Pt-SDB疏水催化剂的粒径效应

制备了三种不同粒径的Pt-聚苯乙烯-二乙烯基苯(SDB)催化剂(1.0、2.0、4.0mm),并对比研究了三种催化剂的水-氢交换反应性能。研究表明:同一工艺条件下制备的催化剂,催化反应的同位素交换效率随着粒径的增大而降低,催化剂的粒径效应明显;为了减小粒径效应,优化了催化剂的还原温度,当粒径从1.0mm增至4.0mm时,催化剂的最优还原温度从240℃升高到320℃;进一步结合程序升温还原的方法,分析了还原反应的活化能,发现随着粒径的增大,最优还原温度的升高可能是改善了还原过程中的热量与质量传递。     

Taste perception and purchase intent of oil‐in‐water spreads: effects of oil types and salt (NaCl or KCl) concentrations

Associations of sodium intake with heart‐related problems are creating awareness towards reducing sodium. Potassium chloride (KCl), a substitute for sodium chloride (NaCl), has the disadvantage of imparting bitterness at high concentrations. We evaluated physical characteristics, taste perception and purchase intent of KCl and NaCl in oil‐in‐water spreads/emulsions composed by olive, rice bran and soya bean oils. Consumers (N = 300) evaluated saltiness/bitterness of emulsions prepared with 65% oil, and NaCl (0.5% and 1.0%) or KCl (0.75% and 1.5%). Olive oil spreads (104.07–107.43 Pa s) had higher viscosity compared to other spreads (59.16–74.96 Pa s). Type of oil had significant effects on bitterness, overall taste liking and viscosity. Taste liking decreased due to bitterness of olive oil spreads (mean drop=1.72–2.43). Purchase intent was positively associated with saltiness and pH and increased with oil claims (increase = 1.3%–22.1%) compared to sodium claims (increase = 0.0%–12.9%). These findings are useful for understanding taste perception of emulsions.     

Effects of embedding direct reduction followed by magnetic separation on recovering titanium and iron of beach titanomagnetite concentrate

Embedding direct reduction followed by magnetic separation was conducted to fully recover iron and titanium separately from beach titanomagnetite(TTM).The influences of reduction conditions,such as molar ratio of C to Fe,reduction time,and reduction temperature,were studied.The results showed that the TTM concentrate was reduced to iron and iron-titanium oxides,depending on the reduction time,and the reduction sequence at 1 200°C was suggested as follows:Fe_(2.75)Ti_(0.25)O_4→Fe_2TiO_4→FeTiO_3→FeTi_2O_5.The reduction temperature played a considerable role in the reduction of TTM concentrates.Increasing temperature from 1 100 to 1 200°C was beneficial to recovering titanium and iron,whereas the results deteriorated as temperature increased further.The results of X-ray diffraction and scanning electron microscopy analyses showed that low temperature(≤1 100°C)was unfavorable for the gasification of reductant,resulting in insufficient reducing atmosphere in the reduction process.The molten phase was formed at high temperatures of 1 250-1 300°C,which accelerated the migration rate of metallic particles and suppressed the diffusion of reduction gas,resulting in poor reduction.The optimum conditions for reducing TTM concentrate are as follows:molar ratio of C to Fe of 1.68,reduction time of 150 min,and reduction temperature of 1 200°C.Under these conditions,direct reduction iron powder,assaying 90.28 mass%TFe and 1.73 mass% TiO_2 with iron recovery of 90.85%,and titanium concentrate,assaying 46.24mass% TiO_2 with TiO_2 recovery of 91.15%,were obtained.     

Approximative model reconstruction of cascade systems

This letter considers how to approximately reconstruct a cascade system from a given unstructured system estimate. Many system identification methods, including subspace methods, provide reliable but generally unstructured black-box models. The problem we consider is how to find cascade systems that are close to such black-box models. For this, we use model matching techniques and optimal weighted Hankel-norm approximation to obtain accurate low-order cascade systems. We show that it is possible to bound the reconstruction error in terms of an error tolerance parameter and weighted Hankel singular values. The suggested methods are illustrated on both a numerical example and a real double tank system with experimental data.     

