First-principles study of ground-state properties and high pressure behavior of ThO2

The mechanical properties, electronic structure and phonon dispersion of ground state ThO2 as well as the structure behavior up to 240 GPa are studied using first-principles density-functional theory. Our calculated elastic constants indicate that both the ground-state fluorite structure and high pressure cotunnite structure of ThO2 are mechanically stable. The bulk modulus, shear modulus, and Young's modulus of cotunnite ThO2 are all smaller by approximately 25% compared with those of fluorite ThO2. The Poisson's ratios of both structures are approximately equal to 0.3 and the hardness of fluorite ThO2 is 22.4 GPa. The electronic structure and bonding nature of fluorite ThO2 are fully analyzed, and show that the Th-O bond displays a mixed ionic/covalent character. The phase transition from the fluorite to cotunnite structure is calculated to occur at the pressure of 26.5 GPa, consistent with recent experimental measurement by ldiri et al. [1]. For the cotunnite phase it is further predicted that an isostructural transition takes place in the pressure region of 80-130 GPa.

杯芳烃羧酸萃取稀土、钍与含杯配合物结构研究

本文以大环化合物杯芳烃羧酸为萃取体系，系统考察稀土元素在该体系中的萃取分离性能，比较了钍与稀土元素的萃取性质差异，从而为杯芳烃羧酸在该分离领域中的应用提供一定的实验数据，此外，采用无机水热合成制备了含杯[8]芳烃的三元超分子配位聚合物并表征其结构，具体研究内容如下： 1、 合成杯芳烃并进行化学修饰得萃取剂杯芳烃羧酸，采用熔点测定、元素分析、TG-DTA、FT-IR和1H-NMR等分析方法表征，并利用两相滴定法测定了杯芳烃羧酸的基本常数。 2、 研究杯芳烃羧酸-CHCl3/RE-HCl萃取体系碱金属离子、离子强度、酸度、温度和萃取剂浓度对Eu(III)的萃取分配比影响，并分析其萃取机理。在此基础上，探索杯芳烃羧酸的协同萃取性能，发现杯[4]芳烃羧酸与伯胺N1923的ABC酸碱耦合协萃体系对轻、中、重稀土有不同的协萃能力，协萃系数与原子序数呈“双峰效应”。 3、 在萃取热力学基础上，利用层流恒界面池研究杯[4]芳烃羧酸萃取Nd(III)的动力学性质，确定了萃取反应控制模式随条件不同有所变化，化学反应在相界面上进行，并获得了萃取反应速率方程。 4、 以杯芳烃羧酸-CHCl3/Th-HCl体系研究钍的萃取性能，考察了碱金属离子、离子强度、酸度、温度和萃取剂浓度对Th(IV)的萃取影响，比较其与稀土萃取性能的差异，并在此基础上进一步研究与伯胺N1923协同萃取钍的性能，分析了协同萃取反应机制。 5、 水热合成并表征了含磺化杯[8]芳烃，2，2’-联吡啶与镍的三元超分子配合物。磺化杯[8]在该配合物中呈“双-反向锥式”构型，分子间由氢键和C-H…π相互作用将四核Ni簇连接成三维超分子结构。

包头稀土工业区土壤中钍的环境化学行为

本论文分为两部分：1. 综述部分（第一章和第二章），介绍了我国包头地区稀土工业区钍污染概况，对稀土工业生产造成的放射性生态环境污染进行了分析和归纳；评述了土壤和沉积物中放射性核素污染生态物理化学研究和进展；说明了本研究课题的背景、意义和技术路线。2. 实验部分（第三章至第六章），包括以下几方面内容：土壤样品和高铁矿渣样品中钍的分析方法的建立；对土壤和矿渣样品中钍的形态进行定量分析，考察了土壤性质对土壤中钍形态分布的影响；模拟自然环境，研究钍在土壤-植物系统之间的迁移积累和钍形态的植物可利用性；土壤样品对钍的吸附-解吸行为及其影响因素。 我国包头稀土工业在稀土矿浮选和稀土精矿湿法冶炼过程中产生了大量含放射性钍的废渣、废水和粉尘，对当地生态环境造成严重的破坏和放射性污染。 采用合适内标，ICP-MS法对样品中钍分析，考察了基体干扰、记忆效应和质谱干扰，比较了不同的样品消解方法对钍测定的影响，并用标准土壤样品和标准加入法对方法的准确性进行了评价。分别采用Tessier、BCR和Martínez-Aguirre形态萃取方法对土壤和样品中钍的形态进行分析，通过对总量的回收率和萃取剂选择性比较，选择了Martínez-Aguirre连续萃取法定量样品中钍的形态，并对其进行了优化和评价。考察了土壤性质影响着钍的形态分布。 通过盆栽实验，考察了小麦对根际土壤中钍形态分布以及的在不同生长期对钍的吸收影响。利用相应的材料人工模拟了土壤中钍的形态，对模拟的钍各形态的植物可利用性和植物吸收贡献指数进行评估分析。利用不同的磷酸盐对土壤进行培养处理，考察了磷酸盐的加入对土壤中钍的生物可利用性影响。 实验了土壤样品对钍的吸附-解吸过程，通过吸附容量、分配系数和吸附百分比等参数考察土壤对钍吸附能力，并考察了被土壤吸附钍的解吸行为。通过吸附机理的分析，土壤对钍的吸附作用主要是通过Th(IV)的表面水解吸附模式进行。根据实验结果，土壤样品对溶液中钍的吸附热力学可以用Freundlich方程式来描述，吸附的动力学过程可用Elovich方程描述，并对吸附方式和吸附过程进行论述。实验发现，吸附-解吸条件、土壤性质、外源稀土元素和施肥等对土壤吸附钍有一定影响。

