GREEN CHEMISTRY
·
2014
·Vol. 16
·期 5
·2490-2499
·
IF 6.852
Jinzhu Chen,Kegui Li,Limin Chen,Ruliang Liu,Xing Huang,Daiqi Ye
A series of sulfonic acid-functionalized metal–organic frameworks (MOF-SO3H) were prepared by postsynthetic modification (PSM) of the organic linkers within the MOF with chlorosulfonic acid. The obtained MOF-SO3H, including sulfonic acid-functionalized MIL-101(Cr) [MIL-101(Cr)-SO3H], UIO-66(Zr) [UIO-66(Zr)-SO3H], and MIL-53(Al) [MIL-53(Al)-SO3H], have been systematically studied as solid acids in fructose transformation to 5-hydroxymethylfurfural (HMF). With MIL-101(Cr)-SO3H as catalyst, a HMF yield of 90% with a full fructose conversion was obtained at 120 °C for 60 min in DMSO. The concentration of –SO3H in MOF-SO3H as well as the contribution of Brønsted acidity of MOF-SO3H parallels its –SO3H grafting rate. Under a lower –SO3H grafting level, a good linear correlation between catalytic activity, in terms of turnover frequency, and sulfonic acid-site density of MOF-SO3H was found. Moreover, the sulfonic acid groups, which function as the catalytic sites, are equivalent in all MOF-SO3H for fructose-to-HMF transformation, regardless of precursor MOFs. Both conversions of fructose and selectivities towards HMF increase with the sulfonic acid-site density of MOF-SO3H at an initial stage of fructose-to-HMF transformation. Kinetics studies reveal that the MIL-101(Cr)-SO3H promoted fructose-to-HMF transformation may follow pseudo-first-order kinetics with observed activation energy of 55 kJ mol−1 under the investigated conditions. Moreover, MIL-101(Cr)-SO3H behaves as a heterogeneous catalyst and can be easily recovered and reused. The research highlights a good prospect for catalytic application of MOF-derived solid acid catalysts for biomass carbohydrate valorization.
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高影响因子
RSC Advances
·
2013
·Vol. 4
·期 8
·4194-4202
·
IF 2.562
Jinzhu Chen,Guoying Zhao,Limin Chen
Direct conversion of fructose into 5-hydroxymethylfurfural (HMF) and alkyl levulinate is achieved by making use of ionic liquid-based polyoxometalate salts (IL-POMs) as solid acid catalysts. Among these solid acids, phosphotungstic acid-derived IL-POM shows the highest catalytic performance in both the HMF and ethyl levulinate (EL) formation. A study for optimizing the reaction conditions such as the reaction time and the temperature has been performed. High HMF and EL yields of up to 99% and 82%, respectively, are obtained from fructose under the investigated conditions. Moreover, the generality of the catalyst is further demonstrated by processing representative di- and polysaccharides such as sucrose and inulin with good yields to HMF (76% from inulin and 48% from sucrose) and EL (67% from inulin and 45% from sucrose), again under mild conditions, thereby eliminating the separate hydrolysis step before the dehydration reaction. The catalyst recycling experiment indicates that the adsorption and accumulation of oligomeric products on the catalyst surface results in a partial deactivation of catalyst. The mechanism research reveals that a major pathway for EL formation involves a fructose-to-HMF transformation followed by HMF etherification and rehydration of HMF-ether to give EL. The research highlights an efficient, environment-friendly and recyclable solid acid for biomass valorization.
