Anodic behaviour of oxidised Ni–Fe alloys in cryolite–alumina melts

Nickel-iron alloys have been identified as promising inert anode candidates for the Hall–Héroult process. In this study, binary Ni–Fe alloys of various compositions were subjected to short-term galvanostatic electrolysis in a cryolite–alumina bath at 960 °C. Prior to electrolysis, the anodes were oxidised at 800 °C for 48 h, forming a protective scale. Fe₂O₃, Ni_xFe_3−xO₄ and Ni_xFe_{1 − x}O were identified as the major scale components using a combination of X-ray diffraction (XRD) analysis and energy dispersive X-ray spectroscopy (EDX). Anodes having Ni content of 50–65 wt% performed adequately during short-term electrolysis, operating at a steady potential of 3–3.5 V vs. AlF₃/Al. Overall, it was found that the pre-formed oxide scale was effective in reducing anode wear and fluoridation. In the absence of a pre-formed scale, anodes were shown to undergo appreciable internal corrosion and/or passivation due to metal fluoride formation. Analysis of the anodes following electrolysis was performed using XRD and electron microprobe analysis (EPMA).     

Theoretical challenges in understanding the inhibition mechanism of aluminum corrosion in basic media in the presence of some p-phenol derivatives

Using quantum electrochemical/thermodynamical approaches based on coupled cluster/polarized continuum models and density functional theory (CM/PCM–DFT), we investigated the corrosion inhibition mechanism of Al/NaOH system in the presence of some p-phenol derivatives. The influencing parameters on inhibitory action, i.e. charges on oxygen and hydrogen atoms of hydroxyl group, charge transfer, interaction energy, molecular activity and softness, electric dipole moment and de-solvation free energy, were determined for both neutral and deprotonated species at metal|solution interface. A good correlation was observed between these parameters and inhibition efficiency data reported in the literature. By introducing an appropriate thermodynamic procedure, we also determined the proton-loss tendency of the molecules nearby interface. The results were amazing and revealed a complicated protonation/deprotonation cycle for inhibitor species inside electrical double layer; the corrosive agents in the vicinity of metal surface become locally neutralized and pushed away.     

氯化镁老卤微量SO4^2-的分析和深度分离工艺

察尔汗盐湖老卤是优质的电解镁原料,老卤中含有微量SO42-杂质。本文针对察尔汗盐湖卤水建立了卤水中微量SO42-的分析方法,并分析了分析方法的可靠性。电解镁过程对SO42-敏感,要求原料老卤中的SO42-含量必须≤30 mg/L,常规SO42-脱除手段已经不能进行老卤中的SO42-的深度分离。本文针对察尔汗盐湖老卤的特殊体系,开发了自然蒸发结晶与反应相结合的工艺进行SO42-的深度分离,使得SO42-的含量满足电解要求。     

The physical–chemical properties and electrocatalytic performance of iridium oxide in oxygen evolution

An IrO₂ anode catalyst was prepared by using the Adams method for the application of a solid polymer electrolyte (SPE) water electrolyzer. The effect of calcination temperature on the physical–chemical properties and the electrochemical performance of IrO₂ were examined to obtain a low loading and a high catalytic activity of oxygen evolution at the electrode. The physical–chemical properties were studied via thermogravimetry–differential scanning calorimetry (TG–DSC), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical activity was investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronopotentiometry in 0.1 mol L⁻¹ H₂SO₄ at room temperature. The optimum condition was found to be at the calcination temperature of 500 °C, where the total polarization reached a minimum at high current densities (>200 mA cm⁻²). The optimized catalyst was also applied to a membrane electrode assembly (MEA) and stationary current–potential relationships were investigated. With an optimized catalytic IrO₂ loading of 1.5 mg cm⁻² and a 40% Pt/C loading of 0.5 mg cm⁻², the terminal applied potential difference was 1.72 V at 2 A cm⁻² and 80 °C in a SPE water electrolysis cell.     

