Energy Technology
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2013
·
IF 0
Hu Li,Xudong He,Qiuyun Zhang,Fei Chang,Wei Xue,Yuping Zhang,Song Yang
The dehydration of fructose to 5-hydroxymethylfurfural (HMF) in the presence of a SO 3 H-functionalized heteropolyanion-based polymeric hybrid catalyst is investigated. Poly(1-vinyl-3-propane sulfonate imidazolium)-H 3 PW 12 O 40 [poly(VMPS)-PW], a supported ionic liquid catalyst (SILC) was prepared and used as a heterogeneous Brønsted-acidic catalyst. We demonstrate that an 83% yield of HMF can be obtained at 130 ºC after 60 min using DMSO as the solvent, under atmospheric pressure. The catalytic scope of poly(VMPS)-PW is studied by using it as a catalyst for the dehydration of glucose. We demonstrate that the catalyst is also suitable for conversion of glucose to HMF, with a yield of 26 % under mild conditions. Moreover, the acidic hybrid catalyst is easily separated from the reaction mixture by centrifugation. The ability to recycle the catalyst is demonstrated and poly(VMPS)-PW is reused five times without significant loss of activity.
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RSC Advances
·
2014
·Vol. 4
·期 29
·15216-15224
·
IF 3.708
Chong-Wen Jiang,Xin Zhong,Zheng-Hong Luo
5-Hydroxymethylfurfural (5-HMF) which can be produced from cellulose is considered as one of the promising green platform chemicals. In this work, the conversion of cellulose to 5-HMF was carried out through hydrolysis in a batch reactor using the SO42−/Ti-MCM-41 catalyst at a temperature of 463–503 K. Two analytical techniques including the 3,5-dinitrosalicylic acid (DNS) method and high performance liquid chromatography (HPLC) were employed to track the time evolution of the main reagents, i.e., cellulose, 5-HMF and reducing sugar. Based on the typical kinetic experiments for the cellulose hydrolysis, a comprehensive hydrolysis mechanism was introduced to describe the heterogeneous hydrolysis of cellulose to 5-HMF. A corresponding kinetic model was proposed on the basis of the hydrolysis mechanism and the mass balance law. The results show that the predicted data obtained via the suggested model agree well with the experimental results. In addition, some data from the open reports were referred for further model verification in this work. The kinetic model suggested in this work is a mechanism model for the heterogeneous catalytic cellulose hydrolysis process, which is different from the previous first-order kinetic model.
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高影响因子
CATALYSIS TODAY
·
2014
·
IF 3.309
Cong Zhang,Jing Xing,Liang Song,Hongchuan Xin,Sen Lin,Lishu Xing,Xuebing Li
Aqueous phase catalytic upgrading of phenolic monomers to hydrocarbons have been explored using Pd/C combined with HZSM-5 zeolite catalysts in the presence of H 2 . 2-Methoxyl-4-allylphenol (eugenol), which consists of methyl ether bond, hydroxyl group, aromatic ring and propyl olefin bond, was chosen as a classic lignin model compound. This research focuses on the relationship between the acidity of zeolites and the deoxygenation activities basis on the hydrodeoxygenation (HDO) of eugenol. The results indicated that the decrease of Si/Al ratio resulted in the increase of the acidity of the zeolites, which significantly influenced their catalytic performance for product distributions. Over the HZSM-5 (Si/Al = 12.5) catalyst, the 2-methoxyl-4-propylphenol conversion of 86.5% and the hydrocarbon selectivity of 73.4% were obtained with the HDO of eugenol under 513 K and 5 MPa hydrogen pressure. Owing to the lower selectivity of hydrocarbon with HZSM-5 (Si/Al = 50) as acidic catalyst, the pore treatment was used to enlarge the outer surface of zeolite. After modified by alkali-treatment, much more acid active sites were provided for feasible accessibility of oxygenated reactants. The selectivity of hydrocarbons was improved by the alkaline treatment of HZSM-5 zeolite with 0.3 mol L −1 sodium hydroxide solution.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2014
·
IF 2.235
Shuguo Wang,Zehui Zhang,Bing Liu,Jinlin Li
In this study, aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) was studied over a magnetic catalyst [Fe3O4@SiO2-NH2-Ru(III)]. Various reaction parameters were optimized for the oxidation of HMF into DFF. A high DFF of 86.4% and HMF conversion of 99.3% were obtained after 4 h at 120 °C. More importantly, the catalyst also showed high catalytic activity in air, and high HMF conversion of 99.7% and DFF yield of 86.8% were obtained after 16 h. The high catalytic performance of Fe3O4@SiO2-NH2-Ru(III) in air makes this method much more convenient and economical. Moreover, the procedure of the catalyst recycle was simple as the Fe3O4@SiO2-NH2-Ru(III) catalyst could be readily recovered from the reaction mixture by a permanent magnet. The catalyst could be reused several times without significant loss of its catalytic activity.
