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Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides
ACS Central Science ( IF 12.7 ) Pub Date : 2018-06-14 00:00:00 , DOI: 10.1021/acscentsci.8b00223 Anna G. Baldwin 1 , Alexander S. Ivanov 2 , Neil J. Williams 2 , Ross J. Ellis 2 , Bruce A. Moyer 2 , Vyacheslav S. Bryantsev 2 , Jenifer C. Shafer 1
ACS Central Science ( IF 12.7 ) Pub Date : 2018-06-14 00:00:00 , DOI: 10.1021/acscentsci.8b00223 Anna G. Baldwin 1 , Alexander S. Ivanov 2 , Neil J. Williams 2 , Ross J. Ellis 2 , Bruce A. Moyer 2 , Vyacheslav S. Bryantsev 2 , Jenifer C. Shafer 1
Affiliation
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Fundamental understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance for advancing sustainable energy systems. Current investigations in this area are mostly focused on the study of inner-sphere interactions between metal ions and donor groups of ligands, while the effects on the selectivity resulting from molecular interactions in the outer-sphere region have been largely overlooked. Herein, we explore the fundamental origins of the selectivity of the solvating extractant N,N,N′,N′-tetraoctyl diglycolamide (TODGA) for adjacent lanthanides in a liquid–liquid extraction system, which is of relevance to nuclear fuel reprocessing and rare-earth refining technologies. Complementary investigations integrating distribution studies, quantum mechanical calculations, and classical molecular dynamics simulations establish a relationship between coextracted water and lanthanide extraction by TODGA across the series, pointing to the importance of the hydrogen-bonding interactions between outer-sphere nitrate ions and water clusters in a nonpolar environment. Our findings have significant implications for the design of novel efficient separation systems and processes, emphasizing the importance of tuning both inner- and outer-sphere interactions to obtain total control over selectivity in the biphasic extraction of lanthanides.
中文翻译：
外层水团簇可调节二甘醇酰胺的镧系元素选择性
对通过螯合剂选择性识别和分离f嵌段金属离子的基本了解对于推进可持续能源系统至关重要。目前在该领域的研究主要集中在金属离子与配体的供体基团之间的内球相互作用的研究上，而在外球区域中分子相互作用对选择性的影响却被大大地忽略了。在这里，我们探讨了溶剂化萃取剂N，N，N '，N的选择性的基本来源。液-液萃取系统中相邻镧系元素的'-四辛基二甘醇酰胺（TODGA），与核燃料后处理和稀土精制技术有关。结合分布研究，量子力学计算和经典分子动力学模拟的补充研究建立了TODGA共萃取水与镧系元素之间的关系，指出了外层硝酸根离子与水团簇之间氢键相互作用的重要性。非极性环境。我们的发现对新型高效分离系统和方法的设计具有重要意义，强调了调整内-外层相互作用以全面控制镧系元素双相萃取选择性的重要性。
更新日期：2018-06-14
中文翻译：
外层水团簇可调节二甘醇酰胺的镧系元素选择性
对通过螯合剂选择性识别和分离f嵌段金属离子的基本了解对于推进可持续能源系统至关重要。目前在该领域的研究主要集中在金属离子与配体的供体基团之间的内球相互作用的研究上，而在外球区域中分子相互作用对选择性的影响却被大大地忽略了。在这里，我们探讨了溶剂化萃取剂N，N，N '，N的选择性的基本来源。液-液萃取系统中相邻镧系元素的'-四辛基二甘醇酰胺（TODGA），与核燃料后处理和稀土精制技术有关。结合分布研究，量子力学计算和经典分子动力学模拟的补充研究建立了TODGA共萃取水与镧系元素之间的关系，指出了外层硝酸根离子与水团簇之间氢键相互作用的重要性。非极性环境。我们的发现对新型高效分离系统和方法的设计具有重要意义，强调了调整内-外层相互作用以全面控制镧系元素双相萃取选择性的重要性。
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