基于电极生物膜法对饮用水中硝酸盐的反硝化脱氮实验研究

电极生物膜法是近年来发展起来的一项新型水处理技术,具有处理费用低,去除率高,效果稳定,易于控制等优点,在处理低浓度硝酸盐氮污染的地下水和饮用水等方面具有良好的效果。主要研究了不同的碳氮比和电流强度对反硝化脱氮效果的影响,并对硝酸盐氮的测定方法进行了研究。     

Oxygen evolution anodes composed of anodically deposited Mn-Mo-Fe oxides for seawater electrolysis

Preparation of anodes for oxygen evolution in seawater electrolysis was carried out. Manganese-molybdenum double oxides, Mn_1−xMo_xO_2+x, prepared by anodic deposition from MnSO₄-Na₂MoO₄ solutions showed the 100% oxygen evolution efficiency at a current density of 1000 A m⁻² in 0.5 M NaCl at 30 °C and pH 12, but an increase in solution temperature resulted in dissolution of the oxides as molybdate and permanganate ions. In order to increase the stability of the electrodes at higher temperatures the addition of iron to the manganese-molybdenum oxides was performed by anodic deposition in MnSO₄-Na₂MoO₄-FeNH₄(SO₄)₂ solutions. The electrodes thus prepared showed the 100% oxygen evolution efficiency at 1000 A m⁻² in 0.5 M NaCl at 30-90 °C, when proper amounts of molybdenum and iron were contained. The iron addition also enhanced the oxygen evolution efficiency. The electrodes were not composed of oxide mixtures but triple oxides, Mn_1−x−yMo_xFe_yO_2+x−0.5y, consisting of Mn⁴⁺, Mo⁶⁺ and Fe³⁺. The formation of the triple oxides seemed responsible for enhancement of both oxygen evolution efficiency and stability.     

Hydrogen evolution on RuxTi1−xO2 in 0.5 M H2SO4

Hydrogen evolution from 0.5 M H₂SO₄ on Ti electrodes coated with a Ru_xTi_1−xO₂ (x=0.04-0.5) layer has been studied by potentiostatic polarisation, cyclic voltammetry and ac-impedance spectroscopy. The results indicate that after a certain activation period the performance of such an electrode coating is comparable to platinum. The addition of small amounts of sodium molybdate increased the capacitance of the electrode and a reduction of the performance was observed. Increasing the temperature of the pure electrolyte from 20 to 75 °C caused an increase in the rate of the hydrogen evolution and in addition an increase of the electrode capacitance. The electrodes have been found to be rather tolerant to chloride and Fe²⁺ ions, and could hence be promising candidates as catalyst materials for solid polymer water electrolysis systems. From steady state measurements the Tafel slopes were found to change from −105 mV/decade for pure titanium to about −40 mV/decade for the (RuTi)O₂ coated electrodes. The exchange current densities were calculated from the steady state curves, as well as from impedance data, to be about 10⁻⁴ A cm⁻² after activation.     

Non‐asbestos Diaphragms in Chlor‐Alkali Electrolysis

For decades in diaphragm electrolysis, asbestos containing diaphragms have been utilized to separate the anode and cathode compartments. Due to the harmful characteristics of asbestos, its world‐wide prohibition in diaphragm manufacturing is expected. The objective of this work was focussed on the development of a diaphragm with sufficient mechanical and chemical stability to substitute the modified asbestos diaphragm currently used. Suitable materials for the manufacture of non‐asbestos diaphragms were identified and a deposition technology was developed which fulfils the requirements of industrial production plants.     

电解法在环保领域中的应用

综合分析了近年来电解法在环保领域中的应用及研究进展情况.重点阐明电解法处理重金属废水、碱性废水、酸性废水、含氰废水、制药废水和有机废水,同时提出了电解法废水处理技术目前存在的问题及今后发展的方向.     

H2S低电耗电解制H2新方法

A new technique of lower electricity consumption electrolysis producing H2 has been developed, and the factors affecting producing H2 production were investigated. The results found that under the same electrolysis conditions, H2 production on the cathode increased with increasing electrolyte solution alkalinity; but decreased with increasing zinc ion concentration in the electrolyte solution. The results also revealed that H2 production on the cathode fluctuated with increasing electrolysis voltage, and reached a maximum when the voltage was at 0. 6 V. In a certainty range, it would be favorable to reduce the electricity consumption in H2 production with increasing electrolyte solution alkalinity; but the electricity consumption would be increase when electrolysis voltage was higher. Compared with producing H2 from H2O, the electrolysis voltage was lower by about IV, and the electricity consumption of H2 also decreased by 50% .