煤电化学气化法制氢的动力学研究

研究了煤电化学气化法由水制氢的反应机理,实验验证了非电化学反应4Fe~(3 ) C 2H_2O→4Fe~(2 ) 4H~ CO_2是存在的。同时,通过实验得到了过程的动力学模型或     

Electrochemical noise analysis of cathodically polarised AISI 4140 steel. I. Characterisation of hydrogen evolution on vertical unstressed electrodes

For investigating stressed carbon-steel electrode (AISI 4140) cracking induced by hydrogen embrittlement with the electrochemical noise (EN) technique, the contribution of the evolving hydrogen bubbles to the EN has to be determined. Under cathodic current control, various reasons may explain the fluctuations of the electrode potential. In the first paper of this series the electrolyte resistance (ER) fluctuations, which yield ohmic-drop fluctuations, were analysed for unstressed vertical tensile specimens. A simplified model was proposed to tentatively derive the characteristic parameters of the gas evolution, such as the bubble mean size and evolution mean rate, from the power spectral density (PSD) of the ER fluctuations. However, results in only qualitative agreement with optical observations were obtained, indicating that the complicated screening and dragging effects of rising bubbles have to be taken into account in the modelling for vertical electrodes. The electrode potential fluctuations of unstressed tensile specimens were investigated in the second paper of this series and the influence of a stress was examined in the third paper.     

Electrochemical noise analysis of cathodically polarised AISI 4140 steel. II. Identification of potential fluctuation sources for unstressed electrodes

In this second part of the study of electrochemical noise (EN) generated by hydrogen evolution on a vertical cylindrical AISI 4140 steel electrode under galvanostatic control in 0.5 M sulphuric acid, the potential fluctuations induced by the growth and detachment of hydrogen bubbles at the electrode surface were analysed. They could be related to fluctuations of various quantities: electrode active surface due to bubble screening effects, concentration of dissolved hydrogen in the electrolyte close to the electrode surface, and metal-hydrogen interactions (MHI) on or beneath the electrode surface. The existence of MHI and their influence on faradaic potential fluctuations could be revealed by comparing the noise features on steel and platinum. The influence on EN of the charging cathodic current density, the presence of dissolved oxygen in the solution, and the electrode rotation speed was investigated in the absence of stress applied to the electrode. In the third paper of this series, the effect of hydrogen embrittlement on potential fluctuations of stressed electrodes will be examined.     

Structural and electrochemical properties of mixed calcium-zinc spinel ferrites nanoparticles

In the current work, we provide the electrochemical (EC) characteristics and considerable size of Ca-doped ZnFe₂O₄ nanoparticles. Mixed transition metal oxides are widely used as excellent electrode materials in superior supercapacitors because of their superior capacitance, low cost, and environmental friendliness. The prepared nanoparticles were characterized by X-ray diffraction (XRD), Field-emission scanning electron microscope (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), and EC methods. The results exhibited that the as-synthesized nanoparticles had a cubic spinel crystal structure and efficient EC properties. The EC properties of the prepared electrodes were explored by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS) studies. The Ca_0.1Zn_0.9Fe₂O₄ electrode demonstrated a specific capacitance (SC) ～208 Fg^-1 at a 2 mV/s scan rate due to significant morphological behavior. Therefore may be the prepared materials are the finest electrodes for supercapacitor applications.     

制氢技术发展概况

氢能是一种新型的洁净能源，是新能源研究中的热点，氢源则是氢能应用的关键，在介绍实验室制氢原理的基础上，系统地论述了目前国内外各种工业制氢方法，指出了制氢技术的研究热点和发展方向，并对适用于PEMFC备用电站的制氢技术进行了讨论。     

ELECTROCHEMICAL ANALYSIS USING ANGULAR POLARIZATION MODULATED ATIR SPECTROMETRY AND FLUOROMETRY

The absence of suitable in situ methods for obtaining electrical (charge-potential) and chemical information at electrode/electrolyte interfaces has represented a serious experimental incapacity in a broad range of fundamental and applied areas. This paper addresses the use of attenuated total internal reflection spectrometry and total internal fluorometry in conjunction with system modulation, both electrical cell control and spatially selective optical polarization, to probe this experimentally difficult region. Although applications of these techniques to electrolyte/solid electrode interfaces under equilibrium conditions will be described, emphasis will be given to interfacial characteization under current densities that significantly depart from equilibrium. The experimental configurations and difficulties in such measurements will also be addressed.     

ELECTROCHEMICAL ANALYSIS USING ANGULAR POLARIZATION MODULATED ATIR SPECTROMETRY AND FLUOROMETRY

The absence of suitable in situ methods for obtaining electrical (charge-potential) and chemical information at electrode/electrolyte interfaces has represented a serious experimental incapacity in a broad range of fundamental and applied areas. This paper addresses the use of attenuated total internal reflection spectrometry and total internal fluorometry in conjunction with system modulation, both electrical cell control and spatially selective optical polarization, to probe this experimentally difficult region. Although applications of these techniques to electrolyte/solid electrode interfaces under equilibrium conditions will be described, emphasis will be given to interfacial characteization under current densities that significantly depart from equilibrium. The experimental configurations and difficulties in such measurements will also be addressed.     