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高影响因子
GREEN CHEMISTRY
·
2013
·Vol. 15
·期 10
·2895-2903
·
IF 6.828
Ruliang Liu,Jinzhu Chen,Xing Huang,Limin Chen,Longlong Ma,Xinjun Li
A series of sulfonic acid-functionalized carbon materials (C–SO3H), including poly(p-styrenesulfonic acid)-grafted carbon nanotubes (CNT-PSSA), poly(p-styrenesulfonic acid)-grafted carbon nanofibers (CNF-PSSA), benzenesulfonic acid-grafted CMK-5 (CMK-5-BSA), and benzenesulfonic acid-grafted carbon nanotubes (CNT-BSA), have been studied for fructose dehydration to 5-hydroxymethylfurfural (HMF) and fructose alcoholysis to alkyl levulinate. A study for optimizing the reaction conditions such as the catalyst loading, the reaction time, and the temperature has been performed. Under the optimal conditions, high HMF and ethyl levulinate yields of up to 89% and 86%, respectively, are obtained. The catalytic activities of C–SO3H for the conversions of fructose into both HMF and ethyl levulinate follow the order of their acid strength. The relationship between the catalytic activity and acid density of C–SO3H shows a linear correspondence in the fructose dehydration to HMF. The facile separation, ease of recovery, and high thermal stability make the developed C–SO3H efficient and environment-friendly catalytic materials for transforming biomass carbohydrate into fine chemicals.
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高影响因子
Journal of Energy Chemistry
·
2016
·
IF 2.322
Xiaofang Liu,Hu Li,Hu Pan,Heng Zhang,Shan Huang,Kaili Yang,Wei Xue,Song Yang
In this work, a series of MIL-101-SO 3 H( x ) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural (EMF) in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran (THF). The influence of –SO 3 H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO 3 H (100) at 130 °C for 15 h. The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers (PCPs) for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.
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高影响因子
Journal of Food Measurement and Characterization
·
2016
·Vol. 11
·期 2
·696-703
·
IF 0.521
Kong Lu,Zhao Xin-Huai
Three acids (acetic, propionic and butyric acids) yielded from simulated colonic fermentation of inulin and xylo-oligosaccharides (XOS) in the absence and presence of six exogenous strains were investigated in this study. Both inulin and XOS were fermented by fecal extract (FE) prepared from healthy adults and by an exogenous strain for 48 h, and three acids generated in fermentation products at five time periods were detected by gas chromatography. Inulin and XOS during fermentation were capable of producing more propionic and butyric acids, respectively, whilst inoculation using one strain culture into fermentation systems mostly increased yields of three acids. In inulin-containing fermentation systems, these strains increased yields of propionic and butyric acids by 6–34 and 206–250%, respectively. In XOS-containing fermentation systems, these strains did not enhance yield of propionic acid, but increased yield of butyric acid by 50–96%. In general, Lactobacillus brevis, Lactobacillus plantarum, Lactobacillus rhamnosus, Enterococcus faecalis and Enterococcus faecium were more efficient than Lactobacillus acidophilus to increase yields of propionic and butyric acids. It is thus concluded that the six strains in total displayed beneficial effects on simulated fermentation of inulin and XOS through enhancing yields of three acids especially propionic and butyric acids with healthcare functions.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2016
·
IF 5.31
Zhenzhen Yang,Wei Qi,Renliang Huang,Jie Fang,Rongxin Su,Zhimin He
Functionalized silica nanoparticles with strong acidity and different hydrophobicity were successfully synthesized by an alkali co-condensation method. The structure of the hydrophobic solid acids were characterized, and the catalytic properties were investigated in fructose dehydration to 5-hydroxymethylfurfural (5-HMF). Experiment results indicated that catalyst hydrophobicity has a positive influence on both 5-HMF yield and selectivity. The highest yield of 5-HMF (87%) with full conversion of fructose was obtained when the most hydrophobic solid acid (SiNP-SO 3 H-C 16 ) was used as the catalyst. The reason can be interpreted as the hydrophobic groups in the silica nanoparticles can effectively isolate SO 3 H groups with water molecules in the reaction system, and thus hinder the rehydration of 5-HMF, which is the main side-reaction in 5-HMF formation. Other important reaction parameters such as reaction medium, temperature, time and catalyst loading were also studied for fructose dehydration. Recycling and control experiments demonstrated the good reusability and stability of the functionalized silica nanoparticles. Furthermore, inulin was also used as a feedstock for 5-HMF production and gave a high 5-HMF yield of 65% in the catalysis of a moderate hydrophobic silica nanoparticle.
