- Selective hydrogenation of bio-based 5-hydroxymethyl furfural to 2,5-dimethylfuran over magnetically separable Fe-Pd/C bimetallic nanocatalyst
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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.
- Talpade, Abhijit D.,Tiwari, Manishkumar S.,Yadav, Ganapati D.
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- Synthesis and ring opening reactions of 2-glyco-1,4-dimethyl-3-nitro-7-oxabicyclo[2.2.1]hept-5-enes
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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.
- Araújo, Noelia,Gil, María V.,Román, Emilio,Serrano, José A.
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- 2,5-DMF production through hydrogenation of real and synthetic 5-HMF over transition metal catalysts supported on carriers with different nature
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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.
- Iriondo,Mendiguren,Güemez,Requies,Cambra
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- Studies of synergy between metal-support interfaces and selective hydrogenation of HMF to DMF in water
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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.
- Goyal, Reena,Sarkar, Bipul,Bag, Arijit,Siddiqui, Nazia,Dumbre, Deepa,Lucas, Nishita,Bhargava, Suresh Kumar,Bordoloi, Ankur
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- A High-Throughput Composite Catalyst based on Nickel Carbon Cubes for the Hydrogenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran
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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.
- Mani, Christian Mbaya,Braun, Max,Molinari, Valerio,Antonietti, Markus,Fechler, Nina
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- The role of Ru and RuO2 in the catalytic transfer hydrogenation of 5-hydroxymethylfurfural for the production of 2,5-dimethylfuran
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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.
- Jae, Jungho,Zheng, Weiqing,Karim, Ayman M.,Guo, Wei,Lobo, Raul F.,Vlachos, Dionisios G.
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- One-pot production of 2,5-dimethylfuran from fructose over Ru/C and a Lewis-Br?nsted acid mixture in: N, N -dimethylformamide
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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.
- Wei, Zuojun,Lou, Jiongtao,Li, Zhenbin,Liu, Yingxin
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- Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals
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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.
- Binder, Joseph B.,Raines, Ronald T.
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- MWW layered zeolites modified with niobium species - Surface and catalytic properties
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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.
- Wojtaszek-Gurdak, Anna,Zielinska, Martyna,Ziolek, Maria
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- Supported Pd-Au bimetallic nanoparticles as an efficient catalyst for the hydrodeoxygenation of vanillin with formic acid at room temperature
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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
- Cai, Chun,Lu, Guoping,Wu, Pengyu,Zhao, Danxia
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p. 1096 - 1102
(2022/02/17)
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- Metal Catalyst and Hydrogen Gas-Free Selective Reduction of Biomass-Derived Substituted Furfuraldehyde to Alkyl Furan as a Key Biofuel Additive
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A metal catalyst and a hydrogen gas-free approach has been developed for selective reduction of aldehyde to an alkyl group of different substituted furan compounds. In this process, hydrazine hydrate under basic conditions at reflux temperature selectively participated in the reduction of the aldehyde moiety to the corresponding alkyl group of highly reactive furan compounds in a selective manner. The developed protocol was applied for selective and scalable reduction of 5-hydroxymethylfurfural (5-HMF) up to 250 g to 5-methylfurfuryl alcohol (MFA) in a 70% yield. Under the same process, furfuraldehyde was also tested in a 250 g reaction for 2-methylfuran (MF) synthesis in a highly selective manner and the product was distilled out from a single-pot reaction with gas chromatography (GC) purity ≥90%. The scope of the process was further extended for different substituted furfuraldehydes successfully. In addition, the protocol is found to be efficient for scalable production and easy separation of the product.
- Chauhan, Arvind Singh,Kumar, Ajay,Das, Pralay
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supporting information
p. 892 - 899
(2021/04/12)
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- METAL CATALYST AND HYDROGEN GAS FREE APPROACHES FOR SELECTIVE REDUCTION OF ALDEHYDE TO METHYL GROUP OF DIFFERENT SUBSTITUTED FURANS
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The present invention relates to 5-methyl substituted furan compounds of general formula (I) and process for the preparation thereof: OR1R2 R3CH3(I) Particularly, the present invention relates to a metal catalyst and hydrogen gas free, atom-economy, highly selective and low-cost process for the preparation of methyl substituted furan compounds from different aldehyde substituted furan compounds.
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Page/Page column 18
(2021/08/27)
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- Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
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Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C?O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C?OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H?.
- Hu, Bin,Warczinski, Lisa,Li, Xiaoyu,Lu, Mohong,Bitzer, Johannes,Heidelmann, Markus,Eckhard, Till,Fu, Qi,Schulwitz, Jonas,Merko, Mariia,Li, Mingshi,Kleist, Wolfgang,H?ttig, Christof,Muhler, Martin,Peng, Baoxiang
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supporting information
p. 6807 - 6815
(2021/02/01)
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- Formic acid enabled selectivity boosting in transfer hydrogenation of 5-hydroxymethylfurfural to 2,5-furandimethanol on highly dispersed Co-Nxsites
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Catalytic transfer hydrogenation (CTH) reaction is considered as a potential route for upgrading bio-based carbonyl compounds to their corresponding alcohols. Herein, ordered mesoporous N-doped carbon confined Co-Nx(Co-NC) was adopted as a catalyst for converting cellulose-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandimethanol (FDM) using formic acid (FA) as a hydrogen donor. Different catalysts and preparation methods were screened, by varying cobalt phases and template removal procedures. It is found that highly dispersed N-confined Co species (Co-Nx) other than naked Co NPs acted as catalytic species for the CTH of HMF with FA, which gave 86% yield of FDM at 100% HMF conversion. Kinetic experiments revealed that, compared with molecular hydrogen, Co-NC could effectively accelerate HMF hydrogenation and suppress as-formed FDM hydrogenolysis in the presence of FA, which is ascribed to its superior activity toward hydrogen transfer from FA and fast desorption toward FDM. Mechanism studies indicated that C-H dissociation of FA could be the rate-determining step in the CTH reaction, and the hydrogenation of HMF could proceed through an intermolecular hydride transfer route. This work shows that the bifunctional nature of the catalyst is critical in the efficient CTH of biomass-derived carbonyl compounds and provides insights toward the rational design of such catalysts.
