两种水溶性配体萃取分离钚离子的配位化学理论研究。

IF 3.3 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - An Asian Journal Pub Date : 2025-09-26 DOI:10.1002/asia.202500835

Pin-Wen Huang, Peng Ren, Ming Qi

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引用次数: 0

摘要

三价锕系元素（An3 +: Am, Cm, Bk, Cf）的纯化和相互分离在核废料处理中提出了重大挑战。阐明剥离配体的络合机制对配体的发育至关重要。考虑到放射毒性，量子化学方法是必不可少的。该DFT研究了An3 +离子与水溶性配体H2L2 、H2L2 的螯合作用。可能的反萃取配合物([AnLi（H2O）ⱼ]+,AnLi（NO3)(H2O)k）表现出几乎相同的几何形状，An─O/N键长度变化较小。分析表明，与N杂环供体（吡啶/吡嗪）相比，邻羧酸O的二胺N原子的螯合能力增强。关键是，An3 +与供体原子（NAM、OCA、NPY/PZ）之间的相互作用强度和部分共价以Cm为转折点呈现明显的双峰变化。这种趋势可能源于Am/Bk/Cf的5f轨道与配体2p轨道之间的轨道能量匹配比Cm更紧密。热力学分析表明H2L2的反萃取能力较强，而H2L2的ᶻ在Am/Eu分离方面表现优异。反应自由能的下降-上升趋势与共价变化一致，表明这四种离子具有潜在的基团内分离能力。估计分离因子SFAm/Cm、SFBk/Cm和SFCf/Cm在2.45-3.45之间。

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Theoretical Study on Coordination Chemistry of Two Water-Soluble Ligands for Stripping Separation of Transplutonium Ions.

Purification and mutual separation of trivalent actinides (An³⁺: Am, Cm, Bk, Cf) present significant challenges in nuclear waste treatment. Elucidating complexation mechanisms with stripping ligands is crucial for ligand development. Given the radiotoxicity, quantum chemical methods are essential. This DFT study investigates chelation of An³⁺ ions with water-soluble ligands H₂L²ᵖʸ and H₂L²ᵖᶻ. Probable back-extraction complexes ([AnLⁱ(H₂O)ⱼ]⁺, AnLⁱ(NO₃)(H₂O)^k) exhibit near-identical geometries with minor An─O/N bond length variations. Analyses reveal enhanced chelating ability for diamine N atoms adjacent to carboxylate O versus N-heterocyclic donors (pyridine/pyrazine). Crucially, interaction intensity and partial covalency between An³⁺ and donor atoms (N_AM, O_CA, N_PY/PZ) display a distinct bimodal variation with Cm as the turning point. This trend likely originates from closer orbital energy matching between the 5f orbitals of Am/Bk/Cf and ligand 2p orbitals compared to Cm. Thermodynamic analyses demonstrate superior back-extraction ability for H₂L²ᵖʸ, while H₂L²ᵖᶻ excels in Am/Eu separation. The downward-upward trend in reaction free energies aligns with covalency variations, suggesting potential intra-group separation capability for all four ions. Estimated separation factors SF_Am/Cm, SF_Bk/Cm, and SF_Cf/Cm are projected within 2.45-3.45.

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来源期刊

Chemistry - An Asian Journal 化学-化学综合

CiteScore

7.00

自引率

2.40%

发文量

535

审稿时长

1.3 months

期刊介绍： Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).