The nature of unsupported uranium-ruthenium bonds: a combined experimental and theoretical study

Four new uranium-ruthenium complexes, [(Tren(TMS))URu(η(5)-C(5)H(5))(CO)(2)] (9), [(Tren(DMSB))URu(η(5)-C(5)H(5))(CO)(2)] (10), [(Ts(Tolyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (11), and [(Ts(Xylyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (12) [Tren(TMS)=N(CH(2)CH(2)NSiMe(3))(3); Tren(DMSB)=N(CH(2)CH(2)NSiMe(2)tBu)(3)]; Ts(Tolyl)=HC(SiMe(2)NC(6)H(4)-4-Me)(3); Ts(Xylyl)=HC(SiMe(2)NC(6)H(3)-3,5-Me(2))(3)], were prepared by a salt-elimination strategy. Structural, spectroscopic, and computational analyses of 9-12 shows: i) the formation of unsupported uranium-ruthenium bonds with no isocarbonyl linkages in the solid state; ii) ruthenium-carbonyl backbonding in the [Ru(η(5)-C(5)H(5))(CO)(2)](-) ions that is tempered by polarization of charge within the ruthenium fragments towards uranium; iii) closed-shell uranium-ruthenium interactions that can be classified as predominantly ionic with little covalent character. Comparison of the calculated U-Ru bond interaction energies (BIEs) of 9-12 with the BIE of [(η(5)-C(5)H(5))(3)URu(η(5)-C(5)H(5))(CO)(2)], for which an experimentally determined U-Ru bond disruption enthalpy (BDE) has been reported, suggests BDEs of approximately 150 kJ mol(-1) for 9-12.     

硫化纳米零价铁去除水溶液中铀的机理

研究了铀溶液初始pH、HCO－₃质量浓度和硫化纳米零价铁(sulfidized nano-scale zerovalent iron,SnZVI)投加量对SnZVI去除铀的动力学过程的影响,并通过SEM、XRD和XPS阐明SnZVI去除铀的机理。球形SnZVI颗粒直径为100~200 nm,比表面积为43.5 m²/g。SnZVI颗粒中含有Fe和FeS,且Fe(0)和Fe(Ⅱ)含量超过80%。SnZVI去除铀的动力学过程符合准一级动力学模型。增加SnZVI投加量,反应后溶液中铀质量浓度低于0.05 mg/L,但是pH升高及HCO－₃质量浓度增加导致SnZVI去除铀的速率降低。SnZVI去除铀的负荷达到2 452.92 mg/g,且反应后颗粒中约85%的铀为U(IV)和U(V)。研究结果表明,SnZVI可通过表面官能团的吸附作用及Fe(0)的还原作用快速分离水溶液中的铀。     

某铀矿细菌菌群柱浸过程中的硫强化作用及其机理分析

评估了由Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans和Leptospirillum ferriphilum组成的混合菌群在柱式反应器中浸出某复杂铀矿的硫强化作用及其可行性。在77 d细菌柱浸过程中,硫强化(8 g/kg)后,铀的浸出率达到了约83.61%,与对照组相比,增加了10%。利用扫描电镜和X射线荧光光谱仪对矿渣进行了表征,结果表明硫强化后的矿渣表面有细菌侵蚀的痕迹且孔隙度增大。细菌群落分析表明,硫强化后浸出液中的优势种群从Leptospirillum ferriphilum转变为Acidithiobacillus ferrooxidans,且Leptospirillum ferriphilum在下层矿石表面占比从强化前的4.3%增加到了40.74%,和Acidithiobacillus thiooxidans保持了较好的平衡。此外,动力学分析表明,铀矿细菌柱浸动力学模型更遵循了通过中间产物层控制的内部扩散模式,且硫强化能够增强铀的浸出动力学。最后,建立了一个与细菌群落和化学反应相关联的硫强化生物浸铀的机制模型。     