- Xu, Ling,Nie, Renfeng,Chen, Xujie,Li, Yanchen,Jiang, Yuxi,Lu, Xiuyang
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p. 1451 - 1457
(2021/03/14)
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- Tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural over a Ni3Fe intermetallic supported Pt single-atom site catalyst
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Single-atom site catalysts (SACs) have been used in multitudinous reactions delivering ultrahigh atom utilization and enhanced performance, but it is challenging for one single atom site to catalyze an intricate tandem reaction needing different reactive sites. Herein, we report a robust SAC with dual reactive sites of isolated Pt single atoms and the Ni3Fe intermetallic support (Pt1/Ni3Fe IMC) for tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural (5-HMF). It delivers a high catalytic performance with 99.0% 5-HMF conversion in 30 min and a 2, 5-dimethylfuran (DMF) yield of 98.1% in 90 min at a low reaction temperature of 160 °C, as well as good recyclability. These results place Pt1/Ni3Fe IMC among the most active catalysts for the 5-HMF hydrodeoxygenation reaction reported to date. Rational control experiments and first-principles calculations confirm that Pt1/Ni3Fe IMC can readily facilitate the hydrodeoxygenation reaction by a tandem mechanism, where the single Pt site accounts for C-O group hydrogenation and the Ni3Fe interface promotes the C-OH bond cleavage. This interfacial tandem catalysis over the Pt single-atom site and Ni3Fe IMC support may develop new opportunities for the rational structural design of SACs applied in other heterogeneous tandem reactions.
- Meng, Ge,Ji, Kaiyue,Zhang, Wei,Kang, Yiran,Wang, Yu,Zhang, Ping,Wang, Yang-Gang,Li, Jun,Cui, Tingting,Sun, Xiaohui,Tan, Tianwei,Wang, Dingsheng,Li, Yadong
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p. 4139 - 4146
(2021/04/02)
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- Magnetic gold-cobalt composite catalyst as well as preparation method and application thereof
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The invention provides a magnetic gold-cobalt composite catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The magnetic cobalt-cobalt composite catalyst comprises a magnetic cobalt oxide carrier and a gold-cobalt alloy loaded on the surface of the magnetic cobalt oxide carrier. The chemical composition of the magnetic cobalt oxide carrier is CoO. x , 1 _AOMARKENCODTX0AOA x _AOMARKENCODELTA AOA 1.5. In the catalyst provided by the invention, a metal synergistic effect is generated between gold and cobalt in the gold-cobalt alloy. CoOx A large number of surface defects are found in the invention, and a large number of reaction active sites are provided. The catalytic activity of the catalyst for 5 -hydroxymethylfurfural hydrogenation preparation 2, 5 -dimethylfuran is improved, the conversion rate 5 - hydroxymethylfurfural is high, 2,5 -dimethylfuran is high in yield and selectivity.
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Paragraph 0094-0098; 0101-0106
(2021/08/25)
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- Pt-Carbon interaction-determined reaction pathway and selectivity for hydrogenation of 5-hydroxymethylfurfural over carbon supported Pt catalysts
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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.
- Wang, Xiaofeng,Zhang, Chengcheng,Jin, Baitang,Liang, Xinhua,Wang, Qingfa,Zhao, Zhe,Li, Qingbo
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p. 1298 - 1310
(2021/03/14)
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- Method for preparing 2, 5-dimethylfuran through catalytic hydrogenation of 5-hydroxymethylfurfural
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The invention relates to a method for preparing 2, 5-dimethylfuran through catalytic hydrogenation of 5-hydroxymethylfurfural, i.e., 5-hydroxymethylfurfural is subjected to selective hydrogenation reaction under the action of a NiFe and reduced graphene oxide composite material catalyst to generate 2, 5-dimethylfuran. The NiFe/rGO catalyst does not need to be subjected to high-temperature pre-reduction treatment before being used, reaction is carried out for 3 h under the conditions of 200 DEG C and the hydrogen pressure of 2 MPa, the conversion rate of 5-hydroxymethylfurfural can reach 100%, and the yield and selectivity of 2, 5-dimethylfuran can reach 97%. The NiFe/rGO catalyst needing no reduction pretreatment has higher catalytic activity and selectivity than Ni/rGO, Fe/rGO, NiFe/Al2O3, NiFe/HY and NiFe/SiO2 catalysts, is cheaper than noble metal catalysts such as Pt and Pd, and has industrial application value.
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Paragraph 0030-0072
(2021/05/12)
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- Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
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Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.
- Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
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supporting information
p. 9029 - 9039
(2021/06/28)
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- Multifunctional NiCoTi?Catalyst Derived from Layered Double Hydroxides for Selective Hydrogenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran
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Multifunctional NiCoTi metal oxide catalysts (denoted herein as NiCoTi-x, where x is the molar ratio Ni + Co:Ti) were successfully prepared by thermal treatment of NiCoTi layered double hydroxide (LDH) precursors. The NiCoTi-x catalysts were then applied to the hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). The Ni:Co:Ti molar ratio in the catalysts was found to strongly influence both catalyst activity and product selectivity. A NiCoTi-8 catalyst, containing Ni, Co and Ti in a 4:4:1 molar ratio (i.e. Ni + Co/Ti = 8), displayed outstanding performance for HMF hydrogenation at 200?°C and 1.5?MPa, evidenced by a 90.7% HMF conversion and 95.8% selectivity to DMF. Graphic Abstract: A ternary metal oxide catalyst derived from a layered double hydroxide was proposed for the efficient and selective hydrogenation of 5-hydroxymethylfurfural to 2,5-methylfuran.[Figure not available: see fulltext.]
- Ma, Ning,Song, Yong,Han, Feng,Waterhouse, Geoffrey I. N.,Li, Yan,Ai, Shiyun
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p. 517 - 525
(2020/07/28)
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- Ni-Al/CoOx-catalyzed hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran at low temperatures without external hydrogen
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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.
- An, Yadan,Bai, Guoyi,Bian, Gang,Li, Tianming,Niu, Libo,Xia, Zhanghui
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p. 7763 - 7772
(2021/10/12)
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- Direct Visualization of Substitutional Li Doping in Supported Pt Nanoparticles and Their Ultra-selective Catalytic Hydrogenation Performance
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It has only recently been established that doping light elements (lithium, boron, and carbon) into supported transition metals can fill interstitial sites, which can be observed by the expanded unit cell. As an example, interstitial lithium (intLi) can block H filling octahedral interstices of palladium metal lattice, which improves partial hydrogenation of alkynes to alkenes under hydrogen. In contrast, herein, we report intLi is not found in the case of Pt/C. Instead, we observe for the first time a direct ‘substitution’ of Pt with substitutional lithium (subLi) in alternating atomic columns using scanning transmission electron microscopy-annular dark field (STEM-ADF). This ordered substitutional doping results in a contraction of the unit cell as shown by high-quality synchrotron X-ray diffraction (SXRD). The electron donation of d-band of Pt without higher orbital hybridizations by subLi offers an alternative way for ultra-selectivity in catalytic hydrogenation of carbonyl compounds by suppressing the facile CO bond breakage that would form alcohols.