beta-delayed fission of Ac-228

The basic process of an exotic decay mode namely P-delayed fission is simply introduced. The progress status of the study in the world is essentialized. The observation of P-delayed fission of Ac-228 is reported. The radium was radiochemically separated from natural thorium. Thin Ra sources in which Ac-228 was got through Ra-228 ->(beta-) Ac-228 were prepared for observing fission fragments from beta-delayed fission Ac-228. They exposed to the mica fission track detectors, and measured by an HPGe gamma-ray detector. The beta-delayed fission events of Ac-228 were observed and its beta-delayed fission probability was found to be (5 +/- 2) x 10(-12).

Production cross section of Th-236 in the interaction of U-238 with 60 MeV/u O-18 ions

The neutron-rich target-like isotope Th-236 has been produced in the U-238-2p multinucleon transfer reaction between a 60 MeV/u O-18 beam and natural U-238 targets. The activities of thorium were determined after radiochemical separation of Th from the mixture of uranium and reaction products. The Th-236 isotope was identified by the characteristic gamma-rays of 642.2, 687.6 and 229.6 keV. The production cross section of Th-236 was determined to be 250 +/- 50 mu b.

Production cross-section of Th-236 in the interaction of U-238 with 60MeV/u O-18 Ions

The neutron-rich target-like isotope Th-236 was produced in U-238-2p multinucleon transfer reaction between a 60MeV/u O-18 beam and nature U-238 targets. The thorium activities were radiochemically separated from the mixture of uranium and reaction products. The isotope Th-236 was identified by 642.2keV, 687.6keV and 229.6keV characteristic gamma-rays. The production cross section of Th-236 has been determined to be 250 +/- 50 mu b.

Search for beta-delayed fission of Ac-228

Radium was radiochemically separated from natural thorium. Thin Ra-228 ->beta Ac-228 sources were prepared and exposed to mica fission track detectors, and measured by an HPGe gamma-ray detector. The beta-delayed fission events of Ac-228 were observed and its beta-delayed fission probability was found to be (5 +/- 2)x10(-12).

Extraction and recovery of cerium(IV) along with fluorine(I) from bastnasite leaching liquor by DEHEHP in [C(8)mim]PF6

BACKGROUND: Ionic liquids (ILs) as environmentally benign solvents have been widely studied in the application of solvent extraction. However, few applications have been successfully industrialized because of the difficult stripping of metal ions or the loss of components of the ILs. More work needs to be done to investigate the extraction behaviour of IL-based extraction systems. In this work, the extraction behaviour of Ce(IV), Th(IV) and some trivalent rare earth (RE) nitrates by di(2-ethylhexyl) 2-ethylhexylphosphonate (DEHEHP) in the IL, 1-methyl-3-octylimidazolium hexafluorophosphate ([C(8)mim]PF6), was investigated and compared with that in the n-heptane system. In particular, the effect of F(I) on the extraction mechanism for Ce(IV) and its separation from Th(IV) was investigated. Otherwise, the recovery efficiency of Ce(IV) and F(I) from a practical bastnasite leach liquor was examined using IL based extraction.

Assembly of polyoxometalates on carbon nanotubes paste electrode and its catalytic behaviors

Carbon nanotubes paste (CNTP) electrode was prepared with multi-walled carbon nanotubes and methyl silicone oil. Polyoxometalates (POMs) were assembled on the electrode surface with different methods, and investigated by cyclic voltammetry and Raman spectroscopy. Experiments showed that POMs/CNTP electrode prepared by direct method had better performance. K6P2Mo18O62 center dot 14H(2)O (P2Mo18) assembled CNTP electrode (P2Mo18/CNTP) electrode possessed good reversibility and could catalyze the reduction of bromate and iodate in 0.1 M H2SO4 Solution. Further, the multilayer films of P2Mo18 assembled CNTP electrodes were fabricated by layer-by-layer technique, which showed higher electrocatalytic activities. All these POMs assembled CNTP electrodes prepared exhibited good stability.