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高影响因子
ACS Catalysis
·
2014
·
IF 7.572
Jinzhu Chen,Ruliang Liu,Yuanyuan Guo,Limin Chen,Hui Gao
A catalyst of palladium [Pd/MIL-101(Al)-NH2] supported on amine-functionalized Metal–Organic Frameworks (MOFs) allows selective hydrogenation of biomass-based 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethyl-tetrahydrofuran (DHMTHF) with 2,5-dihydroxymethylfuran (DHMF) as an observed “intermediate”. The Pd/MIL-101(Al)-NH2 was prepared by using a direct anionic exchange approach and subsequent gentle reduction. The presence of free amine moieties in the frameworks of MIL-101(Al)-NH2 is suggested to play a key role on the formation of uniform and well-dispersed palladium nanoparticles on the support. The adsorption experiments reveal that the amine-functionalized MOF supports show preferential adsorption to hydrogenation intermediate DHMF than in the case of reactant HMF owing to an enhanced hydrophilic nature of DHMF as well as improved hydrogen bonding interactions between DHMF and the MOF support, which promotes a further hydrogenation of DHMF to DHMTHF upon the in situ formation of DHMF over Pd/MIL-101(Al)-NH2. Moreover, our results also indicate that the observed high selectivity toward DHMTHF form HMF is closely related to the cooperation between the metallic site and the free amine moiety on the MOF support. Under the optimal conditions, a maximum DHMTHF yield of 96% with a full conversion of HMF is obtained by using Pd/MIL-101(Al)-NH2 (Pd 3.0 wt %) catalyst at a low reaction temperature of 30 °C in aqueous medium. The research thus highlights new perspectives for aluminum-based and amine-functionalized MOF material for biomass transformation.
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POLYMER COMPOSITES
·
2014
·Vol. 36
·期 9
·1597-1605
·
IF 1.455
Ruxangul Jamal,Ahmat Ali,Li Zhang,Yakupjan Osman,Adalet Rahman,Tursun Abdiryim
Poly(3′,4′-ethylenedioxy-2,2′:5′,2″-terthiophene)/ZnO(poly(TET)/ZnO) composites with the ratio of poly(TET) and nano-ZnO from 3:1 to 1:3 were synthesized by hand grinding and ball milling methods, respectively. The photocatalytic activities of the composites were examined through the degradation processes of methylene blue (MB) solution under UV light irradiation, and the possible mechanism for the photocatalytic activity enhancement by synergetic effects between nano-ZnO and poly(TET) was proposed. The results showed that the strong interactions between the poly(TET) and nano-ZnO occurred in the case of ball milling method. The results also proved that the crystallinity of ZnO was not disturbed in both of methods, and the nano-ZnO was uniformly distributed in polymer matrix in the case of ball milling method. The comparative studies showed that the addition of the nano-ZnO could enhance the photocatalytic activities of the composites. The highest degradation efficiency (100%) at 3 h under UV light irradiation occurred in the case of poly(TET)/ZnO(1:1) synthesized by ball milling method. Furthermore, the nanocompsosite displayed higher photocatalytic activity than nano-ZnO, which was due to the holes ( h + ) transferring from the valence band of ZnO to the polymer backbone and the adsorption of MB molecules in polymer matrix via π–π conjugation between MB and aromatic regions of the poly(TET). POLYM. COMPOS., 36:1597–1605, 2015. © 2014 Society of Plastics Engineers
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CLINICAL AND EXPERIMENTAL PHARMACOLOGY AND PHYSIOLOGY
·
2014
·Vol. 42
·期 2
·146-153
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IF 2.405
Xiao-Yun Hu,Ji-Yun Liang,Xue-Jun Guo,Li Liu,Ya-Bing Guo