- Chen, Tianyi,Foo, Christopher,Zheng, Jianwei J. W.,Fang, Huihuang,Nellist, Peter,Tsang, Shik Chi Edman
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supporting information
p. 12041 - 12046
(2021/07/14)
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- Iodine-catalyzed alcohol disproportionation method
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The invention relates to the technical field of catalysis, in particular to an iodine-catalyzed alcohol disproportionation method which comprises the following steps: sequentially adding alcohol, iodine and a solvent into a high-temperature and high-pressure reaction kettle, introducing a certain amount of nitrogen, conducting reacting for a certain time, collecting an organic phase after the reaction is ended, and conducting fractionating to obtain corresponding alkane and aldehyde/ketone. Alcohol disproportionation is efficient and atom-economical conversion without any additional oxidizing agent and reducing agent, and hydrocarbon and aldehyde/ketone molecules which are easy to separate can be formed at the same time. Meanwhile, the method has wide functional group tolerance, various substrate samples including aryl alcohol derivatives, heterocyclic alcohol derivatives, allyl alcohol derivatives and dihydric alcohol are tested, and the result shows that most of the substrate samples show good or extremely good yield.
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Paragraph 0032-0033
(2021/06/13)
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- Tris(2-aminoethyl)amine/metal oxides hybrid materials—preparation, characterization and catalytic application
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Three different metal oxides (basic MgO, basic-acidic Al2O3 and acidic-basic Nb2O5) characterized by comparable surface areas (MgO—130 m2/g; Al2O3—172 m2/g and Nb2O5—123 m2/g) and pore systems (domination of mesopores with narrow pore size distribution) were modified with tris(2-aminoethyl)amine (TAEA) via two methods: (i) direct anchoring of amine on metal oxide and (ii) anchoring of amine on metal oxide functionalized with (3-chloropropyl)trimethoxysilane. The obtained hybrid materials were characterized in terms of effectiveness of modifier anchoring (elemental analysis), their structural/textural properties (nitrogen adsorption/desorption, XRD), acidity/basicity of support (2-propanol dehydration and dehydrogenation, dehydration and cyclization of 2,5-hexanedione), states of modifier deposited on supports (XPS, FTIR, UV–VIS) and the strength of interaction between the modifier and the support (TG/DTG). It was evidenced that acidic-basic properties of metal oxides as well as the procedure of modification with TAEA determined the ways of amine anchoring and the strength of its interaction with the support. The obtained hybrid materials were tested in Knoevenagel condensation between furfural and malononitrile. The catalysts based on MgO showed superior activity in this reaction. It was correlated with the way of TAEA anchoring on basic MgO and the strength of modifier anchoring on the support. To the best of our knowledge tris(2-aminoethyl)amine has not been used as a modifier of solid supports for enhancement of the catalyst activity in Knoevenagel condensation.
- Stawicka, Katarzyna,Ziolek, Maria
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- Self-tuned properties of CuZnO catalysts for hydroxymethylfurfural hydrodeoxygenation towards dimethylfuran production
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5-Hydroxymethylfurfural (HMF) is a very valuable platform molecule obtained from biomass. It can be catalytically transformed to many industrially relevant products of both oxidation and reduction reactions. In this work, we showed that robust CuZnO can be an efficient, self-tuned catalyst for 2,5-dimethylfuran (DMF) (biofuel additive) synthesis. We showed that CuZnO catalysts can be further activated in the reaction environment and this process depends strongly on the initial catalyst properties and therefore on the catalyst preparation method. Smaller copper particles are more active but more prone to carbon deposit formation. Based on activity tests and extensive characterization, we have concluded that both Cun+ and Cu0 sites are necessary for high HMF conversion. While these two sites favor high conversion and high 2,5-bishydroxymethylfuran (BHMF) yield, the in situ formation of Lewis acid sites is proposed to be necessary for achieving a high DMF yield.
- Brzezińska, Magdalena,Keller, Nicolas,Ruppert, Agnieszka M.
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p. 658 - 670
(2020/02/27)
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- Multistep Engineering of Synergistic Catalysts in a Metal-Organic Framework for Tandem C-O Bond Cleavage
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Cleavage of strong C-O bonds without breaking C-C/C-H bonds is a key step for catalytic conversion of renewable biomass to hydrocarbon feedstocks. Herein we report multistep sequential engineering of orthogonal Lewis acid and palladium nanoparticle (NP) catalysts in a metal-organic framework (MOF) built from (Al-OH)n secondary building units and a mixture of 2,2′-bipyridine-5,5′-dicarboxylate (dcbpy) and 1,4-benzenediacrylate (pdac) ligands (1) for tandem C-O bond cleavage. Ozonolysis of 1 selectively removed pdac ligands to generate Al2(OH)(OH2) sites, which were subsequently triflated with trimethylsilyl triflate to afford strongly Lewis acidic sites for dehydroalkoxylation. Coordination of Pd(MeCN)2Cl2 to dcbpy ligands followed by in situ reduction produced orthogonal Pd NP sites in 1-OTf-PdNP as the hydrogenation catalyst. The selective and precise transformation of 1 into 1-OTf-PdNP was characterized step by step using powder X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, inductively coupled plasma mass spectrometry, infrared spectroscopy, and X-ray absorption spectroscopy. The hierarchical incorporation of orthogonal Lewis acid and Pd NP active sites endowed 1-OTf-PdNP with outstanding catalytic performance in apparent hydrogenolysis of etheric, alcoholic, and esteric C-O bonds to generate saturated alkanes via a tandem dehydroalkoxylation-hydrogenation process under relatively mild conditions. The reactivity of C-O bonds followed the trend of tertiary carbon > secondary carbon > primary carbon. Control experiments demonstrated the heterogeneous nature and recyclability of 1-OTf-PdNP and its superior catalytic activity over the homogeneous counterparts. Sequential engineering of multiple catalytic sites in MOFs thus presents a unique opportunity to address outstanding challenges in sustainable catalysis.
- Brzezinski, Carter,Chen, Justin S.,Feng, Xuanyu,Lin, Wenbin,Song, Yang,Xu, Ziwan
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supporting information
p. 4872 - 4882
(2020/04/01)
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- Hydroconversion of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran and 2,5-Dimethyltetrahydrofuran over Non-promoted Ni/SBA-15
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The selective hydroconversion of 5-hydroxymethylfurfural (HMF) to biofuels is currently highly sought-for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non-promoted Ni/SBA-15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5-dimethylfuran (DMF) and to 2,5-dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5-methylfurfural (MFFR) as intermediate, though the route via 2,5-bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates.
