Thermoelectric hydrogen sensor using Li x Ni1-x O synthesized by molten salt method

Li-doped NiO was synthesized by molten salt method. LiN_O3-LiOH flux was used as a source for Li doping. NiCl₂ was added to the molten Li flux and then processed to make the Li-doped NiO material. Li:Ni ratios were maintained from 5: 1 to 30: 1 during the synthetic procedure and the chemical compositions after characterization were found from Li_0.08Ni_0.92O to Li_0.16Ni_0.84O. Li doping did not change the basic cubic structural characteristics of NiO as evidenced by XRD studies; however, the lattice parameter decreased from 0.41769 nm in pure NiO to 0.41271 nm in Li_0.16Ni_0.84O. Hydrogen gas sensors were fabricated by using these materials as thick films on alumina substrates. The half surface of each sensor was coated with the Pt catalyst. The sensor, when exposed to the hydrogen gas blended in air, heated up the catalytic surface leaving the rest half surface (without catalyst) cold. The thermoelectric voltage thus built up along the hot and cold surface of the Li-doped NiO made the basis for detecting hydrogen gas. The linearity of the voltage signal vs H₂ concentration was checked up to 4% of H₂ in air (as higher concentrations above 4.65% are explosive in air) using Li_0.10Ni_0.90O as the sensor material. The response time T₉₀ and the recovery time RT90 were less than 25 sec. H₂ concentration from 0.5% to 4% showed a good linearity against voltage. There was minimum interference of other gases and hence H₂ gas can easily be detected.     

An economic receding horizon optimization approach for energy management in the chlor-alkali process with hybrid renewable energy generation

This paper presents a methodology for the application of receding horizon optimization techniques to the problem of optimally managing the energy flows in the chlor-alkali process using a hybrid renewable energy system (HRES). The HRES consists of solar and wind energy generation units and fuel cells to supply energy. The HRES is also connected to the grid and allows for buying or selling electricity from and to the grid. Initially, detailed models of each system component are introduced as the basis for the simulation study. Energy management strategies are then developed to realize the objectives of meeting production requirements while minimizing the overall operating and environmental costs. Sensitivity and uncertainty analyses are carried out to elucidate the key parameters that influence the energy management strategies. Finally, production demand response is integrated into the proposed methodology.     

钛酸钾品须填充UHMWPE复合材料的摩擦磨损性能研究

用钛酸钾晶须(PTW)对超高摩尔质量聚乙烯(UHMWPE)进行填充改性,考察了复合材料的摩擦磨损性能,研究了其结晶情况,观察了磨损表面形貌并分析了其机理.结果表明随着PTW用量的增加,复合材料的硬度、结晶度以及维卡软化点都有所增大.PTW提高了复合材料的耐磨性,但摩擦系数有所上升.PTW的加入使得UHMWPE的磨损机理从黏着磨损和塑性变形改变成疲劳磨损和轻微的塑性变形,提高了其抗磨粒磨损的性能.     

Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm⁻¹. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.     

Exploring single electrode reactions in polymer electrolyte fuel cells

Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway.     

循环法生产K2SO4的工艺研究

开展了以ＫＣＩ、（ＮＨ＿４）＿２ＳＯ＿４为原料制备Ｋ＿２ＳＯ＿４的研究工作。确定了循环比、洗涤条件与反应时间。Ｋ＿２总转化率达７５％，产品收率约９７％；产品中Ｃｌ含量为０．５％～１．５％。     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.     

Understanding aluminum behaviour in aqueous alkaline solution using coupled techniques: Part I. Rotating ring-disk study

Rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) measurements have been undertaken to study the behaviour of pure aluminum electrodes in alkaline media. The measurements did consist of linear sweep voltammetry from anodic to cathodic potentials on 4N, 5N or 5N5-aluminum samples in 4 M aqueous potassium hydroxide solution. In the potential range studied (−0.7 V versus NHE to −2.5 V versus NHE) the aluminum undergoes oxidation/dissolution into aluminates anions at high electrode potential while it yields strong hydrogen evolution at low potentials. Thanks to the RRDE technique, we show that hydrogen starts to evolve from the aluminum electrode even above the open circuit potential. Also, the oxidation state of superficial aluminum varies according to the electrode potential: whereas non-conducting aluminum oxides are present above the open-circuit potential hindering hydrogen evolution reaction (HER), they tend to disappear below the ocp, due to the strong hydrogen evolution, following the probable porous oxide layer blow up induced by the hydrogen bubbles formation. In consequence at very low potential, HER occurs on bare aluminum, HER kinetics being much faster than on oxide-covered aluminum.     

Physical crosslinking effects in α,ω-dihydroxy terminated polybutadienes

Structure and molecular dynamics of α,ω-dihydroxy terminated polybutadienes of varying number averaged molecular weight (1320-10?500 g/mol) have been investigated by Fourier-transformed infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). DSC and DRS revealed an increase in the glass transition temperature upon decrease of the molecular weight, accompanied by an increasing dynamic fragility m (or steepness index) of the dielectric α-process. This correlation between T_g and m for different molecular weights indicates the presence of a physical network, where H-bonded end-group clusters act as temporary crosslinks. From the dielectric relaxation strength Δ?_α(M_n), the fraction of associated hydroxy groups (f_bond) was estimated showing a peak value for the two but shortest polymers, a behaviour that strongly resembles the molecular weight dependence of the fragility. By considering the quantity f_bond(M_n) in a modified Fox-Flory approach, the measured T_g(M_n) behaviour could be reproduced in a satisfying way. FTIR results support this general picture and show a considerable dependence of the extent of hydrogen bonding and formation of hydroxy groups associates on the molecular weight. Further, WAXS and DSC results disprove the idea of formation of pseudo-crystalline hydrophobic microdomains in these compounds as suggested by other authors.     

Mechanistic investigation of hydrogen-enhanced anodic dissolution of X-70 pipe steel and its implication on near-neutral pH SCC of pipelines

The effects of hydrogen-charging on anodic dissolution of pipe steel under near-neutral pH condition were studied by electrochemical techniques. Hydrogen-charging enhances the anodic dissolution rate of the steel. The hydrogen-enhanced dissolution increases with increasing charging current density. The hydrogen effect is attributed to the alteration of chemical potential and exchange current density of steel. Hydrogen-charging affects the corrosion process of the steel. In particular, at a high charging current density, a layer of corrosion product forms on the electrode surface to change corrosion potential and interfacial double-charge layer capacitance as well as charge-transfer resistance. The hydrogen effect factor for enhanced anodic dissolution of steel at an anodic potential of −0.4 V (SCE) is 1.53 only. Hydrogen-enhanced anodic dissolution of steel by itself may not be the major factor contributing to the high rate of crack growth in pipe steel in near-neutral pH electrolyte. A further investigation of the synergistic effect of hydrogen and stress on dissolution at the crack-tip is essential to determine the mechanism of near-neutral pH stress corrosion cracking of pipelines.