铀(VI)和磷酸三丁酯配合物在离子液体中的电化学行为研究

选择磷酸三丁酯（TBP）作为配体,考察铀酰—TBP配合物在1-丁基-3-甲基咪唑双三氟甲基磺酰亚胺盐（[Bmim][NTf2]）离子液体的萃取及电化学行为。发现铀（VI）经过两步单电子还原为铀（IV）,且铀（V）至铀（IV）的还原电位（-2.7 V Vs.Pt）超过此体系的电化学窗口,电沉积物为U3（PO3）4,继续热处理电沉积产物约573 K时转化为UP2O7。此研究表明离子液体可能在乏燃料金属的电化学分离中表现出乐观的前景。     

椎1600新型高效铀水冶固定床离子交换装置概述

椎1600新型高效铀水冶固定床离子交换装置主要用于从铀矿石的浸出液中分离提取含铀化合物。该装置主要结构---离子交换塔底部的出液结构的使用,在保证液体顺畅流过的前提下,减少了离子交换树脂的磨损,防止了树脂的泄露,确保了树脂在两个塔间的转移。经现场试验,该装置独特的工作方式有效解决了原固定床树脂板结、中毒等难题,提高了生产效率和经济效益。     

降雨入渗对尾矿坝稳定性的影响

通过对某尾矿坝进行ABAQUS二维建模,运用了修正Mohr-Coulomb破坏准则建立了在降雨入渗条件下坝体的非饱和土流固耦合有限元计算模型;通过采用合适的土-水特征曲线得到了非饱和边坡变形与应力的若干模拟结果并与实测结果进行对比分析。研究成果为继续研究尾矿坝在降雨入渗条件下的稳定性分析提供了基础。     

浅析尾矿库勘察中的钻探工艺

尾矿库勘察中钻探工艺的选取在一定程度上决定了勘察精度,也直接影响着施工成本,笔者根据多年来的现场钻探施工管理,剖析了在钻探施工过程中应着重注意的问题,总结出一套较为行之有效的施工工艺,以飨读者,供同类工程参考。     

Reactions of uranium atoms with ammonia: infrared spectra and quasi-relativistic calculations of the U:NH3, H2N--UH, and HN==UH2 complexes

Ammonia molecules interact with U atoms, and the resulting U:NH3 complex rearranges upon visible irradiation to form the H2N--UH and HN==UH2 molecules in excess argon. These products are identified by functional group frequencies, 15NH3 and ND3 isotopic shifts, and comparison to frequencies calculated by using density functional theory. The N==U pi bond in HN==UH2 is enhanced by partial triple-bond character through N(2p) to U(5f) conjugation, which is comparable to that found in the analogous HN==ThH2 molecule. These products also form complexes with additional ammonia molecules in the matrix. The interesting higher-energy N[triple chemical bond]UH3 complex is not formed.     

[U(bipy)4]: A Mistaken Case of U0?

After more than 50 years, the synthesis and electronic structure of the first and only reported “U⁰ complex” [U(bipy)₄] ( 1 ) has been reinvestigated. Additionally, its one‐electron reduced product [Na(THF)₆][U(bipy)₄] ( 2 ) has been newly discovered. High resolution crystallographic analyses combined with magnetic and computational data show that 1 and its derivative 2 are best described as highly reduced species containing mid‐to‐high‐valent uranium ligated by redox non‐innocent ligands.     

Facile CO Cleavage by a Multimetallic CsU2 Nitride Complex

Uranium nitrides are important materials with potential for application as fuels for nuclear power generation, and as highly active catalysts. Molecular nitride compounds could provide important insight into the nature of the uranium–nitride bond, but currently little is known about their reactivity. In this study, we found that a complex containing a nitride bridging two uranium centers and a cesium cation readily cleaved the C≡O bond (one of the strongest bonds in nature) under ambient conditions. The product formed has a [CsU₂(μ‐CN)(μ‐O)] core, thus indicating that the three cations cooperate to cleave CO. Moreover, the addition of MeOTf to the nitride complex led to an exceptional valence disproportionation of the CsU^IV–N–U^IV core to yield CsU^III(OTf) and [MeN=U^V] fragments. The important role of multimetallic cooperativity in both reactions is illustrated by the computed reaction mechanisms.     

The water-exchange mechanism of the [UO(2)(OH(2))(5)](2+) ion revisited: the importance of a proper treatment of electron correlation

The water-exchange mechanism of [UO(2)(OH(2))(5)](2+) has been reinvestigated by using ab initio molecular orbital (MO) methods. The geometries and the vibrational frequencies were computed with CAS-SCF(12/11)-SCRF and CAS-SCF(12/11)-PCM methods, which take into account static electron correlation (using the complete active space self-consistent field (CAS-SCF) technique, based on an active space of 12 electrons in 11 orbitals) and hydration (using the self-consistent reaction field (SCRF) and polarizable continuum model (PCM) techniques). The total energies were computed with multiconfiguration quasi-degenerate second-order perturbation theory, the MCQDPT2(12/11)-PCM method, which treats static and dynamic electron correlation as well as hydration. The adequacies of other currently used quantum chemical methods, MP2, CCSD(T), B3 LYP, and BLYP, are discussed. For the associative and dissociative pathways, thermodynamic activation parameters (DeltaH( not equal), DeltaS( not equal), and DeltaG( not equal)) were computed. For the associative mechanism, the calculated DeltaH( not equal) and DeltaG( not equal) values agree with experiment, whereas for the dissociative mechanism, they are higher by approximately 20 kJ mol(-1). The dissociative mechanism is preferred for substitution reactions of uranyl(VI) complexes with ligands that are stronger electron donors than water. The question of whether a concerted (I(a) or I(d)) or a stepwise (A or D) mechanism operates is discussed on the basis of the computed lifetime of the respective intermediate, and the duration of the vibration with which the intermediate is transformed into the product.