- Chen, Shuo,Ciotonea, Carmen,De Oliveira Vigier, Karine,Jér?me, Fran?ois,Wojcieszak, Robert,Dumeignil, Franck,Marceau, Eric,Royer, Sebastien
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p. 2050 - 2059
(2020/03/04)
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- Highly active bifunctional Pd-Co9S8/S-CNT catalysts for selective hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran
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A series of Pd-Co bimetallic catalysts were smoothly synthesized using sulfur-modified carbon nanotubes (S-CNT) as support by impregnation method. Those catalysts were characterized by XRD, XPS, TEM, SEM, H2-TPR, TGA, and nitrogen adsorption-de
- Liao, Weiping,Zhu, Zhiguo,Chen, Naimeng,Su, Ting,Deng, Changliang,Zhao, Yuchao,Ren, Wanzhong,Lü, Hongying
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- 2,5-dimethylfuran and method for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural
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The invention provides a 2,5-dimethylfuran and a method for preparing the 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural. The method comprises the following steps: the 5-hydroxymethylfurfural and a catalyst react in an alcohol solvent in a nitrogen atmosphere at 200-250 DEG C for 1-7 h, solid-liquid separation is performed after the reaction, and the obtained liquid phase product iscollected, and is purified to obtain the 2,5-dimethylfuran, wherein the active component of the supported copper-based catalyst is CuO, the carrier is MgO-ZrO2, and alcohol in the alcohol solvent isselected from than one or more of methanol, isopropanol and 2-butanol. The biomass derivative 5-hydroxymethylfurfural is used as a raw material, the supported copper-based material is used as the catalyst, the alcohol solvent is used as a hydrogen donor, and a noble metal catalyst and high-pressure hydrogen which is difficult to store and transport are not needed, so that the reaction condition ismild, the reaction raw material is a renewable biomass derivative, and a new way is further provided for utilization of renewable biomass energy.
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Paragraph 0019; 0036-0059
(2020/05/30)
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- Highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran at low temperature over a Co-N-C/NiAl-MMO catalyst
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Currently there is tremendous interest in the discovery of catalysts which can selectively hydrogenate biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). Herein, a highly selective catalyst for this transformation was developed, by adsorption of a cobalt porphyrin (CoTAPP) onto a nickel-aluminium layered double hydroxide (NiAl-LDH) support, followed by a pyrolysis step at 500 °C under a N2 atmosphere. The obtained catalyst (denoted here as Co-N-C/NiAl-MMO), comprising cobalt species (Co0 and CoOx) and N-doped carbon on a NiAl mixed metal oxide support, showed outstanding initial selectivity (99.9%) for the hydrogenation of HMF to DMF at 170 °C in tetrahydrofuran (THF). This is one of the highest selectivities reported to date for this reaction, with the reaction temperature being very mild. After 3 cycles of catalytic tests, with catalyst regeneration by heating at 300 °C in N2 between tests, the HMF conversion efficiency and DMF selectivity of Co-N-C/NiAl-MMO had both decreased by >70% compared to the initial values. This deactivation resulted from the loss of surface basic sites needed for H2 activation, as well as a change in the Co speciation on the catalyst surface (i.e. Co0 oxidation to CoOx). Results guide the development of improved catalysts for the selective conversion of HMF to DMF. This journal is
- Ai, Shiyun,Han, Feng,Li, Yan,Ma, Ning,Song, Yong,Waterhouse, Geoffrey I. N.
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p. 4010 - 4018
(2020/08/28)
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- Efficient Cu catalyst for 5-hydroxymethylfurfural hydrogenolysis by forming Cu-O-Si bonds
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Selective hydrogenolysis of C-O bonds of biomass derived precursors has been identified as a promising and essential way to produce fuel additives. Supported transition metals were explored to give efficient reactivity commonly based on a bifunctionality strategy. Here, we report that covalent bonding between SiO2 and Cu features a homologous bifunctional catalyst with metallic Cu and Lewis acidic Cu cations. The catalyst gave superior reactivity for the conversion of 5-hydroxymethylfurfural into 2,5-dimethylfuran. Lewis acidic cations had more predominant roles than metallic sites for C-O hydrogenolysis by stretching and dissociating C-O bonds, whereas they remained inactive for CC bonds. The results rationalize the valence-state-sensitive catalysis for chemistry involving C-O cleavage. The covalent metal-O-Si bonding provides an alternative for developing efficient catalysts since silicates with such a feature are versatile in nature.
- Fang, Zhen,Kong, Xiao,Li, Luping,Peng, Bo,Zhu, Yifeng,Zhu, Yulei
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p. 7323 - 7330
(2020/11/25)
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- Tantalum vs Niobium MCF nanocatalysts in the green synthesis of chromene derivatives
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TaMCF silicas modified with alkaline metals can be considered a novel family of highly efficient bifunctional catalysts involved in the synthesis of chromene derivatives, from salicylaldehyde 2 and acetonitrile compounds, under mild conditions, showing enhanced catalytic performance than their NbMCF analogues. The observed reactivity was mainly attributed to the higher basicity of the Me/TaMCF but also the texture of the samples. The Me/TaMCF silicas showed higher Br?nsted basicity than the Nb ones as indicated by the stronger interaction between alkali metals and Ta in the UV–vis and the test reaction experiments. On the other hand, the basicity of Me/TaMCF together the reactivity degree and steric hindrance of the starting acetonitriles are key factors influencing the reaction selectivity. In conclusion, the basicity of the samples plays an important role initiating the reaction by activation of nucleophile but also a compromise between alkaline cation size and basicity is required.
- Smuszkiewicz, Agata,López-Sanz, Jesús,Sobczak, Izabela,Martín-Aranda, Rosa M.,Ziolek, Maria,Pérez-Mayoral, Elena
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- METHOD FOR PREPARING 2,5-DIMETHYLFURAN BY DIRECTLY CATALYZING CARBOHYDRATE USING MODIFIED PD/C
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A preparation method of an acidic and hydrophobic Pd/C catalytic material comprises performing a simple treatment with chlorosulfonic acid and trimethylchlorosilane, washing and drying a treatment product to obtain a modified Pd/C catalytic material. A method for preparing 2,5-methylfuran by catalyzing a carbohydrate with modified Pd/C comprises: dissolving the carbohydrate in alcohol, allowing a reaction to proceed with modified Pd/C as a catalyst and polymethylhydrosiloxane as a hydrogen donor at a temperature of 80?140° C. for 1-5 hours, and performing centrifugation to separate the catalyst from the product. The content of the modified Pd/C content is 1-3 mol % relative to the carbohydrate; the polymethylhydrosiloxane amount is equivalent to 4-10 times the carbohydrate amount, and the carbohydrate concentration in the alcohol is 2-6 wt %. The method overcomes the defect of being difficult to prepare the 2,5-methylfuran by directly catalyzing the carbohydrate, and features moderate reaction conditions and high activity.
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Paragraph 0046
(2019/06/07)
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- Catalytic in-situ hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Cu-based catalysts with methanol as a hydrogen donor
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A series of Cu-based catalysts with different supports were synthesized and studied for the in situ hydrogenation of 5-hydroxymethylfurfural (5-HMF) to dimethylfuran (DMF) using methanol as an economical hydrogen donor. The structures and properties of the four catalysts (Cu/Al2O3, Cu/ZnO, Cu/ZrO2, and Cu/CeO2) were characterized using X-ray diffraction (XRD), temperature-programmed reduction (H2-TPR), and temperature-programmed desorption of ammonia (NH3-TPD). The experimental results showed that the use of different supports for the Cu-based catalysts significantly influenced their activity for both H2 production from methanol and hydrogenation of 5-HMF. The catalyst Cu/Al2O3 showed the best catalytic activity, which can be attributed to the highest activity for the in situ H2 production from methanol, smallest Cu crystallite size, and strongest acidity. The effects of the substrate concentration, catalyst loading, and reaction temperature and time on the in situ hydrogenation of 5-HMF were systematically investigated to determine the optimum reaction conditions.
