New synthetic pathway towards BTrzPhen-tetraol: a hydrophilic 2,9-bis-triazolyl-1,10-phenanthroline ligand for selective americium stripping

Abstract

Selectively separating Am(iii) from nuclear waste streams is an extremely challenging task due to the presence of the trivalent lanthanides and Cm(iii). 1,10-Phenanthroline ligands decorated with 1,2,4-triazines or 1,2,3-triazoles have emerged as promising extractants for achieving such separation. In this article, a new robust synthetic pathway towards the hydrophilic, CHON compliant bistriazoylphenanthroline ligand BTrzPhen-tetraol is reported. BTrzPhen-tetraol was synthesised both as the hydrochloride and as a free base with overall yields of 66% and 48%, respectively. The ligand demonstrated excellent solubility and stability in dilute nitric acid solutions, with no observable decomposition after three days in 0.5 mol L−1 HNO3 at 50 °C. Additionally, it exhibited rapid stripping kinetics for Am(iii) and Eu(iii). Liquid-liquid extraction experiments conducted with BTrzPhen-tetraol, TODGA, and radiotracers of Am(iii), Cm(iii), and Eu(iii) yielded maximum Eu(iii)/Am(iii) and Cm(iii)/Am(iii) separation factors of 84 and 2.4, respectively, at 0.26 mol L−1 HNO3. Notably, the separation factors achieved with BTrzPhen-tetraol are comparable to those of existing systems. While only a minor influence of the BTrzPhen concentration on the distribution ratios of Am and Cm was observed under the given conditions, these results highlight the effectiveness of hydrophilic BTrzPhen ligands for selective americium stripping and encourage further optimisation to enhance performance.