Summary The development of chemoresistance may reduce the efficacy of chemotherapeutic drugs for treating hepatocellular carcinoma (HCC). In the present study, the effects of apigenin on intensifying the chemosensitivity of HCC cells and an HCC xenograft model in response to 5-fluorouracil (5-FU) were investigated. Sub-toxic concentrations of apigenin (4 μ mol/L) significantly enhanced the cytotoxicity of 5-FU (100 μ g/mL) in HCC cells. In vivo , combined treatment with apigenin (20 mg/kg, five times/week for 3 weeks) and 5-FU (20 mg/kg for 5 consecutive days) significantly inhibited the growth of HCC xenograft tumours. Annexin V–propidium iodide dual staining assays, terminal deoxyribonucleotidyl transferase-mediated dUTP–digoxigenin nick end-labelling assays and western blotting analysis were used to confirm the synergistic effects of apigenin and 5-FU on HCC apoptosis. Coincubation of HCC cells with apigenin and 5-FU increased levels of reactive oxygen species (ROS), which was followed by a decrease in the mitochondrial membrane potential (ΔΨm). In addition, combined triggered the mitochondrial apoptotic pathway, as indicated by decreased Bcl-2 expression and loss of ΔΨm, with significant activation of caspase 3 and poly(ADP-ribose) polymerase. The present study is the first to demonstrate that apigenin may potentiate the cytotoxicity of 5-FU in HCC via inhibition of ROS-mediated drug resistance and concurrent activation of the mitochondrial pathways of apoptosis.
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PubMed
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CHEMICAL ENGINEERING JOURNAL
·
2015
·
IF 4.321
Langchang Gao,Kejian Deng,Judun Zheng,Bing Liu,Zehui Zhang
In this study, a new method was developed for the oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) over Merrifield resin supported Co(II)–meso-tetra(4-pyridyl)-porphyrin (abbreviated as Merrifield resin-Co-Py). Diffuse reflectance spectra showed that Co(II)–meso-tetra(4-pyridyl)-porphyrin was successfully bonded on the Merrifield resin. The Merrifield resin-Co-Py catalyst was used for the oxidation of HMF into FDCA, and several parameters were studied. Tert-butyl hydroperoxide was the best oxidant among other common oxidants. The reaction solvent greatly affected both HMF conversion and product selectivity. High HMF conversion of 95.6% and FDCA yield of 90.4% were obtained at 100 °C after 24 h. Time course of HMF conversion over Merrifield resin-Co-Py showed that 2,5-diformylfuran was the intermediate for the conversion of HMF into FDCA. The catalyst could be reused without the significant loss of its catalytic activity.
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JOURNAL OF CHROMATOGRAPHY A
·
2015
·
IF 4.169
Qing Wang,Zhi-Yuan Luo,Mao Ye,Yu-Zhuo Wang,Li Xu,Zhi-guo Shi,Lanying Xu
The zirconia-coated silica (ZrO 2 /SiO 2 ) material was obtained by coupling layer-by-layer (LbL) self-assembly method and sol–gel technology, to take dual advantages of the suitable porous structure of SiO 2 and basic resistance of ZrO 2 . Adenosine 5′-monophosphate (5′-AMP) was then self-assembled onto ZrO 2 /SiO 2 via Lewis acid–base interaction, generating 5′-AMP-ZrO 2 /SiO 2 . The chromatographic properties of 5′-AMP-ZrO 2 /SiO 2 were systemically studied by evaluating the effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the 5′-AMP-ZrO 2 /SiO 2 possessed hydrophilic interaction chromatographic (HILIC) property comprising hydrophilic, hydrogen-bonding, electrostatic and ion-exchange interactions. For basic analytes, the column efficiency of ZrO 2 /SiO 2 and 5′-AMP-ZrO 2 /SiO 2 was superior to the bare ZrO 2 , and different selectivity was obtained after the introduction of 5′-AMP. For acidic analytes, good resolution was obtained on 5′-AMP-ZrO 2 /SiO 2 while the analysis failed on the bare ZrO 2 column owing to strong adsorption. Hence, the proposed 5′-AMP-ZrO 2 /SiO 2 had great potential in analyzing acidic compounds in HILIC mode. It was an extended application of ZrO 2 based SP.