- Zhang, Zihao,Wang, Changxue,Gou, Xin,Chen, Hao,Chen, Kequan,Lu, Xiuyang,Ouyang, Pingkai,Fu, Jie
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p. 245 - 250
(2018/12/05)
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- Preparation of nickel (oxide) nanoparticles confined in the secondary pore network of mesoporous scaffolds using melt infiltration
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Effective encapsulation strategies are highly sought-after in heterogeneous catalysis for preparing highly active and stable metal (oxide) nanocatalysts. Herein, we report an optimized Melt Infiltration (MI) procedure to confine nickel(oxide) nanoparticles (NPs) into hierarchical microporous-mesoporous scaffolds. Three SBA-15 silicas were synthesized in order to obtain different degrees of interconnectivity between the main mesopores. The impact of the SBA-15 pore characteristics, i.e., this interconnectivity, also named secondary intra-wall porosity (IWP), on the final nickel (oxide) NPs size and localization has been specifically investigated. Using MI, which consisted in the diffusion of the precursor in the liquid state inside the porosity of the support in the presence of the native surfactant occluding the pores, a selective localization of the NiO NPs inside the IWP was obtained, without large NPs plugging the main mesopores if IWP pores connecting the main mesopores do exist. When IWP – selective localization – occurs for the NPs, they show a size directly depending on the IWP dimensions. The obtained materials were tested, after reduction, in the hydrogenation reactions of cinnamaldehyde and 5-hydroxymethylfurfural. The catalytic results underline the positive effect of IWP - confinement of NPs to obtain and maintain an elevated dispersion of the metallic Ni active phase and to reach a high catalytic activity in hydrogenation under mild reaction conditions.
- Chen,Ciotonea,Ungureanu,Dumitriu,Catrinescu,Wojcieszak,Dumeignil,Royer
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- A non-noble bimetallic alloy in the highly selective electrochemical synthesis of the biofuel 2,5-dimethylfuran from 5-hydroxymethylfurfural
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The conversion of HMF to DMF has received great attention due to its potential as a gasoline alternative. Electrosynthesis is a powerful green tool due to its significant advantages and provides an efficient and environmentally friendly route. In this work, the process uses water as the hydrogen source in the electro-catalytic reduction of 5-hydromethylfurfural (HMF) for the synthesis of 2,5-dimethyl-furan (DMF). The performance of a non-noble CuNi bimetallic electrode was investigated in the electro-catalytic hydrogenation of HMF. The electrodes prepared were characterized using XRD, SEM, XPS, and BET techniques. 88.0% faradaic efficiency of DMF and 91.1% conversion selectivity of DMF were achieved. The CuNi bimetallic electrode also displayed a good stability during the reduction of HMF to DMF.
- Zhang, Yan-Ru,Wang, Bing-Xin,Qin, Lei,Li, Qiang,Fan, Yong-Ming
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supporting information
p. 1108 - 1113
(2019/03/11)
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- Towards Improved Biorefinery Technologies: 5-Methylfurfural as a Versatile C6 Platform for Biofuels Development
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Low chemical stability and high oxygen content limit utilization of the bio-based platform chemical 5-(hydroxymethyl)furfural (HMF) in biofuels development. In this work, Lewis-acid-catalyzed conversion of renewable 6-deoxy sugars leading to formation of more stable 5-methylfurfural (MF) is carried out with high selectivity. Besides its higher stability, MF is a deoxygenated analogue of HMF with increased C/O ratio. A highly selective synthesis of the innovative liquid biofuel 2,5-dimethylfuran starting from MF under mild conditions is described. The superior synthetic utility of MF against HMF in benzoin and aldol condensation reactions leading to long-chain alkane precursors is demonstrated.
- Galkin, Konstantin I.,Ananikov, Valentine P.
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p. 185 - 189
(2018/12/05)
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- Method for preparing DMF (2,5-dimethylfuran) from HMF (5-hydroxymethylfurfural) by catalytic hydrogenation
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The invention relates to a method for preparing DMF (2,5-dimethylfuran) from HMF (5-hydroxymethylfurfural) by catalytic hydrogenation. According to the method, a Co/rGO (cobalt and reduced graphene oxide) composite is used as a catalyst, the Co/rGO catalyst does not need reduction pretreatment, the conversion rate of HMF can reach 100% at 140-200 DEG C and under 1-2 MPa hydrogen pressure, and theyield of DMF exceeds 90%. The Co/rGO catalyst is cheaper than noble metal catalysts such as Pt and Pd, only C=O/C-O bond is dissociated, and the furan ring and C-C bond are not damaged, so that the catalyst has high selectivity to DMF, does not need pre-reduction treatment and has industrial application value.
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Paragraph 0029; 0030; 0031; 0032-0039
(2019/03/10)
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- Hydrodeoxygenation Using Magnetic Induction: High-Temperature Heterogeneous Catalysis in Solution
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Magnetic heating has recently been demonstrated as an efficient way to perform catalytic reactions after deposition of the heating agent and the catalyst on a support. Here we show that in solution, and under mild conditions of mean temperature and pressure, it is possible to use magnetic heating to carry out transformations that are otherwise performed heterogeneously at high pressure and/or high temperature. As a proof of concept, we chose the hydrodeoxygenation of acetophenone derivatives and of biomass-derived molecules, namely furfural and hydroxymethylfurfural. These reactions are difficult, require heterogeneous catalysts and high pressures, and, to the best of our knowledge, have no precedent in standard solution. Here, hydrodeoxygenations are fully selective under mild conditions (3 bar H2, moderate mean temperature of the solvent). The reason for this reactivity is the fast heating of the particles well above the boiling temperature of the solvent and the local creation of hot spots surrounded by a vapor layer, in which high temperature and pressure may be present. This technology may be practicable for many organic transformations.
