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Theoretical studies on the synergistic extraction of Am3+ and Eu3+ with CMPO–HDEHP and CMPO–HEH[EHP] systems†
Dalton Transactions ( IF 4 ) Pub Date : 2018-03-20 00:00:00 , DOI: 10.1039/c8dt00134k
Pin-Wen Huang 1, 2, 3 , Cong-Zhi Wang 3, 4, 5, 6, 7 , Qun-Yan Wu 3, 4, 5, 6, 7 , Jian-Hui Lan 3, 4, 5, 6, 7 , Gang Song 3, 8, 9, 10 , Zhi-Fang Chai 3, 4, 5, 6, 7 , Wei-Qun Shi 3, 4, 5, 6, 7
Affiliation  

In recent years, there has been a trend to use synergistic systems of neutral and acidic extractants into a single-solvent formulation to achieve Ln3+/An3+ extraction and separation via simplified processing schemes. In this study, geometrical structures, bonding nature, and thermodynamic stabilities of a series of possible extraction complexes of Am3+ and Eu3+ with two neutral-acid synergistic systems (CMPO–HDEHP and CMPO–HEH[EHP]) were theoretically studied using scalar-relativistic density functional theory (DFT). It is found that hydrogen bonds between neutral and acid ligands may greatly influence the Eu3+/Am3+ extraction and separation performance of the two synergistic systems. According to natural bond orbital (NBO) and energy decomposition analyses (EDA), the phosphoryl oxygen atoms of HDEHP or HEH[EHP] have higher affinity for Eu3+ and Am3+ than those of the CMPO ligand. Since weak but different extents of covalency exist in Eu- and Am-complexes, Eu3+/Am3+ separation via these two systems may be attributed to the different compositions of interactions between the metal ions and ligands. Thermodynamic analysis shows that the neutral complexes ML(NO3)2 (M = Eu and Am; L = [CMPO-DEHP] and [CMPO-EH[EHP]]) appear to be the most probable species in the complexation process.

中文翻译:

CMPO-HDEHP和CMPO-HEH [EHP]系统 协同萃取Am 3+和Eu 3+的理论研究

近年来,已经出现了将中性和酸性萃取剂的协同系统用于单一溶剂配方的趋势,以通过简化的处理方案实现Ln 3+ / An 3+的萃取和分离。在这项研究中,从理论上研究了一系列可能的Am 3+和Eu 3+与两个中性酸协同系统(CMPO-HDEHP和CMPO-HEH [EHP])的提取物的几何结构,键合性质和热力学稳定性。使用标量相对论密度泛函理论(DFT)。发现中性和酸性配体之间的氢键可能极大地影响Eu 3+ / Am 3+两种协同系统的提取和分离性能。根据自然键轨道(NBO)和能量分解分析(EDA),与CMPO配体相比,HDEHP或HEH [EHP]的磷酰氧原子对Eu 3+和Am 3+具有更高的亲和力。由于在Eu-和Am-络合物中存在较弱但不同程度的共价,因此通过这两个系统进行Eu 3+ / Am 3+的分离可能归因于金属离子与配体之间相互作用的不同组成。热力学分析表明,中性络合物ML(NO 32(M = Eu和Am; L = [CMPO-DEHP] -和[CMPO-EH [EHP]] -)似乎是络合过程中最可能出现的物种。
更新日期:2018-03-20
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