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PubMed
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2017
·
IF 3.648
Likang Fu,Libo Zhang,Shixing Wang,Jinhui Peng,Gengwei Zhang
A novel adsorbent was synthesized via modifying silica nanoparticles with 3-Amino-5-mercapto-1,2,4-triazole and was used to selectively adsorb silver ions from aqueous solutions. The adsorbent was confirmed by Fourier transform infrared spectroscopy , X-ray photoelectron spectroscopy, transmission electron microscope and Brunauer-Emmett-Teller (BET) surface area analysis. Batch adsorption experiments were carried out to evaluate the adsorption conditions, reusability and selectivity . The results showed that the optimum pH is 5 and the maximum adsorbability was 124.52 mg/g. The adsorption rate was very high and equilibrium was achieved within 20 min. The total adsorption process preferably followed the pseudo-second order kinetics and the Langmuir isotherm model. The sorbent was stable and efficient. After used five times, the adsorbability was 98.72% of the initial adsorbability. Moreover, the adsorbent adsorb selectively Ag + from coexisting ions in aqueous solution.
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ChemSusChem
·
2017
·Vol. 10
·期 8
·1669-1674
·
IF 7.226
Zhongsen Ma,Hualei Hu,Zhongqiang Sun,Wenting Fang,Jian Zhang,Longfei Yang,Yajie Zhang,Lei Wang
Graphical Zeolite catalysis : Zeolite L is synthesized by the hydrothermal method, post-treated by NH 4 exchange to adjust its acidity, and characterized by various techniques. In the dehydration of fructose catalyzed by modified zeolite L in the ionic liquid [bmim]Br, 99.1 % yield of 5-hydroxymethylfurfural (HMF) is obtained. Zeolite L was synthesized by the hydrothermal method and post-treated by NH 4 exchange to adjust its acidity. The samples were systematic characterized by various techniques including XRD, X-ray fluorescence spectroscopy, N 2 adsorption–desorption, scanning electron microscopy, pyridine IR spectroscopy, and NH 3 temperature-programmed desorption. The results demonstrated that the NH 4 -exchange post-treatment increased the surface area, micropore volume, and acidity of zeolite L. The catalytic performance of the samples was tested in the dehydration of fructose to 5-hydroxymethylfurfural (HMF) in ionic liquid (1-butyl-3-methylimidazolium bromide, [bmim]Br). 99.1 % yield of HMF was obtained when the KL-80 °C-1 h sample (KL zeolite treated with 1 m NH 4 NO 3 solution at 80 °C for 1 h) was used. The high efficiency could be attributed to the appropriate acid properties of the catalyst. The zeolite catalyst could be reused four times without significant decrease in activity.
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ChemSusChem
·
2025
·
IF 6.6
Hailu Liu,Jianying Lin,Qiyu Liu,Yuhe Liao,Qiaozhi Ma
Graphical In this study, a typical Lewis acid Sn-β with low B/L ratio were synthesized and used for one-pot conversion of cellulose into 5-HMF in MSH/acetone system. The addition of Sn-β acid compensates for the Lewis acidity deficiency of MSH and efficiently promoted 5-HMF selectivity. Under the optimized reaction condition, a high 66.88 % yield of 5-HMF was obtained from cellulose conversion. The catalyst maintained a stable 5-HMF conversion rate after three cycles, achieving a direct conversion of cellulose to 5-HMF with excellent industrial application prospects. Producing 5-hydroxymethylfurfural (5-HMF) from abundant and renewable cellulose is a practical method for lignocellulosic biomass valorization. Nonetheless, the high crystallinity of cellulose restricts the accessibility of catalysts, and the complex reaction pathway generally results in the formation of intermediate by-products and 5-HMF degradation. Molten salt hydrates (MSHs) are unique in dissolving crystalline cellulose and their weak Brønsted acidity can facilitate cellulose hydrolysis to glucose. In this work, one-pot conversion of cellulose into 5-HMF was carried out in LiBr MSHs/acetone biphasic system. The solid acid, Sn-β, was used in the conversion to compensate for the shortages of MSH Lewis acidity. Under the optimized reaction condition at 180 °C for 20 min, a high 5-HMF yield of 66.88 % was obtained from cellulose conversion. The influences of reaction conditions on 5-HMF production were studied, and the synergistic effects of solvents and solid acid were established. The catalyzed can be readily recycled and regenerated via calcination. This technique provides a theoretical foundation and technical basis for constructing a one-step conversion of commercial cellulose to value-added 5-HMF, which proposes significant effects on lignocellulose valorization.
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