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1.
Chemistry ; 30(20): e202303810, 2024 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-38327129

RESUMEN

2,4-dimethylfuran has a rare disubstitution pattern in the five-membered heterocyclic furan ring that is highly interesting chemically but challenging to access synthetically. We present a heterogeneously catalysed route to synthesise 2,4-dimethylfuran from commonly available 2,5-dimethylfuran using a zeolite packed-bed flow reactor. As supported by DFT calculations, the reaction occurs inside the zeolite channels, where the acid sites catalyse proton transfer followed by migration of a methyl group. The zeotype Ga-silicate (MFI type) appears superior to an aluminium-containing ZSM-5 by demonstrating higher selectivities and slower catalyst deactivation. This work provides new opportunities for the continuous valorisation of bio-feedstock molecules in the perspective of the emerging biorefinery era.

2.
Molecules ; 29(4)2024 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-38398613

RESUMEN

A one-pot, two-step process was developed for the preparation of pyrrole compounds from 2,5-dimethylfuran. The first step was the acid-catalyzed ring-opening reaction of 2,5-dimethylfuran (DF), leading to the formation of 2,5-hexanedione (HD). A stoichiometric amount of water and a sub-stoichiometric amount of sulfuric acid were used by heating at 50 °C for 24 h. Chemically pure HD was isolated, with a quantitative yield (up to 95%), as revealed by 1H-NMR, 13C-NMR, and GC-MS analyses. In the second step, HD was used as the starting material for the synthesis of pyrrole compounds via the Paal-Knorr reaction. Various primary amines were used in stoichiometric amounts. 1H-NMR, 13C-NMR, ESI-Mass, and GC-Mass analyses confirmed that pyrrole compounds were prepared with very good/excellent yields (80-95%), with water as the only co-product. A further purification step was not necessary. The process was characterized by a very high carbon efficiency, up to 80%, and an E-factor down to 0.128, whereas the typical E-factor for fine chemicals is between 5 and 50. Water, a co-product of the second step, can trigger the first step and therefore make the whole process circular. Thus, this synthetic pathway appears to be in line with the requirements of a sustainable chemical process. A pyrrole compound bearing an SH group (SHP) was used for the functionalization of a furnace carbon black (CB). The functionalized CB (CB/SHP) was utilized in place of silica, resulting in a 15% mass reduction of reinforcing filler, in an elastomeric composite based on poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis. Compared to the silica-based composite, a reduction in the Payne effect of about 25% and an increase in the dynamic rigidity (E' at 70 °C) of about 25% were obtained with CB/SHP.

3.
Environ Res ; 226: 115660, 2023 06 01.
Artículo en Inglés | MEDLINE | ID: mdl-36913997

RESUMEN

Eco-friendly renewable energy sources have recommended as fossil fuel alternatives in recent years to reduce environmental pollution and meet future energy demands in various sectors. As the largest source of renewable energy in the world, lignocellulosic biomass has received considerable interest from the scientific community to advance the fabrication of biofuels and ultrafine value-added chemicals. For example, biomass obtained from agricultural wastes could catalytically convert into furan derivatives. Among furan derivatives, 5-hydroxymethylfurfural (HMF) and 2, 5-dimethylfuran (DMF) are considered the most useful molecules that can be transformed into desirable products such as fuels and fine chemicals. Because of its exceptional properties, e.g., water insolubility and high boiling point, DMF has studied as the ideal fuel in recent decades. Interestingly, HMF, a feedstock upgraded from biomass sources can easily hydrogenate to produce DMF. In the present review, the current state of the art and studies on the transformation of HMF into DMF using noble metals, non-noble metals, bimetallic catalysts, and their composites have discussed elaborately. In addition, comprehensive insights into the operating reaction conditions and the influence of employed support over the hydrogenation process have demonstrated.