Preparation of a phosphopolyoxomolybdate P2Mo18O626- doped polypyrrole modified electrode and its catalytic properties

A phosphopolyoxomolybdate (P2Mo18) doped polypyrrole (PPy) modified electrode was prepared in aqueous solution by a one-step method. During the polymerization of PPy, P2Mo18 acted as both catalyst and dopant. The electrochemical behavior of the PPy/P2Mo18 modified electrode before and after the overoxidation of PPy was investigated. Both of these showed a catalytic effect toward bromate. The PPy/P2Mo18 composite film was characterized by chronoamperometry, cyclic voltammetry, the rotating disk electrode technique, X-ray photoelectron spectroscopy and Raman spectroscopy.

Fabrication and electrochemical behavior of a sol-gel-derived carbon ceramic composite electrode entrapping 2 : 18-molybdodiphosphate

A new type of inorganic-organic hybrid material incorporating carbon powder and alpha -type 2:18-molybdodiphosphate (P2Mo18) in a methyltrimethoxysilane (MTMOS) based gel has been produced by a sol-gel process and used to fabricate a chemically modified electrode. The P2Mo18-doped carbon ceramic composite electrode was characterized using SEM and cyclic voltammetry. Square-wave voltammetry with an excellent sensitivity was exploited to conveniently investigate the dependence of current and half-wave potential (E-1/2) on pH. The chemically modified electrode has some advantages over the modified film electrodes constructed by the conventional methods, such as long-term stability, reproducibility, and especially repeatability of surface-renewal by simple polishing in the event of surface fouling or dopant leaching. In addition, the modified electrode shows a good catalytic activity for the electrochemical reduction of bromate in an acidic aqueous solution. (C) 2000 Elsevier Science B.V. All rights reserved.

Sol-gel-derived carbon ceramic composite electrodes bulk-modified with 1 : 12-silicomolybdic acid

1:12-Silicomolybdic acid (SiMo12) doped carbon ceramic composite electrodes were fabricated by incorporating SiMo12 and graphite powder in a methyltrimethoxysilane-based gel and characterized by cyclic and square-wave voltammetry, It was demonstrated that the chemically modified electrodes were suitable for electrocatalytic reduction of bromate, The electrodes had the remarkable advantage of surface renewal owing to bulk modification, as web as simple preparation, good mechanical and chemical stability and reproducibility.

Preparation, structures, and electrochemistry of a new polyoxometalate-based organic/inorganic film on carbon surfaces

The preparation, structure, and electrochemical and electrocatalytical properties of a new polyoxometalate-based organic/inorganic film, composed of cetyl pyridinum 11-molybdovanadoarsenate (CPMVA) molecules, have been studied. Cyclic potential scanning in acetone solution led to a stable CPMVA film formed on a highly oriented pyrolytic graphite (HOPG) surface. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used for characterizing the structure and properties of the CPMVA film. These studies indicated that self-aggregated clusters were formed on a freshly cleaved HOPG surface, while a self-organized monolayer was formed on the precathodized HOPG electrode. The CPMVA film exhibited reversible redox kinetics both in acidic aqueous and in acetone solution, which showed that it could be used as a catalyst even in organic phase. The CPMVA film remained stable even at pH > 7.0, and the pH dependence of the film was much smaller than that of its inorganic film (H4AsMo11VO40) in aqueous solution. The CPMVA film showed strong electrocatalysis on the reduction of bromate, and the catalytic currents were proportional to the square of the concentration of bromate. The new kind of polyoxometalate with good stability may have extensive promise in catalysis.

Sol-gel-derived graphite organosilicate composite electrodes bulk-modified with Keggin-type alpha-germanomolybdic acid

A novel inorganic-organic hybrid material incorporating graphite powder and Keggin-type alpha -germanomolybdic acid (GeMo12) in methyltrimethoxysilane-based gels has been produced by the sol-gel technique and used to fabricate a chemically bulk-modified electrode. GeMo12 acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The GeMo12-modified graphite organosilicate composite electrode was characterized by cyclic and square-wave voltammetry. The modified electrode shows a high electrocatalytic activity toward the reduction of bromate, nitrite and hydrogen peroxide in acidic aqueous solution. In addition, the chemically-modified electrode has some distinct advantages over the traditional polyoxometalate-modified electrodes, such as long-term stability and especially repeatability of surface-renewal by simple mechanical polishing.

Electrochemical behavior of molybdotungsate heteropoly complex with neodymium K10H3[Nd(SiMo7W4O39)(2)]xH(2)O in aqueous solution

The voltammetric behavior of the titled compound (denoted as Nd (SiMo7W4)(2)(13-)) in aqueous solution had been studied. An unusual pH response was discussed. The adsorption of the anion on the dropping mercury electrode and a self-inhibition influence of the adsorbed anions on the redox process of those anions dissolved in solution were found. The electrocatalytic effects of the anion on the bromate reduction were investigated.