- Asensio, Juan M.,Miguel, Ana B.,Fazzini, Pier-Francesco,van Leeuwen, Piet W. N. M.,Chaudret, Bruno
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supporting information
p. 11306 - 11310
(2019/07/12)
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- Application of copper-based catalyst in hydrogenation of 5-hydroxymethylfurfural
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The invention provides application of a copper-based catalyst in hydrogenation of 5-hydroxymethylfurfural. The copper-based catalyst has a chemical formula of Cu/M1M2O, wherein M1 represents one or any of Mg, Co, Zn and Mn, M2 represents one or any of Al, Fe, Mn and Cr, wherein the molar ratio of Cu to M1 is 1:(1-5), and the molar ratio of M1 to M2 is (1-5):1. The copper-based catalyst is preparedby preparing a copper-bearing hydrotalcite-like precursor, and roasting the copper-bearing hydrotalcite-like precursor in H2/N2 mixed atmosphere at 300-500 DEG C. The copper-based catalyst is applicable to the preparation of 2,5-dimethylfuran through selective hydrogenation of 5-hydroxymethylfurfural; since monovalent copper can well adsorb carbon-oxygen single bonds, the copper-based catalyst provides reactive conversion rate of up to 95-100% and DMF (dimethylformamide) selectivity of up to 90-95% when applied to catalyze the hydrogenation of 5-HMF (5-hydroxymethylfurfural).
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Paragraph 0029-0042
(2019/06/27)
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- One pot selective conversion of furfural to Γ-valerolactone over zirconia containing heteropoly tungstate supported on Β-zeolite catalyst
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A series of metal oxide and tungstophosphoric acid (TPA) supported on β-zeolite catalysts were prepared and evaluated for the one pot selective conversion of furfural (FA) to γ-valerolactone (GVL) using transfer hydrogenation approach. The characterizations of the catalysts were derived from N2-adsorption, FT-IR, XRD, XPS and temperature programmed desorption (TPD) techniques. The acid and base sites in the catalysts were estimated by NH3 and CO2 -TPD and FT-IR spectroscopy with pyridine and 2-propanol adsorption. Among the catalysts 20%ZrO2 with 5%TPA on β-zeolite showed high activity with 85% GVL yield. The high Lewis acidic density along with basic sites are responsible for the outstanding catalytic activity of the catalyst. Based on product distribution and catalyst characteristics, a plausible mechanism was proposed. Different reaction parameters were also studied and optimum conditions were established. The catalyst was easily recovered and reused with consistent activity.
- Srinivasa Rao,Krishna Kumari,Koley, Paramita,Tardio,Lingaiah
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- Preparation method of 2,5-dimethylfuran
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The invention discloses a preparation method of 2,5-dimethylfuran. The preparation method comprises the following step of: adding cellulose and manganese acetate into a sodium hydroxide/urea solution,and carrying out carbonization treatment, thus obtaining a catalyst, wherein the catalyst is applied to reaction for synthesizing 2,5-dimethylfuran by 5-hydroxymethylfurfural, and the reaction comprises the following steps of: adding the 5-hydroxymethylfurfural in an organic alcohols solvent, thus preparing a solution; mixing the solution with the catalyst, putting the mixture into a reaction kettle, exhausting air by using nitrogen, heating and stirring, and carrying out hydrodeoxygenation reaction, thus obtaining the 2,5-dimethylfuran. The catalyst provided by the invention is high in activity, high in selectivity and high in yield and has a very good application prospect. According to the preparation method of the 2,5-dimethylfuran by utilizing the catalyst, disclosed by the invention,the operation is easy, the cost is low, organic alcohol is innovatively used as a solvent and a hydrogen donor, the hydrogenation effect is good; the synthesis method is simple, the operation is easy, and the energy consumption is low.
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Paragraph 0028-0037
(2019/04/10)
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- Decomposition of glucose with in situ deoxygenation in a low H2 pressure environment – Pt. II: Bimetallic catalysts
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Bimetallic catalysts, CoFe, NiFe, PdFe, and PtCo were studied for their ability to perform in situ deoxygenation of glucose decomposition production at 350 °C. Catalysts were prepared via co-impregnation and sequential impregnation methods on SiO2/s
- Rogers, Kyle A.,Zheng, Ying
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- CuZnCoOx multifunctional catalyst for in situ hydrogenation of 5-hydroxymethylfurfural with ethanol as hydrogen carrier
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Catalytic in situ hydrogenation of 5-hydroxymethylfurfural (5-HMF) to 2,5-dimethylfuran (DMF) has received a great interest in recent years. However, the issue of the consumption of expensive hydrogen donors, such as secondary alcohols, limits its applica
- Zhang, Zihao,Yao, Siyu,Wang, Changxue,Liu, Miaomiao,Zhang, Feng,Hu, Xiaobing,Chen, Hao,Gou, Xin,Chen, Kequan,Zhu, Yimei,Lu, Xiuyang,Ouyang, Pingkai,Fu, Jie
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p. 314 - 321
(2019/04/26)
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- CNF-functionalization as versatile tool for tuning activity in cellulose-derived product hydrogenation
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Carbon nanofibers (CNFs) have been functionalized by introducing O, N, and P containing groups in order to investigate the effect of support functionalization in Ru catalysed hydroxymethyl furfural (HMF) and levulinic acid (LA) hydrogenation. In the case of HMF, despite the fact that no effect on selectivity was observed (all the catalysts produced selectively gamma-valerolactone (GVL)), the functionalization strongly affected the activity of the reaction. O-containing and N-containing supports presented a higher activity compared to the bare support. On the contrary, in HMF hydrogenation, functionalization of the support did not have a beneficial effect on the activity of a Ru-catalysed reaction with respect to bare support and only CNFs-O behaved similarly to bare CNFs. In fact, when CNFs-N or CNFs-P were used as the supports, a lower activity was observed, as well as a change in selectivity in which the production of ethers (from the reaction with the solvent) greatly increased.
- Jouve, Andrea,Cattaneo, Stefano,Capelli, Sofia,Stucchi, Marta,Evangelisti, Claudio,Villa, Alberto,Prati, Laura
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supporting information
(2019/02/06)
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- Toward an Integrated Conversion of 5-Hydroxymethylfurfural and Ethylene for the Production of Renewable p-Xylene
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The use of biomass as a solution to satisfy the pressing needs for a fully sustainable biocommodity industry has been explored for a long time. However, limited success has been obtained. In this study, a highly effective two-stage procedure for the direct preparation of para-xylene (PX) from 5-hydroxymethylfurfural (HMF) and formic acid in one pot is described; these chemicals are two of the major bio-based feedstocks that offer the potential to address urgent needs for the green, sustainable production of drop-in chemical entities. The use of a robust, efficient heterogeneous catalyst, namely, bimetallic Pd-decorated Au clusters anchored on tetragonal-phase zirconia, is crucial to the success of this strategy. This multifunctional catalytic system can not only facilitate a low-energy-barrier H2-free pathway for the rapid, nearly exclusive formation of 2,5-dimethylfuran (DMF) from HMF but also enable the subsequent ultraselective production of PX by the dehydrative aromatization of the resultant DMF with ethylene. With increasing pressure around the world to move toward a bio-based economy, it is essential that industrially important commodity chemicals can be readily accessed from biomass resources. Para-xylene (PX) synthesis is one such target that is being actively pursued through the development of several biorefinery schemes based on integrated biomass processing. Significant progress has recently been achieved either in the selective synthesis of biorenewable PX from Diels-Alder-like coupling of ethylene with 2,5-dimethylfuran (DMF) or making DMF from 5-hydroxymethylfurfural (HMF) using hydrogen as the terminal reductant. However, a green and direct conversion of HMF, an essential feedstock source for future biorefinery schemes, into PX has yet to be developed. We have established an integrated process that directly converts HMF to PX in a highly compact and hydrogen-independent manner, thereby providing a new perspective on the potential of advanced biorefinery technologies. Cao and colleagues describe an alternative strategy for producing para-xylene through a more sustainable method than the current bio-based approaches. The strategy relies on an integrated conversion of 5-hydroxymethylfurfural with formic acid and ethylene, made possible by the use of a single multifunctional catalyst based on bimetallic Pd-decorated Au deposited on tetragonal-phase zirconia. The proposed process is particularly appealing because it is fully fossil independent, implying a viable and greener biorefinery scheme.