Asunto(s)
Biocombustibles , Lignina , Biomasa , Lignina/química , Furanos
4.
Molecules ; 27(13)2022 Jun 29.
Artículo en Inglés | MEDLINE | ID: mdl-35807429

RESUMEN

5-Hydroxymethylfurfural (5-HMF) has been described as one of the 12 key platform molecules derived from biomass by the US Department of Energy, and its hydrogenation reaction produces versatile liquid biofuels such as 2,5-dimethylfuran (2,5-DMF). Catalytic hydrogenation from 5-HMF to 2,5-DMF was thoroughly studied on the metal nickel catalysts supported on Al2O3-TiO2-ZrO2 (Ni/ATZ) mixed oxides using isopropanol and formic acid (FA) as hydrogen donors to find the best conditions of the reaction and hydrogen donor. The influence of metal content (wt%), Ni particle size (nm), Nickel Ni0, Ni0/NiO and NiO species, metal active sites and acid-based sites on the catalyst surface, and the effect of the hydrogen donor (isopropanol and formic acid) were systematically studied. The structural characteristics of the materials were studied using different physicochemical methods, including N2 physisorption, XRD, Raman, DRS UV-Vis, FT-IR, SEM, FT-IR Pyad, H2-TPD, CO2-TPD, H2-TPR, TEM and XPS. Second-generation 2,5-DMF biofuel and 5-HMF conversion by-products were analyzed and elucidated using 1H NMR. It was found that the Ni0NiO/ATZ3WI catalyst synthesized by the impregnation method (WI) generated a good synergistic effect between the species, showing the best catalytic hydrogenation of 5-HMF to 2,5-DMF using formic acid as a hydrogen donor for 24 h of reaction and temperature of 210 °C with 20 bar pressure of Argon (Ar).


Asunto(s)
Hidrógeno , Níquel , 2-Propanol , Biocombustibles , Furaldehído/análogos & derivados , Furanos , Hidrógeno/química , Hidrogenación , Níquel/química , Espectroscopía Infrarroja por Transformada de Fourier , Titanio
5.
J Environ Sci (China) ; 114: 136-148, 2022 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-35459479

RESUMEN

The atmospheric chemistry in complex air pollution remains poorly understood. In order to probe how environmental conditions can impact the secondary organic aerosol (SOA) formation from biomass burning emissions, we investigated the photooxidation of 2,5-dimethylfuran (DMF) under different environmental conditions in a smog chamber. It was found that SO2 could promote the formation of SOA and increase the amounts of inorganic salts produced during the photooxidation. The formation rate of SOA and the corresponding SOA mass concentration increased gradually with the increasing DMF/OH ratio. The addition of (NH4)2SO4 seed aerosol accelerated the SOA formation rate and significantly shortened the time for the reaction to reach equilibrium. Additionally, a relatively high illumination intensity promoted the formation of OH radicals and, correspondingly, enhanced the photooxidation of DMF. However, the enhancement of light intensity accelerated the aging of SOA, which led to a gradual decrease of the SOA mass concentration. This work shows that by having varying influence on atmospheric chemical reactions, the same environmental factor can affect SOA formation in different ways. The present study is helpful for us to better understand atmospheric complex pollution.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire , Aerosoles , Contaminantes Atmosféricos/análisis , Biomasa , Oxidación-Reducción , Esmog
6.
Angew Chem Int Ed Engl ; 61(34): e202205453, 2022 08 22.
Artículo en Inglés | MEDLINE | ID: mdl-35700334

RESUMEN

One pot synthesis of 2,5-dimethylfuran (2,5-DMF) from saccharides under mild conditions is of importance for the production of biofuel and fine chemicals. However, the synthesis requires a multitude of active sites and suffers from slow kinetics due to poor diffusion in most composite catalysts. Herein, a metal-acid functionalized 2D metal-organic framework (MOF; Pd/NUS-SO3 H), as an ultrathin nanosheet of 3-4 nm with Lewis acid, Brønsted acid, and metal active sites, was prepared based on the diazo method for acid modification and subsequent metal loading. This new composite catalyst gives substantially higher yields of DMF than all reported catalysts for different saccharides (fructose, glucose, cellobiose, sucrose, and inulins). Characterization suggests that a cascade of reactions including polysaccharide hydrolysis, isomerization, dehydration, and hydrodeoxygenation takes place with rapid molecular interactions.


