lewis-Br?nsted acid mixture in: N, N -dimethylformamide
Wei, Zuojun,Lou, Jiongtao,Li, Zhenbin,Liu, Yingxin
, p. 6217 - 6225 (2016)
An efficient catalysis system composed of a Lewis-Br?nsted acid mixture and Ru/C using N,N-dimethylformamide as a solvent was developed for the one-pot conversion of fructose to 2,5-dimethylfuran (2,5-DMF) via the dehydration/hydrogenolysis sequence. The effects of various reaction parameters, such as solvent, catalyst type, catalyst loading, reaction pressure, temperature and time, on single fructose dehydration, 5-hydroxymethylfurfural (5-HMF) hydrogenolysis and the one-pot conversion of fructose to 2,5-DMF were systematically investigated. The results showed that 2,5-DMF could be successfully produced with a yield as high as 66.3 mol% by using a one-pot method directly from fructose under the optimized reaction conditions, which is by far the highest yield ever reported for the production of 2,5-DMF from fructose through a one-pot strategy. The Ru/C catalyst could be reused at least three times with a slight decrease in 2,5-DMF yield.
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.
MWW layered zeolites modified with niobium species - Surface and catalytic properties
Wojtaszek-Gurdak, Anna,Zielinska, Martyna,Ziolek, Maria
, p. 89 - 97 (2019)
New heterogeneous catalysts were obtained by modification of MWW zeolites (MCM-22 and MCM-56) by swelling and pillaring with niobiosilicate, achieved by two different methods. The main differences between these methods were time and temperature at which the modification was carried out, the concentration of a base used during the modification, and the water content in the catalysts used for further modification. The XRD analysis proved that both methods used gave MCM-36 structure, in all cases pillaring led to an increase in surface area, but some differences in final materials were noted, depending on the pillaring procedure. Both NbMCM-36 zeolites exhibited different content of micropores (lower in the zeolites synthesized from MCM-22), different loading with niobium species (higher in the material prepared from MCM-56) and similar acidity strength. Both niobium containing zeolites were active catalysts in liquid phase cyclohexene oxidation with H2O2 and were successfully used in the second run. Niobium played a role of H2O2 activator. Texture parameters and content of niobium was crucial for the effective discoloration of methylene blue with the use of hydrogen peroxide.
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
