4.7 Article

Study on Phenanthroline Carboxamide for Lanthanide Separation: Influence of Amide Substituents

Journal

INORGANIC CHEMISTRY
Volume 60, Issue 17, Pages 13409-13418

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c01729

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The study on the effect of structure modification of phenanthroline carboxamides on lanthanide extraction reveals that tridentate monocarboxamides and tetradentate dicarboxamides show different trends in extraction, preferring light lanthanides. The amide substituents impact the distribution ratio, likely due to a modification in the internal polarity of the molecules. This effect could be extrapolated to other nitrogen-based ligands for further refinement of extraction processes.
Phenanthroline carboxamide compounds are promising for lanthanide intra-series separation. This paper presents a study on the effect of structure modification of phenanthroline carboxamides on the extraction of the whole lanthanide series. The study consists of theoretical calculations, extraction experiments of the 14 stable lanthanides, and extended X-ray absorption fine structure (EXAFS) analyses of Nd and Dy complexes. Tridentate monocarboxamides and tetradentate dicarboxamides show different trends in series extraction, although both preferentially extract the light lanthanides. The amide substituents, although not directly coordinating the metal ions, were also found to impact the distribution ratio, most probably due to a modification in the internal polarity of the molecules. This latter effect, if extrapolated to other nitrogen-based ligands such as pyridines or triazines, can be used to further fine-tune extractants for a process improvement.

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