Electrodialysis with brine solutions oversaturated with calcium sulfate

Electrodialysis (ED) was applied to concentrate brine solutions of various concentrations — similar to effluentsfrom the desalination of brackish and industrial water — to about 20%. The consequent reduction in effluent volumes would facilitate a reduction in disposal costs. The energy requirement for concentrating solutions from 70 to 300 mN (0.4-1.8%) to 3.9 N (20%) was in the range 1.5-7.1 kWh/m³, in contrast to approximately 25 kWh/m³ by thermal evaporation. With the aim of preventing precipitation of CaSO4 on the membranes, laboratory-scale ED experiments were carried out on solutions of different compositions to determine the conditions that would lead to the precipitation of excess gypsum on gypsum seeds in a separate precipitator. The results were then applied in a pilot-scale ED unit in which the brine that circulated through the ED brine cells passed through a separate CaSO, precipitator containing gypsum seeds.     

Synthesis and characterisation of MnGaxCr2−xO4 (0.1≤x≤1) spinels as potential electrode support materials for intermediate-temperature solid oxide fuel cells

MnGa_xCr_2−xO₄ (MGCO, x=0.1, 0.2, 0.4, 0.8, 1) oxides are synthesised using a citric acid nitrate combustion method. The influence of Ga substitution on the structure, electrical conductivity and electrochemical performance are systematically investigated. The chemical and thermal compatibility of MGCO materials with yttrium-stabilised zirconia (YSZ) are also studied. All the samples exhibit a single phase spinel structure. Thermal expansion coefficients (TECs) of the MGCO oxides are in the range of 9–12×10⁻⁶ K⁻¹, indicating a good thermal match with the YSZ electrolyte. No chemical reactions are detected between MGCO materials and YSZ, indicating their good chemical compatibility with YSZ. The magnitude of electrical conductivity of all the obtained samples is in the order of about 10⁻³ S cm⁻¹at 800 °C measured in air. The polarisation resistance reaches a value as low as 5.2 Ω cm² for x=0.4 at 800 °C. The preliminary results demonstrate that MGCO materials could be used as electrode support materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs).     

Effect of electrolyte addition on activity of (Ga1−xZnx)(N1−xOx) photocatalyst for overall water splitting under visible light

Effects of electrolyte addition on photocatalytic activity of (Ga_1−xZn_x)(N_1−xO_x) modified with either Rh_2−yCr_yO₃ or RuO₂ nanoparticles as cocatalysts for overall water splitting under visible light (λ > 400 nm) are investigated. The cocatalyst Rh_2−yCr_yO₃ is confirmed to selectively promote the photoreduction of H⁺, while RuO₂ functions as both H₂ evolution sites and as efficient O₂ evolution sites. The activity of Rh_2−yCr_yO₃-loaded (Ga_1−xZn_x)(N_1−xO_x) is found to be suppressed in the presence of Cl⁻, which undergoes oxidation by photogenerated holes in the valence band of (Ga_1−xZn_x)(N_1−xO_x). Alkaline- and alkaline earth-metal cations in the reactant solution compensate the negative effect of Cl⁻ to a certain extent depending on the metal cation employed. Among the electrolytes examined, the addition of an appropriate amount of NaCl or A₂SO₄ (A = Li, Na, or K) to the reactant solution without pH control is found to increase activity by up to 75% compared to the case without additives. Direct splitting of seawater to produce H₂ and O₂ is also demonstrated using Rh_2−yCr_yO₃-loaded (Ga_1−xZn_x)(N_1−xO_x) catalyst under visible light.     

How good are the Electrodes we use in PEFC?

Basically, companies and laboratories implement production methods for their electrodes on the basis of experience, technical capabilities and commercial preferences. But how does one know whether they have ended up with the best possible electrode for the components used? What should be the (i) optimal thickness of the catalyst layer? (ii) relative amounts of electronically conducting component (catalyst, with support – if used), electrolyte and pores? (iii) “particle size distributions” in these mesophases? We may be pleased with our MEAs, but could we make them better? The details of excellently working MEA structures are typically not a subject of open discussion, also hardly anyone in the fuel cell business would like to admit that their electrodes could have been made much better. Therefore, we only rarely find (far from systematic) experimental reports on this most important issue. The message of this paper is to illustrate how strongly the MEA morphology could affect the performance and to pave the way for the development of the theory. Full analysis should address the performance at different current densities, which is possible and is partially shown in this paper, but vital trends can be demonstrated on the linear polarization resistance, the signature of electrode performance. The latter is expressed through the minimum number of key parameters characterizing the processes taking place in the MEA. Model expressions of the percolation theory can then be used to approximate the dependence on these parameters. The effects revealed are dramatic. Of course, the corresponding curves will not be reproduced literally in experiments, since these illustrations use crude expressions inspired by the theory of percolation on a regular lattice, whereas the actual mesoscopic architecture of MEA is much more complicated. However, they give us a flavour of reserves that might be released by smart MEA design.     

Hydrogen production by electrochemical decomposition of formic acid via solid polymer electrolyte

The aim of this work is to investigate the feasibility of simultaneous hydrogen production by electrochemical decomposition of formic acid via solid polymer electrolyte (SPE) in an electrochemical reactor. Titanium oxide coated with iridium oxide as anode and carbon fibre with Pt catalyst as cathode were used in the experiments.