TY - JOUR
T1 - Aqueous Structure of Lanthanide-EDTA Coordination Complexes Determined by a Combined DFT/EXAFS Approach
AU - Smerigan, Adam
AU - Biswas, Sayani
AU - Vila, Fernando D.
AU - Hong, Jiyun
AU - Perez-Aguilar, Jorge
AU - Hoffman, Adam S.
AU - Greenlee, Lauren
AU - Getman, Rachel B.
AU - Bare, Simon R.
N1 - Funding Information:
The authors thank the National Science Foundation for their support (awards 2133530 and 2133512). They also thank Lars Ostervold and Ruhi Sultana for their help collecting the EXAFS data. DFT simulations were performed on Clemson University’s Palmetto Supercomputing Cluster. Co-ACCESS is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The DMDW simulations used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under contract no. DE-AC02-05CH11231 using NERSC award ERCAP0023078.
Publisher Copyright:
© 2023 American Chemical Society
PY - 2023/9/11
Y1 - 2023/9/11
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.inorgchem.3c01334
DO - 10.1021/acs.inorgchem.3c01334
M3 - Article
C2 - 37624729
AN - SCOPUS:85169926427
SN - 0020-1669
VL - 62
SP - 14523
EP - 14532
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 36
ER -