铀的结构相变及力学性能的第一性原理计算

基于密度泛函理论, 分别计算了α, γ铀的晶格常数、平衡态体积、体弹模量及其导数等, 与实验和其他第一性原理计算结果符合较好; 并根据焓-压强曲线得到了两相的相变压强～111GPa. 通过体心立方结构理想拉伸强度的计算, 分析其在极端加载条件下的结构行为. 另外, 计算了小应变情况下U-Nb (6.25at.%) 的能量-应变关系, 发现对应于剪切模量c’的应变会使得该结构的能量降低, 揭示了该结构的力学不稳定性. 关键词： 铀 相变 理想强度 结构稳定性     

氧化层结构对铀在CO/H_2气氛中表面反应的影响

用Ｘ射线光电子能谱（ＸＰＳ）分析研究了不同氧化层结构的铀金属试样在ＣＯ（２５℃）和Ｈ２（２００℃）气氛中的表面反应。ＣＯ和Ｈ２与铀金属表层反应后，氧化物中氧含量均减少，Ｏ／Ｕ比值随气体进气量的增加而减少。ＣＯ对铀金属表面的还原效果随铀表层氧化程度的提高而增强，并且强于Ｈ２。当表层氧化物较少、氧化程度较低时，铀试样在Ｈ２气氛中发生氢化反应。     

贫铀药型罩材料中微量杂质对聚能射流性能的影响

 通过对贫铀药型罩的静破甲实验，研究了材料中微量元素对射流性能的影响。实验结果表明，贫铀中的碳含量对射流性能起着非常重要的作用，随着碳含量的增加，静破甲威力下降十分显著。最后讨论了有害微量杂质对射流造成影响的原因，指出有害杂质可以以点缺陷形式或向晶界偏聚的形式存在于材料中，它们对材料的滑移变形均起到阻碍作用，其结果造成材料延展性能下降。     

Discovery of powerful uranyl ligands from efficient synthesis and screening

New tripodal gem-(bis-phosphonates) uranophiles were discovered by a screening method that allowed for the selection of ligands with strong uranyl-binding properties in a convenient microtiter-plate format. The method is based on competitive uranium binding by using Sulfochlorophenol S as chromogenic chelate. This dye compound was found to present high uranyl complexation properties and allowed to highlight ligands presenting association constants for UO(2+)(2) up to 10(18) at pH 7.4 and 10(20) at pH 9. A collection of 40 known ligands including polycarboxylate, hydroxamate, catecholate, hydroxypyridonate and hydroxyquinoline derivatives was tested. Also screened was a combinatorial library prepared from seven amine scaffolds and eight acrylates bearing diverse chelating moieties. Among these 96 tested candidates, a tripod derivative bearing gem-bis-phosphonates moieties was found to present the highest complexation properties over a wide range of pH and was further studied.     

236U AMS measurement at CIRCE

In order to measure the isotopic ratio of actinides,the upgrade of the accelerator mass spectrometry system at the Center for Isotopic Research on Cultural and Environmental heritage at the Second University of Naples,Italy,was performed.The beam emittance of 238U and the isotopic abundance sensitivity of 236U were measured on the present beam line.Utilizing a 16-strip silicon detector,the sensitivity of 236U/238U≈ 1×10-11 was obtained.     

原位定向γ能谱测量方法研究

在铀矿床上进行原位定向γ能谱测量时,复杂几何条件下的非定向γ射线会干扰测量结果。为减小上述影响,提出一种定向比例系数法,分别进行了模拟测量和实际测量比对,验证分析测量方法。首先,通过MCNP5程序模拟计算获得铅屏蔽层的定向比例系数和最佳厚度。然后,在NaI探测器的四周包裹铅对标准铀矿模型进行测量。最后,将测量结果与模拟值进行对比。结果表明：采用定向比例系数法进行铀矿原位定向γ能谱测量能有效能减少非定向γ射线对测量结果带来的干扰,可进一步提高铀矿原位γ能谱测量的精度。