Impact of Coordination Modes of N‐Donor Ligands on Am(III)/Eu(III) Separation in Nuclear Waste Water Treatment – A DFT Study. Issue 43 (16th November 2021)

• Record Type: Journal Article
• Authors: Ebenezer, Cheriyan; Solomon, Rajadurai Vijay
• Is Part Of: ChemistrySelect. Volume 6:Issue 43(2021)
• Page Start: 11876
• Page End: 11886
• Publication Date: 2021-11-16
• Subjects: Actinides -- BTP -- BTPhen -- Density functional calculations -- Pypz -- Separation factor; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202102543
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: Detection and degradation of environmental pollutants is always a challenging task, especially in nuclear waste management. The presence of radioactive minor actinides in the spent nuclear fuel from nuclear reactors leads to adverse effects on both humans and the environment. In this context, designing ligands plays a pivotal role in the partitioning process of actinides from lanthanides. Though we have many ligands with varying coordination modes reported, one needs to look deeper into the role and number of coordinating atoms of a ligand to gain a basic understanding of the extraction process. Hence, N‐donor ligands (Pypz, BTP, BTPhen and TPDCA) with a different number of coordinating atoms (two, three, four and five) and their Am/Eu complexes have been considered for this study. Exhaustive density functional theory calculations have been carried out to get an essence of the coordination chemistry of ML(NO3 )3 complexes and how the number of coordinating atoms impacts the selectivity towards Am 3+ over Eu 3+ ions. The calculated thermodynamic parameters shed light on the selectivity of these ligands towards Am(III) over Eu(III). Results reveal that the BTP ligand shows the best selectivity out of all the ligands. We found that the higher the number of coordination modes higher will be the binding energy. However, the selectivity depends on the strength and nature of M−L bonds. In brief, this study offers us insights into the tailoring of ligands with an optimum number of coordinating atoms for Am(III)/Eu(III) stripping in the spent nuclear waste processing. Abstract : The presence of radioactive elements leads to adverse effects on both humans and the environment. In this context, designing ligands plays a pivotal role in the partitioning process of lanthanides from actinides. Hence, ligands (Pypz, BTP, BTPhen, TPDCA) with different numbers of coordinating atoms (two, three, four and five) and their Am/Eu complexes have been considered and studied using relativistic density functional theory calculations.