离子液体中铈的电沉积行为

以一氯丁烷、N-甲基咪唑和KPF6为原料合成了1-丁基-3-甲基咪唑六氟磷酸盐离子液体([BMIM]PF6),用红外光谱(IR)法对合成的[BMIM]PF6进行了结构分析。用循环伏安法分别测试了[BMIM]PF6的电化学窗口和在[BMIM]PF6中加入乙二醇(EG)和CeCl3形成的体系([BMIM]PF6-EG-CeCl3)中Ce(III)的电化学行为。结果表明,在80℃时[BMIM]PF6的电化学窗口为4.0 V,[BMIM]PF6-EG-CeCl3体系中Ce(III)的电沉积是受扩散控制的不可逆电极过程,此过程传递系数α为0.05,扩散系数D0为2.45×10-6cm2·s-1。通过扫描电镜(SEM)观察了Ce在Cu片表面上电沉积层的形貌,发现随着沉积电势的增加,金属铈镀层的颗粒呈从小到大的变化规律。用X射线能量色散谱(EDS)分析了该电沉积层成分发现电沉积镀层为纯金属铈及其氧化物。     

Separation chemistry and clean technique of cerium（IV）： A review

The separation method of changeable valence RE element of cerium(Ce) was reviewed in this paper. Solvent extraction is the most effective and efficient method to separate Ce(IV) from RE(Ⅲ), usually accompanied with fluorine(F) and phosphor(P) from bastnaesite and monazite etc. By roast or wet-air oxidation, Ce(Ⅲ) of bastnaesite and monazite was oxidized into Ce(IV), and Cyanex923 and [A336][P507] have been investigated to co-extract and recover Ce(IV), F and P from H2SO4 leaching liquor, leading to favorable conditions for the subsequent separation of Th(IV) and RE(Ⅲ). The interaction of Ce(IV) and F and/or P enhances the roasting, leaching and extraction of Ce(IV) due to increasing of the stability of Ce(IV), and the formation of CeF3 and CePO4 after reductive stripping will benefit the utilization of F and P. For dealing with RE ores of high-content Ce, the clean process of oxidation roasting and Ce(IV)-F separation for Sichuan bastnaesite highlights the advantages of Ce(IV) based clean technique, which firstly demonstrates the comprehensive utilization of Ce(IV), Th(IV), F and RE(Ⅲ) and prevention of environmental pollution from fountainhead. A preliminary flowsheet of two-step oxidation and extraction of Ce(IV) for Bayan Obo mixed ores was further proposed to process the oxidation and extraction of Ce(IV) in presence of both F and P, indicating the possibility of similar effects with clean process of Sichuan bastnaesite. Ce(IV) separation chemistry and clean technique will open up new realms for light RE resources utilization, meeting "Emission Standards of Pollutants from Rare Earths Industry" promulgated by China's Ministry of Environment Protection(MOP) in 2011.     

Effect of Ni/（La＋Mg） Ratio on Structure and Electrochemical Performance of La-Mg-Ni Alloy System

As the alloy with the most suitable Ni/(La+ Mg) ratio has higher capacity and good cycle stability,theeffects of Ni/(La+Mg) ratios on the electrochemical performances of the La0.80 Mg0.20 Nix (x= 3.5 to 5.0) alloys have been investigated to find the most suitable Ni/(La+ Mg) ratio.The results of XRD and SEM observations show that the phase composition of the alloys varies with different Ni/(La+Mg) ratios.When Ni/(La+Mg) is notmore than 4.25,all the alloys contain LaNi5 and (La,Mg)2Ni7 phases,in addition,the LaMg and (La,Mg)Ni3 phases exist in the x=3.5 and 3.75 alloys,respectively.The LaMg2Ni9 phase exists in the x=4.25 alloy.There are the LaNi5 and LaMg2 Ni9 phases in the x= 4.5,4.75,and 5.0 alloys.The phase abundance and cell volume change with different Ni content.When the Ni/(La+Mg) ratio is not more than 4.25,the alloys possess excellent activation capability,however,the activation capabilities of the alloys decrease with a further increase in the Ni/(La+Mg)ratio.With increasing the Ni/(La+ Mg) ratio,the maximum discharge capacities,the medium voltages,and the cycle stabilities of the alloys first increase and then decrease.When the Ni/(La+Mg) ratio is 3.75,the corresponding alloyhas the maximum discharge capacity among all the alloys.However,the cycle stability of the Ni/(La+ Mg)= 4.0 alloy is better than that of the others.     

Effect of cerium content on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex（x=0-1.0） alloys

Effect of Ce addition on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex (x=0, 0.5at.%, 0.8at.% and 1.0at.%) alloys was studied by X-ray diffraction, scanning electron microscopy and P-C-isotherm measurements. The results indicated that Ce addition was a useful way to improve the flatness of the plateau and increase hydrogen storage capacity of Ti24Cr17.5V50Fe8.5 alloy. It was indicated that both homogenization of composition and increase of hydrogen diffusion coefficient were the main reasons for improving the hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex alloys.     

Extraction mechanism of cerium（Ⅳ） in H2SO4/H3PO4 system using bifunctional ionic liquid extractants

The extraction of Ce（Ⅳ） in H2SO4/H3PO4 system was investigated systematically using bifunctional ionic liquid extractants（Bif-ILES） [A336][P507],[A336][P204] and [A336][C272] in n-heptane.The effects of H2SO4 concentration,extractant concentration and salting-out agent concentration were observed in detail.The extraction mechanism of Ce（Ⅳ） in H2SO4/H3PO4 system was obtained.The comparison with other extractants such as Cyanex923,TBP was also studied.Thermodynamic functions of the extraction reaction were calculated,showing that the extraction was an exothermic process.The separation of Ce（Ⅳ） from RE（Ⅲ） and Th（Ⅳ） was also investigated.The result indicated that Ce（Ⅳ） could be selectively extracted in this system.CePO4 nanoparticles were obtained in the process of stripping using H2O2 in H2SO4/H3PO4 system.X-ray diffraction（XRD）,scanning electron microscopy（SEM） and spectroscopy were adopted for the characterization of the sample.     

Corrosion of Alloy Steel in 30% Ethylene Glycol Solution and CrO_4~（2-） Under Hydrodynamic Condition

 The electrochemical behavior of steel alloy in 30% ethylene glycol-water solution at different solution rotating speeds was investigated by polarization curves and AC impedance measurements. The results obtained showed that corrosion rate did not change significantly at different rotating speeds. The effect of chromate as the inhibitor was studied and high inhibition efficiency was obtained. It was found that surface passivation occurred in the presence of the inhibitor. The inhibiting effect of the chromate was explained on the basis of the competitive adsorption between the inorganic anions and the aggressive Cl- and the adsorption isotherm basically obeys the Langmuir adsorption isotherm. Thermodynamic parameters for inhibitor adsorption were determined and results reveal that the adsorption process is spontaneous.