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RESEARCH ON CHEMICAL INTERMEDIATES
·
2016
·Vol. 42
·期 12
·8305-8319
·
IF 1.833
Nie Guangxia,Tong Xinli,Zhang Yangyang,Liang Mao,Zhuang Xuli,Xue Song
Abstract The efficient production of 5-hydroxymethyl furfural (HMF) from carbohydrates is achieved in the presence of polyaniline-based solid catalysts. The composite polyaniline–graphite oxide (PANI–GO) is prepared from in situ polymerization of aniline in the solution of colloidal GO which was obtained from oxidation of graphite with Hummers’ method. Moreover, the SO
2 4
/PANI and SO
2− 4
/PANI–GO materials were synthesized from the sulfation of PANI and PANI–GO by a 70 % sulfuric acid solution. All obtained samples are respectively characterized with XRD, TG, FTIR, SEM and TEM techniques to reveal the physical properties and structures of these materials. When these materials were used in the dehydration of d -fructose, it was found that the PANI–GO and SO
2− 4
/PANI–GO as the catalyst exhibited prominent activities in which 80.7 and 72.4 % yields of HMF were obtained in N -methylpyrrolidone solvent at 160 °C for 4 h. In addition, the effects of reaction temperature, time, solvents and the recycling of PANI–GO material were also investigated. The material provides a promising method for the catalytic conversion of other biomass feedstocks. Graphical Abstract
Metal-free and efficient conversion of different carbohydrates to 5-hydroxymethyl furfural (HMF) with a novel PANI–GO catalyst has been successfully performed.
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Catalysis Science & Technology
·
2016
·Vol. 6
·期 20
·7586-7596
·
IF 5.287
Xiangcheng Li,Qineng Xia,Van Chuc Nguyen,Kaihao Peng,Xiaohui Liu,Nadine Essayem,Yanqin Wang
An efficient and selective production of 5-hydroxymethylfurfural (HMF) from carbohydrates is achieved in the presence of mesoporous AlSiO catalysts in a THF/H2O–NaCl biphasic system. These mesoporous AlSiO catalysts are prepared by a facile sol–gel method and have tunable acidity. Their acidic sites are characterized and quantified by NH3-TPD, microcalorimetry of NH3 adsorption and Py-FTIR, then correlated with the catalytic isomerization and dehydration of glucose to HMF. The detailed studies show that the AlSiO-20 catalyst with a Si/Al ratio of 18 is favorable for HMF production due to its inherently high surface area, high amounts of acid sites and a suitable Brønsted/Lewis acid ratio. Over the AlSiO-20 catalyst, an HMF yield of 63.1% is obtained at 160 °C for 1.5 h in the biphasic THF/H2O–NaCl medium with 10 wt% glucose in water. Further conducting the amplification experiment 30 times, the HMF yield still reaches 60.2% and the yield has no obvious decline after four catalytic cycles; this is the best result for an amplification experiment of HMF from glucose over a heterogeneous catalyst so far. After separation, HMF can be used for the production of 2,5-furandicarboxylic acid (FDCA) and as high as 95% FDCA yield is obtained over the Pt/C catalyst. Furthermore, the AlSiO catalyst demonstrates excellent activity in the conversion of disaccharides, polysaccharides and even lignocellulosic biomass, indicating it would be a promising catalyst for the conversion of glucose and glucose-based carbohydrates to HMF in industry applications.
