Aqueous Structure of Lanthanide-EDTA Coordination Complexes Determined by a Combined DFT/EXAFS Approach

Adam Smerigan, Sayani Biswas, Fernando D. Vila, Jiyun Hong, Jorge Perez-Aguilar, Adam S. Hoffman, Lauren Greenlee, Rachel B. Getman, Simon R. Bare

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4 Scopus citations


Sustainable production of rare earth elements (REEs) is critical for technologies needed for climate change mitigation, including wind turbines and electric vehicles. However, separation technologies currently used in REE production have large environmental footprints, necessitating more sustainable strategies. Aqueous, affinity-based separations are examples of such strategies. To make these technologies feasible, it is imperative to connect aqueous ligand structure to ligand selectivity for individual REEs. As a step toward this goal, we analyzed the extended X-ray absorption fine structure (EXAFS) of four lanthanides (La, Ce, Pr, and Nd) complexed by a common REE chelator, ethylenediaminetetraacetic acid (EDTA) to determine the aqueous-phase structure. Reference structures from density functional theory (DFT) were used to help fit the EXAFS spectra. We found that all four Ln-EDTA coordination complexes formed 9-coordinate structures with 6 coordinating atoms from EDTA (4 carboxyl oxygen atoms and 2 nitrogen atoms) and 3 oxygen atoms from water molecules. All EXAFS fits were of high quality (R-factor < 0.02) and showed decreasing average first-shell coordination distance across the series (2.62-2.57 Å from La-Nd), in agreement with DFT (2.65-2.56 Å from La-Nd). The insights determined herein will be useful in the development of ligands for sustainable rare earth elements (REE) separation technologies.

Original languageEnglish (US)
Pages (from-to)14523-14532
Number of pages10
JournalInorganic chemistry
Issue number36
StatePublished - Sep 11 2023

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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