- Tao, Lei,Yan, Tian-Hao,Li, Wenqin,Zhao, Yi,Zhang, Qi,Liu, Yong-Mei,Wright, Mark M.,Li, Zhen-Hua,He, He-Yong,Cao, Yong
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supporting information
p. 2212 - 2227
(2018/10/02)
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- Hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over supported Pt-Co bimetallic catalysts under mild conditions
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Highly dispersed Pt-Co bimetallic catalysts were deposited on multi-walled carbon nanotubes (MWCNTs) by atomic layer deposition. High-resolution TEM and TPR analyses verified the formation of Pt-Co bimetallic particles. Catalysts were applied for the hydrogenolysis of 5-hydroxymethyfurfural (HMF) to 2,5-dimethyfuran (DMF). A high yield of DMF (>90%) was achieved in the hydrogenolysis of HMF over the optimized Pt-Co/MWCNTs catalyst after 8 h of reaction time under 10 bar H2 at 160 °C. Through a series of experiments and comparison, the synergistic effect among Pt, Co, and MWCNTs was investigated. The results revealed that the synergistic effect between Pt-Co and MWCNTs played an important role in the improvement of selectivity to DMF for Pt-Co/MWCNTs bimetallic catalysts. In addition, steric hindrance appeared when Co loading in Pt-Co/MWCNTs was high and it affected the activity of the Pt-Co bimetallic catalysts. However, moderate activity can inhibit the production of byproducts and thereby improve the yield of DMF.
- Wang, Xiaofeng,Liu, Yuzi,Liang, Xinhua
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p. 2894 - 2902
(2018/06/29)
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- In situ MnOx/N-doped carbon aerogels from cellulose as monolithic and highly efficient catalysts for the upgrading of bioderived aldehydes
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Herein, we report a sustainable route to in situ synthesize a monolithic MnOx/N-doped carbon aerogel catalyst (Mn-NCA) by pyrolysing MnO(OH)2-cellulose aerogel precursors based on an alkali-urea aqueous system. The as-obtained Mn-NCA showed highly efficient catalytic activity for the transfer hydrogenation of a broad range of biomass-derived aldehydes, yielding 90-100% conversion and 64-100% selectivity to the corresponding alcohols under mild conditions in an oven without agitation. A combination of controlled experiments and detailed characterization studies indicated that the superior performance of Mn-NCA is attributed to the monolithic three-dimensional (3D) hierarchical porous architecture and the synergistic effects between homogeneously dispersed MnOx nanoparticles (NPs) and urea-derived basic sites. The monolithic feature of Mn-NCA exhibits superior dispersibility and separability compared to conventional centrifugation and filtration techniques in a powdery catalytic system. Moreover, a possible reaction mechanism is proposed. Our work provides a new method for developing highly efficient monolithic catalysts from renewable biopolymers for biomass valorization.
- Zhou, Shenghui,Chen, Guixian,Feng, Xiao,Wang, Ming,Song, Tao,Liu, Detao,Lu, Fachuang,Qi, Haisong
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p. 3593 - 3603
(2018/08/17)
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- Method to prepare 2,5-dimethylfuran by in-situ hydrogenation of 5-hydroxymethylfurfural
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The invention relates to a method to prepare 2,5-dimethylfuran by in-situ hydrogenation of 5-hydroxymethylfurfural. The method includes: mixing 5-hydroxymethylfurfural, primary alcohol and a Cu-basedcatalyst, heating to 150-250 DEG C, and enabling reaction to occur for 0.5-7 h to obtain 2,5-dimethylfuran; the Cu-based catalyst is three-way catalyst Cu-ZnO-CoOx. The method gains further increasedconversion rate of 5-hydroxymethylfurfural and further improved selectivity of 2,5-dimethylfuran as preparation conditions are optimized.
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Page/Page column 6-9
(2018/10/11)
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- METHOD FOR PRODUCING FURAN DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a method for easily obtaining furan derivative using unpurified hydroxymethylfurfural and/or furfural without purification when carrying out oxidation reaction or reduction reaction in which hydroxymethylfurfural and/or furfural obtained by reacting saccharides such as cellulose, starch, glucose, fructose or the like is a raw material. SOLUTION: In the method, a corresponding compound is easily obtained by oxidation reaction or reduction reaction without purification by removing reaction inhibiting impurities by adding adsorbent such as alumina to biomass-derived hydroxymethyl-furfural solution or furfural solution. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0039
(2018/06/30)
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- Ruthenium on carbonaceous materials for the selective hydrogenation of HMF
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We report the use of Ru catalysts supported in the activated carbon (AC) and carbon nanofibers (CNFs) for the selective production of liquid fuel dimethylfuran (DMF) and fuel additives alkoxymethyl furfurals (AMF). Parameters such as the reaction temperature and hydrogen pressure were firstly investigated in order to optimise the synthesis of the desired products. Simply by using a different support, the selectivity of the reaction drastically changed. DMF was produced with AC as support, while a high amount of AMF was produced when CNFs were employed. Moreover, the reusability of the catalysts was tested and deactivation phenomena were identified and properly addressed. Further studies need to be performed in order to optimise the stability of the catalysts.
- Cattaneo, Stefano,Naslhajian, Hadi,Somodi, Ferenc,Evangelisti, Claudio,Villa, Alberto,Prati, Laura
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- A Pd-Catalyzed in situ domino process for mild and quantitative production of 2,5-dimethylfuran directly from carbohydrates
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An in situ domino process has been developed to be highly efficient for direct and mild conversion of various hexose sugars to the biofuel 2,5-dimethylfuran in almost quantitative yields, without separation of unstable intermediates at 120 °C in n-butanol, by using polymethylhydrosiloxane and hydrophobic Pd/C as a H-donor and a bifunctional catalyst, respectively. Among the cascade reactions, the hydrosilylation process was confirmed by deuterium-labeling and kinetic studies to be favorable for sugar dehydration and exclusively acts on deoxygenation of in situ formed intermediates including furanic alcohols and aldehydes to DMF via a hydride transfer process that was facilitated by an alcoholic solvent. The catalytic system is more selective than the H2- participated counterpart, and could be scaled up with only 0.04 mol% catalyst loading, giving DMF in a comparable yield of 85%. Moreover, Pd(0) was demonstrated to be the active species for deoxygenation, and the heterogeneous catalyst exhibited good recyclability with little elemental leaching.