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AICHE JOURNAL
·
2016
·Vol. 63
·期 1
·257-265
·
IF 2.98
Haizhou Lin,Qingang Xiong,Yuan Zhao,Jingping Chen,Shurong Wang
In this work, a green reaction system of CO 2 -water-isopropanol was developed for 5-hydroxymethylfurfural (HMF) production. The conversion of fructose in a CO 2 -water system was first investigated, and the results showed this system could promote the formation of HMF compared to a pure water system. Then, isopropanol was introduced into the CO 2 -water system and the HMF formation became better because the solvent effect of isopropanol increased the tautomeric composition of fructofuranose, which was easy to form HMF. The existence of isopropanol was found to greatly suppress secondary reactions where HMF was converted to levulinic acid and insoluble humin. Meanwhile, the effects of reaction parameters on the conversion of fructose to HMF in the CO 2 -water-isopropanol system were analyzed, and a high HMF yield of 67.14% was obtained. Finally, to further illustrate the merits of CO 2 -water-isopropanol system, productions of HMF from other carbohydrates were tested and satisfactory yields were achieved. © 2016 American Institute of Chemical Engineers AIChE J , 63: 257–265, 2017
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Food & Function
·
2016
·Vol. 7
·期 11
·4637-4643
·
IF 2.686
Chun Chen,Qiang Huang,Xiong Fu,Rui Hai Liu
This study investigated the in vitro fermentation of polysaccharides from Morus alba L., the contribution of its carbohydrates to the fermentation, and the effect on the composition of gut microbiota. Over 48 h of fermentation, the pH value in the fecal culture decreased from 7.12 to 6.14, and the total short chain fatty acids (SCFA) and acetic, propionic, and butyric acids all significantly increased. After 48 h of fermentation, 45.36 ± 1.36% of the total carbohydrates in the polysaccharide, including 35.72 ± 1.51% of arabinose, 23.1 ± 1.19% of galactose, 41.43 ± 1.52% of glucose, 26.36 ± 1.93% of rhamnose and 65.57 ± 1.07% of galacturic acid, were consumed. The increase in acetic and butyric acids was primarily due to the fermentation of galactose and galacturonic acid in the polysaccharide, while the increase in propionic acid resulted mainly from the fermentation of arabinose and glucose. In addition, the polysaccharide could modulate the gut microbiota composition by increasing the Bacteroidetes population and decreasing the Firmicutes population. The results may facilitate the development of food products known as prebiotics, aimed at improving gastrointestinal health.
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PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2016
·
IF 3.782
Yunchuan Qi,Meiling Yang,Wenhui Xu,Sha He,Yi Men
Three polysaccharide- graphene oxide composite materials (PS-GO) were synthesized from graphene oxide (GO) and natural polysaccharides, which compounds were tested for removal of organic dyes from aqueous solutions. These adsorbents were characterized by Fourier transform infrared spectroscopy (FT-IR), Raman spectrometer, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), N 2 adsorption-desorption isotherms and UV–vis spectrum. The adsorption properties of PS-GO towards four organic dyes were investigated along with measured effects on adsorption by initial concentration, temperature, contact time and pH value. Resulting adsorption isotherms , thermodynamics and kinetics were analyzed systematically. In these tests, PS-GO composite materials were found to be more efficient than as-prepared GO as adsorbents for the removal of both cationic and anionic organic dyes.
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PubMed
高影响因子
Journal of Energy Chemistry
·
2016
·
IF 2.322
Ran An,Guizhuan Xu,Chun Chang,Jing Bai,Shuqi Fang
Butyl levulinate (BL) is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the catalysis of metal sulfates was developed. The catalytic activity of a series of metal sulfates for the synthesis of BL from fructose was investigated. Among various metal sulfates, ferric sulfate Fe 2 (SO 4 ) 3 was found to be the most efficient catalyst, which gave a remarkably high BL yield of 62.8 mol% under the conditions of 463 K, 3 h, a catalyst dosage of 5.0 g/L, and fructose concentration of 25 g/L. Different carbohydrates including glucose, cellulose , inulin and sucrose were also used for one-pot synthesis of BL with the catalysis of Fe 2 (SO 4 ) 3 , showing the yields of 39.6, 30.5, 56.6 and 50.1 mol%, respectively. In addition, the recycling and reuse of Fe 2 (SO 4 ) 3 was studied by characterizing them using powder X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS). A plausible reaction pathway for the one-pot synthesis of BL from fructose was proposed. This study provides a facile and feasible way for the synthesis of BL from biomass.
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