Electrochemically reduced Pt oxide thin film as a highly active electrocatalyst for direct ethanol alkaline fuel cell

The Pt oxide thin film and Pt thin film were prepared by reactive sputtering and the electrocatalytic activity of the ethanol oxidation reaction was investigated in a KOH solution for developing the alkaline direct ethanol fuel cells. After electrochemical reduction by passing a cathodic electric charge, the Pt oxide thin film showed 29 times larger ethanol oxidation current than the Pt thin film. This superior activity was caused by an increase in the electrochemical active surface area and the existence of residual oxygen, which was confirmed by cyclic voltammetry and XPS measurement. Due to the contribution of the residual oxygen, the rate-determining step of the ethanol oxidation reaction might change, because the Tafel slope of the Pt oxide thin film during the ethanol oxidation reaction was changed by electrochemical reduction. Despite the total Pt amount in the Pt oxide thin film being smaller than that in the Pt thin film, the Pt oxide thin film showed excellent ethanol oxidation activity. Therefore, the Pt oxide treated by electrochemical reduction may be a promising anode catalyst for the direct ethanol fuel cells.     

Numerical investigation of thermal disassociation of ZnO for hydrogen production: Parametric study and reactor configuration

The present research is focused on the two‐step ZnO/Zn thermochemical water splitting cycle for hydrogen production. In the present paper, the numerical modeling of the first step, which involves endothermic reduction of zinc oxide (ZnO), is carried out in a cylindrical reactor using Computational Fluid Dynamics (CFD). The parametric study shows that the fractional conversion of ZnO increases with an increase in the flow rate of ZnO, while it decreases with an increase in the ZnO particle diameter and carrier gas mass flow rate. Six different reactor configurations are also assessed comprehensively. It is observed that a cylindrical reactor with a tangential inlet at the top plane and a tangential outlet at the bottom plane has higher robustness to the variation of various operating parameters with consistently high ZnO fractional conversion. Copyright © 2013 John Wiley & Sons, Ltd.     

Influence of different carbon nanostructures on the electrocatalytic activity and stability of Pt supported electrocatalysts

Commercially available graphitized carbon nanofibers and multi-walled carbon nanotubes, two carbon materials with very different structure, have been functionalized in a nitric–sulfuric acid mixture. Further on, the materials have been platinized by a microwave assisted polyol method. The relative degree of graphitization has been estimated by means of Raman spectroscopy and X-ray diffraction while the relative concentration of oxygen containing groups has been estimated by X-ray photoelectron spectroscopy, which resulted in a graphitic character trend: Pt/GNF > Pt/F-GNF ? Pt/MWCNT > Pt/F-MWCNT. Transmission electron microscopy showed that the Pt particle size is around 3 nm for all samples, which was similar to the crystallite size obtained by X-ray diffraction. The activity towards electrochemical reduction of oxygen has been quantified using the thin-film rotating disk electrode, which has shown that all the samples have a better activity than the commercially available electrocatalysts. The trend obtained for the graphitic character maintained for the electrochemical activity, while the reverse trend has been obtained for the accelerated ageing test. Long-term potential cycling has demonstrated that the functionalization improves the stability for multi-walled carbon nanotubes, at the cost of decreased activity.     

Oxygen-dependent enhancement of hydrogen production by engineering bacterial hemoglobin in Escherichia coli

H₂ production under aerobic conditions has been proposed as an alternative method to overcome the fundamentally low yield of H₂ production by fermentative bacteria by maximizing the number of electrons that are available for H₂. Here, we engineered Vitreoscilla hemoglobin (VHb) in Escherichia coli to study the effects of this versatile oxygen (O₂)-binding protein on oxic H₂ production in a closed batch system that was supplemented with glucose. The H₂ yields that were obtained with the VHb-expressing E. coli were greatly enhanced in comparison to the negative control cells in culture that started with high O₂ tensions. The formate hydrogen lyase (FHL) activity of oxically cultured, VHb-expressing cells was also much higher than that of the negative control cells. Through inhibitor studies and time-course experiments, VHb was shown to contribute to the improved H₂ yield primarily by increasing the efficiency of cellular metabolism during the aerobic phase before the onset of H₂ production and not by working as an O₂-scavenger during H₂ production. This new approach allowed more substrate to remain to be further utilized for the production of more H₂ from limited resources. We expect that VHb can be successfully engineered in potential aerobic H₂-producing microbial systems to enhance the overall H₂ production yield. In addition, the remarkably high FHL activity of oxically grown, VHb-expressing cells may make this engineered strain an attractive whole-cell biocatalyst for converting formate to H₂.