Heterogeneous catalysis, which has served well the petrochemical industry, may valuably contribute towards a bio-based economy by sustainably enabling selective reactions to renewable chemicals. Carbohydrate-containing matter may be obtained from various widespread sources and selectively converted to furanic platform chemicals: furfural (Fur) and 5-(hydroxymethyl)furfural (Hmf). Valuable bioproducts may be obtained from these aldehydes via catalytic transfer hydrogenation (CTH) using alcohols as H-donors under relatively moderate reaction conditions. Hafnium-containing TUD-1 type catalysts were the first of ordered mesoporous silicates explored for the conversion of Fur and Hmf via CTH/alcohol strategies. The materials promoted CTH and acid reactions leading to the furanic ethers. The bioproducts spectrum was broader for the reaction of Fur than of Hmf. A Fur reaction mechanism based on literature data was discussed and supported by kinetic modelling. The influence of the Hf loading and reaction conditions (catalyst load, type of alcohol H-donor, temperature, initial substrate concentration) on the reaction kinetics was studied. The reaction conditions were optimized to maximize the yields of 2-(alkoxymethyl)furan ethers formed from Fur; up to 63% yield was reached at 88% Fur conversion, 4 h/150 °C, using Hf-TUD-1(75), which was a stable catalyst. The Hf-TUD-1(x) catalysts promoted the selective conversion of Hmf to bis(2-alkoxymethyl)furan; e.g., 96% selectivity at 98% Hmf conversion, 3 h/170 °C for Hf-TUD-1(50). 相似文献
Considerable efforts have been made to utilize agricultural and forest residues as biomass feedstock for the production of second-generation bioethanol as an alternative fuel. Fermentation utilizing strains of Zymomonas mobilis and the use of simultaneous saccharification and fermentation (SSF) process has been proposed. Statistical experimental design was used to optimize the conditions of SSF, evaluating solid content, enzymatic load, and cell concentration. The optimum conditions were found to be solid content (30%), enzymatic load (25 filter paper units/g), and cell concentration (4 g/L), resulting in a maximum ethanol concentration of 60 g/L and a volumetric productivity of 1.5 g L?1?h?1. 相似文献
The choice of electrode material and surface preparation method are usually dictated by the suitability of the electrode to observe an electrochemical parameter, such as heterogeneous electron transfer rate, surface coverage, or redox potential. Thus, the glassy carbon (GC) and platinum (Pt) electrodes were modified with multiwalled carbon nanotubes (MWCNT) by direct “casting” modification using nine different aliquots of solvents. After drying at room temperature, the modified electrode showed distinct redox peaks corresponding to ferrocyanide oxidation/reduction. Using chemometrics, the cyclic voltammograms with higher current intensity were obtained for those in which ethanol, water and acetone as dispersing agents were used for GCE and dimethylformamide, water and acetone for Pt electrode modification. 相似文献
In this work, the catalytic activity of carbon nanotubes (CNTs), carbon black (CB), and CNT-CB counter electrodes in the I−/I3− reduction reaction is reported and compared with the Pt counter electrode. The fabricated counter electrodes were evaluated in dye-sensitized solar cells (DSSCs). The results indicate that the best cathodes were made from CNT10 (240 μm) and CB with a charge transfer resistance (RCT) of 2.70 Ω, and when the complete device shows 19.83 Ω of internal series resistance (RS), the photovoltaic parameters of these cells were JSC = 10.47 mA cm−2; VOC = 0.70 V; and FF = 57.90, with an efficiency of 4.29%, indicating a better interaction between the CNT10 in the 3D network of the counter electrode, generating a good charge transfer kinetics, in comparison with only CNT10 or CB.
Xylanases (EC3.2.1.8) catalyze the hydrolysis of xylan, the major constituent of hemicellulose. The use of these enzymes could
greatly improve the overall economics of processing lignocellulosic materials for the generation of liquid fuels and chemicals.
The hyperthermophilic archaeon Pyrodictium abyssi, which was originally isolated from marine hot abyssal sites, grows optimally at 97°C and is a prospective source of highly
thermostable xylanase. Its endoxylanase was shown to be highly thermostable (over 100 m in at 105°C) and active even at 110°C.