Asunto(s)
Furanos , Estructuras Metalorgánicas , Catálisis , Dominio Catalítico , Furanos/química , Ácidos de Lewis
7.
Molecules ; 26(3)2021 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-33572680

RESUMEN

A Burkholderia gladioli strain, named BBB-01, was isolated from rice shoots based on the confrontation plate assay activity against several plant pathogenic fungi. The genome of this bacterial strain consists of two circular chromosomes and one plasmid with 8,201,484 base pairs in total. Pangenome analysis of 23 B. gladioli strains suggests that B. gladioli BBB-01 has the closest evolutionary relationship to B. gladioli pv. gladioli and B. gladioli pv. agaricicola. B. gladioli BBB-01 emitted dimethyl disulfide and 2,5-dimethylfuran when it was cultivated in lysogeny broth and potato dextrose broth, respectively. Dimethyl disulfide is a well-known pesticide, while the bioactivity of 2,5-dimethylfuran has not been reported. In this study, the inhibition activity of the vapor of these two compounds was examined against phytopathogenic fungi, including Magnaporthe oryzae, Gibberella fujikuroi, Sarocladium oryzae, Phellinus noxius and Colletotrichumfructicola, and human pathogen Candida albicans. In general, 2,5-dimethylfuran is more potent than dimethyl disulfide in suppressing the growth of the tested fungi, suggesting that 2,5-dimethylfuran is a potential fumigant to control plant fungal disease.


Asunto(s)
Antifúngicos/metabolismo , Antifúngicos/farmacología , Burkholderia gladioli/metabolismo , Compuestos Orgánicos Volátiles/metabolismo , Compuestos Orgánicos Volátiles/farmacología , Enfermedades de las Plantas/microbiología , Enfermedades de las Plantas/prevención & control
8.
Angew Chem Int Ed Engl ; 60(2): 624-629, 2021 Jan 11.
Artículo en Inglés | MEDLINE | ID: mdl-33078542

RESUMEN

The heterogeneous metal-organic framework Bi-BTC successfully catalyzed the synthesis of para-xylene from bio-based 2,5-dimethylfuran and acrylic acid in a promising yield (92 %), under relatively mild conditions (160 °C, 10 bar), and with a low reaction-energy barrier (47.3 kJ mol-1 ). The proposed reaction strategy also demonstrates a remarkable versatility for furan derivatives such as furan and 2-methylfuran.

9.
Indoor Air ; 24(1): 59-70, 2014 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-23631597

RESUMEN

Identifying and quantifying secondhand tobacco smoke (SHS) that drifts between multiunit homes is critical to assessing exposure. Twenty-three different gaseous and particulate measurements were taken during controlled emissions from smoked cigarettes and six other common indoor source types in 60 single-room and 13 two-room experiments. We used measurements from the 60 single-room experiments for (i) the fitting of logistic regression models to predict the likelihood of SHS and (ii) the creation of source profiles for chemical mass balance (CMB) analysis to estimate source apportionment. We then applied these regression models and source profiles to the independent data set of 13 two-room experiments. Several logistic regression models correctly predicted the presence of cigarette smoke more than 80% of the time in both source and receptor rooms, with one model correct in 100% of applicable cases. CMB analysis of the source room provided significant PM2.5 concentration estimates of all true sources in 9 of 13 experiments and was half-correct (i.e., included an erroneous source or missed a true source) in the remaining four. In the receptor room, CMB provided significant estimates of all true sources in 9 of 13 experiments and was half-correct in another two.


Asunto(s)
Contaminación del Aire Interior/análisis , Material Particulado/química , Contaminación por Humo de Tabaco/análisis , Compuestos Orgánicos Volátiles/análisis , Movimientos del Aire , California , Modelos Logísticos , Tamaño de la Partícula
10.
Combust Flame ; 161(3): 780-797, 2014 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-24518851

RESUMEN

This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model.

11.
ChemSusChem ; : e202401017, 2024 Jun 24.
Artículo en Inglés | MEDLINE | ID: mdl-38924639

RESUMEN

2, 5-Dimethylfuran (DMF), which is a promising new-generation liquid biofuel, has attracted widespread attention owing to the sustainability of biomass-derived energy sources. In this study, a highly dispersed zirconia-supported nickel catalyst (CA-Ni/ZrO2) was prepared via citric acid-assisted wetness impregnation for the selective hydrogenolysis of 5-hydroxymethylfurfural (HMF) to produce DMF. The characterization results confirmed the presence of Zr3+ species in the mesoporous CA-Ni/ZrO2 catalyst and the formation of oxygen vacancies during its preparation, which led to the formation of a large number of catalytically active sites for the adsorption and activation of the C=O/C-O groups. Under appropriate reaction parameters, an excellent DMF selectivity of 99.1 % and an HMF conversion of 98.4 % were achieved. A suitable kinetic model revealed that DMF was preferentially formed via the 2,5-dihydroxymethylfuran intermediate route, although a 5-methylfurfural route was also observed. Additionally, the interaction between Ni and ZrO2 significantly affected the stability of the catalyst. This study will provide guidelines for optimizing the catalytic conversion of furan derivatives over heterogeneous catalysts.