- Li, Hu,Zhao, Wenfeng,Riisager, Anders,Saravanamurugan, Shunmugavel,Wang, Zhongwei,Fang, Zhen,Yang, Song
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p. 2101 - 2106
(2017/07/22)
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- METHOD FOR PREPARING 2,5-DISUBSTITUTED FURAN COMPOUND
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Disclosed is a method for preparing a 2,5-disubstituted furan compound. The 2,5-disubstituted furan compound is prepared in a simple, convenient and highly efficient way by reacting 2,3-dicarboxylic anhydride-7-oxabicyclo[2.2.1]hept-5-ene and/or furan with an acylating reagent and/or an alkylating reagent. The preparation method is simple and efficient, has a short process and less by-products, and the 2,5-disubstituted furan compound prepared by using the method has a high purity, and can satisfy the requirements for being used as a raw material for engineering plastics, such as high-performance polyesters, epoxy resins, polyamides, polyurethanes and the like, and as a chemical raw material and a pharmaceutical intermediate raw material.
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Paragraph 00102
(2017/11/30)
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- Exploiting H-transfer as a tool for the catalytic reduction of bio-based building blocks: The gas-phase production of 2-methylfurfural using a FeVO4 catalyst
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Over the past decade, a great deal of effort has been devoted to developing reductive processes in the field of biomass valorisation for the sustainable production of bio-fuel additives and chemicals. Catalytic transfer hydrogenation, which uses alcohol as the hydrogen source, is an interesting approach that avoids the use of both high H2 pressure and precious metal catalysts. In this work, the vapour-phase production of 2-methylfuran from biomass-derived furfural (FU), using methanol as the H-transfer agent and FeVO4 catalyst, was studied. At a temperature of 320°C it was possible to achieve 80% yield of 2-methylfuran, with small amounts of 2,5-dimethylfuran and 2-vinylfuran as by-products. Catalyst characterization highlighted that FeVO4 reduction took place under the studied conditions, leading to the in situ development of a true active phase. The study of the reaction network permitted us to infer on the relative contribution of H-transfer and hydrogenation, the latter from the in situ generated formaldehyde and H2, to 2-methylfuran, formation. The reported results indicate the potential application of H-transfer with FeVO4 catalysts as an efficient process for the selective de-oxygenation of biomass-derived molecules.
- Grazia,Bonincontro,Lolli,Tabanelli,Lucarelli,Albonetti,Cavani
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p. 4412 - 4422
(2017/09/26)
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- A continuous flow process for the production of 2,5-dimethylfuran from fructose using (non-noble metal based) heterogeneous catalysis
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The abundant carbohydrate fructose is converted into two biofuel molecules, namely 2,5-dimethylfuran (DMF) and ethyl levulinate (EL) in a simple cascade flow reactor. With an overall yield of 85% (38.5% of 2,5-dimethylfuran and 47% of ethyl levulinate), the main remainder is unconverted fructose. The two column flow reactor set-up enables the adjustment of temperatures and reaction times in such a way that the reactive intermediate hydroxymethylfurfural (5-HMF) is generated in optimal yields and converted into the stable DMF immediately. The process is so simple and fast (20 min) that economic and sustainable production of these fuels and platform chemicals can be envisioned. A remaining minor char formation is regarded to be the major problem which has to be addressed by catalyst development.
- Braun, Max,Antonietti, Markus
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p. 3813 - 3819
(2017/08/26)
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- Hydrodeoxygenation of cellulose pyrolysis model compounds using molybdenum oxide and low pressure hydrogen
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A molybdenum oxide catalyst in a low pressure hydrogen atmosphere was used for the hydrodeoxygenation (HDO) of pulsed injections of cellulose pyrolysis model compounds to examine reaction products. Higher catalyst loadings (≥20: 1 catalyst: cellulose injection) in the HDO reactor were found to preferentially produce alkanes, while at lower loadings (≤10: 1 catalyst: cellulose injection) alkene selectivity was increased. However, as the amount of catalyst was decreased, the pyrolysis vapors were not completely deoxygenated. The HDO of monofunctional oxygenated C4 compounds found hydroxyl groups to be the most readily reacted and ether linkages to be the most recalcitrant. In general, the reactivity towards deoxygenation of the tested oxygen-containing functional groups was observed to be C-OH > C=O > C-OC. Several cellulose pyrolysis model compounds were also tested, including methyl glyoxal, glycolaldehyde, furfural, 5-hydroxymethylfurfural, and levoglucosan, and found the same general trend to occur, except for levoglucosan, which was totally reacted and did not yield any oxygenated low molecular weight compounds despite containing two ether linkages. Across the compounds, the general reaction pathway was observed to include carbonyl/alcohol hydrogenation/dehydrogenation, deoxygenation, and alkene isomerization and hydrogenation.
- Nolte, Michael W.,Saraeian, Alireza,Shanks, Brent H.
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supporting information
p. 3654 - 3664
(2017/08/10)
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- Direct one-pot conversion of monosaccharides into high-yield 2,5-dimethylfuran over a multifunctional Pd/Zr-based metal-organic framework@sulfonated graphene oxide catalyst
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A one-pot conversion of monosaccharides (fructose and glucose) into high-yield 2,5-dimethylfuran (2,5-DMF) is demonstrated over a multifunctional catalyst obtained by loading Pd on a Zr-based metal-organic framework (UiO-66) that is deposited on sulfonated graphene oxide (Pd/UiO-66@SGO). The Br?nsted acidity associated with UiO-66@SGO activates the fructose dehydration to form 5-hydroxymethylfurfural (5-HMF), while the Pd nanoparticles further convert 5-HMF to 2,5-DMF by hydrogenolysis and hydrogenation. The results show that under the optimized reaction conditions of 160 °C and 1 MPa H2 in tetrahydrofuran for 3 h, the yield of 2,5-DMF is as high as 70.5 mol%. This value is higher than the previously reported values, and the direct conversion of fructose can be achieved without additional purification of 5-HMF from the reaction mixture. In addition, for the first time, glucose is converted to 2,5-DMF with a high yield of 45.3 mol%. A recyclability test suggests that the 4.8 wt% Pd loaded on the UiO-66@SGO catalyst can be re-used up to five times.
- Insyani, Rizki,Verma, Deepak,Kim, Seung Min,Kim, Jaehoon
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p. 2482 - 2490
(2017/07/17)
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