The growth of the deep-sea archaeon P. abyssi was investigated using different culture techniques. Among the carbohydrates used, beech wood xylan, birch wood glucuronoxylan
and the arabinoxylan from oats pelt appeared to be good inducers for endoxylanase and β-xylosidase production. The highest
production of arabinofuranosidase, however, was detected in the cell extracts after growth on xylose and pyruvate, indicating
that the intermediate of the tricarboxylic acid cycle acted as a nonrepressing carbon source for the production of thi enzyme.
Electron microscopic studies did not show a significant difference in the cell surface (e.g., xylanosomes) when P. abyssi cells were grown on different carbohydrates. The main kinetic parameters of the organism have been determined. The cell yield
was shown to be very low owing to incomplete substrate utilization, but a very high maximal specific growth rate was determined
(μmax=0.0195) at 90°C and pH 6.0. We also give information on the problems that arise during the fermentation of this hyperthermophilic
archaeon at elevated temperatures. 相似文献
This review covers two aspects concerning cooperativity in multiple weak bonds: a summary of literature results and a theoretical study of a complete series of model complexes. All the 15 combination of five weak bonds were explored: hydrogen bonds, hydric bonds, dihydrogen bonds, halogen bonds and ion–π interactions. Since in several cases there were no examples reported, a systematic exploration has been carried out on simple models at the MP2/aug-cc-pVTZ level. The results thus obtained have been analyzed using the atoms in molecules methodology. 相似文献
Different kinds of modifiers and coatings on the integrated platform of transversely heated graphite atomizer (THGA) have
been tested for the simultaneous determination of two group of elements: the first, the more volatile, formed by arsenic,
bismuth, lead, antimony and selenium; the second, the less volatile, formed by cobalt, chromium, cupper, iron and manganese
in milk by electrothermal atomic absorption spectrometry. Different Rh-modifiers were studied, such as Rh-coated platforms
(Rh), carbide plus rhodium coated platforms (W-Rh, Zr-Rh), carbide-coated platforms (W and Zr) with co-injection of RhCl3, solutions and uncoated platforms with injection of solutions of Pd(NO3)2, Mg(NO3)2, and RhCl3. Milk samples were diluted 1:10 in 1.0% HNO3 and injected into the tube. The mass of modifier deposited and co-injected in the tube and the use of end capped tubes were
also evaluated in order to improve the electrothermal behavior of analytes. Integrated platform pretreated with W plus co-injection
RhCl3 for first group and pretreated with W-Rh for second group were elected. For 20 μL injected samples the analytical curves
in the 5.0–20.0 μg L−1 concentration range have good linear correlation coefficients (r > 0.998). Relative standard deviations (n = 12) are <6% and the calculated characteristic masses are between 5 pg and 62 pg.
Correspondence: Gian Paulo G. Freschi, Faculdade de Ciências Exatas e Tecnologia, Universidade Federal da Grande Dourados,
PO Box 332, 79.804-970, Dourados-MS, Brazil; Instituto de Química, Universidade Estadual Paulista, PO Box 355, 14801-970 Araraquara-SP,
Brazil 相似文献
The interaction of arsenic(V) and arsenic(III) oxyanions with metal cations was investigated by potentiometry under temperature and ionic strength conditions approaching those prevailing in natural waters. The selection includes the major metal cations and some other ions of high environmental relevance. Ionic pairs [M(AsVO4)]?, [M(HAsVO4)] and [M(H2AsIIIO3)]+ formation is suggested for all +2 metal cations, based on the potentiometric results. These ion-pairs between arsenic anions and other metal cations are hardly ever mentioned or taken into account when arsenic speciation in natural waters is considered. These results provide the basis for studying arsenic speciation in natural aquatic systems, on which environmental fate, bioavailability and toxicity of the element depend. Some extrapolations to the conditions of the natural waters are presented as well as some insights into the adsorption process onto hydrous oxides. 相似文献