12.
Heliyon ; 10(5): e26690, 2024 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-38455557

RESUMEN

One of the most promising solutions to the current energy crisis is an efficient catalytic transformation of abundant low-cost renewable raw biomass into high-quality biofuel. Herein, a highly effective catalyst was constructed systematically for the selective synthesis of 2,5-dimethylfuran (DMF) biofuel from biomass-derived 5-hydroxymethylfurfural (HMF) via green catalytic transfer hydrogenolysis (CTH) using a nitrogen-doped ordered mesoporous carbon (N-CMK-1) decorated ruthenium (Ru)-based catalyst in i-propanol as hydrogen source. The structures and properties of different catalysts were characterized by different characterization techniques such as FTIR, XRD, N2-sorption, CO2-sorption, TGA, TEM, ICP-AES, CHNO analysis, and acid-base back titration. A complete HMF conversion with a high DMF yield of 88% was achieved under optimized reaction conditions. Regarding substrate conversion and product yield, the influence of reaction temperature, time, and hydrogen donors was thoroughly investigated. The nitrogen-promoted carbon support enhanced the dispersion of Ru due to the formation of appropriate basic site density which could efficiently promote the activation of alcohol hydroxyl in i-propanol and subsequent release of active hydrogen species. In the meantime, highly dispersed surface Ru nanoparticles (NPs) were beneficial for hydrogen transfer and activation of both carbonyl and hydroxyl groups in HMF. Moreover, Arrhenius kinetic analysis was studied by identifying 5-methyl furfural (5-MF) and 2,5-bishydroxymethylfuran (BHMF) as two key intermediates that dominate a distinct reaction pathway during hydrogenolysis of HMF to DMF via CTH. Furthermore, high stability without obvious loss of activity after three consecutive cycles was observed in a fabricated N-CMK-1 decorated Ru-based catalyst as a result of superior metal-support interaction and the mesoporous framework nature of the catalyst. These findings would not only offer a robust catalyst synthetic approach but also open a new avenue for the exploitation of biomass to specialty chemicals and advanced biofuels.

13.
EFSA J ; 22(4): e8721, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38585220

RESUMEN

Following a request from the European Commission, EFSA was asked to deliver a scientific opinion on the proposed modification of the terms of the authorisation regarding the maximum inclusion level of a feed additive consisting of 4-hydroxy-2,5-dimethylfuran-3(2H)-one for cats and dogs. 4-Hydroxy-2,5-dimethylfuran-3(2H)-one is currently authorised for use as a sensory additive (functional group: flavouring compounds) for cats and dogs at a recommended maximum content of 5 mg/kg complete feed. The applicant is requesting a modification of the authorisation to increase the recommended maximum content of the additive up to 25 mg/kg complete feed for cats and dogs. Based on the toxicological data available, the FEEDAP Panel concludes that 4-hydroxy-2,5-dimethylfuran-3(2H)-one is safe for dogs at 25 mg/kg feed and for cats at 18 mg/kg feed. The additive is irritant to skin, eyes and to the respiratory tract and is a skin sensitiser. No further demonstration of efficacy is necessary.

14.
Environ Sci Pollut Res Int ; 30(42): 95828-95839, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37561291

RESUMEN

There is growing evidence suggesting that exposure to volatile organic compounds (VOCs) can pose significant health risks, including interference with the function of the reproductive system. However, there has been a lack of research focused on the impact of common environmental VOCs on the levels of sex hormones in the general female population. In this study, we conducted a cross-sectional analysis utilizing the database of the National Health and Nutrition Examination Survey (NHANES, 2013-2016). A total of 2633 participants were included in this study. The Pearson correlation model revealed the potential of co-exposure or co-toxicity between benzene and 2,5-dimethylfuran. According to GLM models, we discovered a significant positive association between blood levels of 2,5-dimethylfuran and benzene with testosterone levels in women. Subgroup analysis further identified that the women with underweight and healthy weight might be the high-risk subgroup. Bayesian kernel machine regression (BKMR) was applied to further assess the univariate and bivariate exposure-response relationships between multiple VOCs. Our research systemically formulated the possible relationship between exposure to VOCs and female sex hormones, indicating the role of VOCs as a risk factor for endocrine disruption, especially benzene and 2,5-dimethylfuran. These findings have important implications for public health and call for further investigation.


Asunto(s)
Contaminantes Atmosféricos , Compuestos Orgánicos Volátiles , Humanos , Femenino , Compuestos Orgánicos Volátiles/análisis , Estudios Transversales , Exposición a Riesgos Ambientales/análisis , Encuestas Nutricionales , Benceno/análisis , Contaminantes Atmosféricos/análisis , Teorema de Bayes , Hormonas Esteroides Gonadales/análisis
15.
Food Chem Toxicol ; 172: 113544, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-36464108

RESUMEN

The safety of flavoring agents has been evaluated according to classification by chemical structure and using a decision tree approach. The genotoxic potential found in some flavoring agents has highlighted the importance of efficient toxicity studies. We performed a comprehensive toxicity analysis using reporter gene transgenic rats to assess the safety of 3-acetyl-2,5-dimethylfuran (ADF), a flavoring agent exhibiting genotoxic potential in silico and in vitro assays. Male F344 gpt delta rats were given 0, 30, or 300 mg/kg body weight/day ADF by gavage for 13 weeks. In serum biochemistry analyses, triglyceride, total cholesterol, phospholipid, and total protein levels and albumin/globulin ratios were significantly altered in the 30 and 300 mg/kg groups. Histopathologically, nasal cavity toxicity and hepatocellular hypertrophy were observed in the 300 mg/kg group. In the livers of 300 mg/kg group, a significant increase in gpt mutant frequencies were observed along with ADF-specific DNA adduct formation. The number and area of glutathione S-transferase placental form-positive foci were significantly increased in the same group. Thus, ADF affected nasal cavity, liver, and lipid metabolism and showed genotoxicity and possible carcinogenicity in the liver. Overall, our comprehensive toxicity study using gpt delta rats provided insights into the safety evaluation of ADF.


Asunto(s)
Aromatizantes , Placenta , Embarazo , Ratas , Femenino , Animales , Ratas Endogámicas F344 , Pruebas de Mutagenicidad , Ratas Transgénicas , Hígado , Daño del ADN
16.
ChemSusChem ; 15(13): e202102532, 2022 Jul 07.
Artículo en Inglés | MEDLINE | ID: mdl-34997695

RESUMEN

Catalytic hydrogenolysis of biobased furan aldehydes (i. e., 5-methylfurfural, 5-hydroxymethylfurfural) to 2,5-dimethylfuran has gained extensive interest for biomass-derived fuels and chemicals. Herein, a class of NiCo2 O4 -supported palladium with considerable oxygen defects was synthesized by hydrogen plasma etching and phosphating methods. The oxygen defects not only promoted the hydrogenation of the C=O group but also enhanced the accessibility of coordinatively unsaturated metal cations with Lewis acidity for the hydrogenolysis of the C-OH group. Meanwhile, the additional Brønsted acidity in Pd/NiCo2 O4-x obtained by phosphating could further strengthen the hydrogenolysis ability by the etherification route of C-OH. Finally, Pd/NiCo2 O4-x exhibited the most effective performance with 2,5-dimethylfuran yields of 92.9 and 90.5 % from 5-methylfurfural and 5-hydroxymethylfurfural, respectively. These catalytic mechanisms were confirmed by in-situ infrared spectroscopy and control experiments. Furthermore, the catalyst showed outstanding recycling stability. This work shows powerful synergistic catalysis in the hydrogenolysis reaction by multifunctional active sites.


Asunto(s)
Aldehídos , Furanos , Catálisis , Furanos/química , Oxígeno , Paladio/química
17.
ChemSusChem ; 15(13): e202200193, 2022 Jul 07.
Artículo en Inglés | MEDLINE | ID: mdl-35333002

RESUMEN

Designing highly efficient and low-cost catalysts for conversion of renewable biomass into high value-added chemicals and biofuels is important and challenging. Herein, a non-noble Ni-Mn bifunctional catalyst supported on activated carbon (Ni-Mn/AC) was developed by an incipient wetness impregnation method. The catalyst was found to be economic and efficient for the selective hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural (5-HMF) to 2,5-dimethylfuran (2,5-DMF). The optimal Ni-Mn/AC (Ni/Mn=3) catalyst achieved 98.5 % 2,5-DMF yield with 100 % conversion of 5-HMF under mild reaction conditions of 180 °C, 2.0 MPa H2 for 4 h. Furthermore, the catalyst exhibited outstanding reusability and could be recycled eight times without loss of activity. The addition of Mn not only enhanced the reactivity of 5-HMF but also resulted in the dominant reaction pathway shift from the hydrogenation of the C=O bond to the hydrogenolysis of C-OH bond, which was attributed to the synergy of highly dispersed Ni metallic nanoparticles and moderate Lewis acid sites from MnOx as revealed by detailed characterizations.


Asunto(s)
Carbón Orgánico , Furaldehído , Catálisis , Furaldehído/análogos & derivados , Furaldehído/química , Furanos
18.
Front Chem ; 10: 907649, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35651715

RESUMEN

The catalytic hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is a promising route towards sustainable liquid fuels with a high energy density. Herein, a novel CuCoNiAl-containing mixed metal oxide catalyst (CuCoNiAl-MMO) was prepared by calcination a layered double hydroxide (LDH) precursor in N2 at 500 °C, then applied for the catalytic hydrogenolysis of HMF to DMF. The effects of reaction time, reaction temperature and hydrogen pressure on DMF selectivity were investigated. Under relatively mild reaction conditions (180°C, 1.0 MPa H2, 6.0 h), CuCoNiAl-MMO showed both a high initial activity and selectivity for hydrogenolysis of HMF to DMF, with HMF conversion rate of 99.8% and DMF selectivity of 95.3%. Catalysts characterization studies using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) revealed the presence of various metal oxides and metallic copper on the surface of the CuCoNiAl-MMO catalyst, with the presence of mixed metal-oxide-supported metallic Cu nanoparticles being responsible good hydrogenolysis activity of the catalyst for selective DMF synthesis.

19.
Front Chem ; 10: 882670, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35494636

RESUMEN

A new type of biomass-based liquid fuel, 2,5-dimethylfuran (DMF), has attracted significant attention owing to its unique physical properties and carbon neutrality. It can be obtained from the hydrogenation of 5-hydroxymethylfurfural (HMF), an important biomass platform compound. In this study, we developed a nitrogen-doped carbon-confined CuCo bimetallic catalyst with a popcorn-like structure for the selective hydrogenation of HMF with high efficiency and adequate stability. Under optimized conditions, 100% HMF conversion and 93.7% DMF selectivity were achieved. The structure of the catalyst was characterized using XRD, XPS, SEM, and TEM. It was observed that carbon spheres, which were covered by nitrogen-doped carbon nanotubes, uniformly formed, while metal particles were confined in the nitrogen-doped carbon nanotubes. The popcorn-like structure exhibited a larger surface area and provided more contact sites, while the confined metal particles were the main active sites. The synergistic effect between Cu and Co was beneficial for DMF selectivity.

20.
Front Chem ; 10: 979353, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-36072701

RESUMEN

Efficient conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to renewable fuels such as 2,5-dimethylfuran (DMF) and 2,5-dimethyltetrahydrofuran (DMTHF) is of significance for sustainable energy supply. For efficient catalyst design, it is important to understand the catalytic behavior and clarify the influence of physico-chemical properties of catalyst on reaction performance. Herein, to study the structure-activity relationships of monometallic Cu catalysts for HMF hydrogenolysis, a series of Cu/SiO2 catalysts with different physico-chemical properties were prepared and compared for their catalytic performance in HMF hydrogenolysis. It was found that Cu/SiO2-HT-8.5 catalyst prepared by hydrothermal method showed excellent activity in HMF hydrohydrolysis reaction. Under the optimal reaction condition, the total yield of liquid fuels reaches 91.6% with 57.1% yield of DMF and 34.5% yield of DMTHF in THF solvent. Characterizations such as XRD, H2-TPR, N2-adsorption/desorption, TEM and XPS revealed that the Cu particles in the Cu/SiO2-HT-8.5 catalyst have uniform size and high dispersion. The Cu species and the SiO2 support have relatively weak interaction and are easy to be reduced to Cu0, which makes it show excellent activity in the hydrogenolysis of HMF.

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