Abstract
Selective extraction of palladium from high-level liquid waste (HLLW) is desirable for the sustainable development of nuclear energy and resource recovery. In this work, three tridentate 2,6-bis-triazolyl-pyridine ligands (L-I, L-II, and L-III) bearing different alkyl side chains were synthesized and systematically studied for the complexation and extraction of palladium. Altering the alkyl side chains of the ligands led to pronounced differences in extraction performance. Among the three ligands, L-II decorated with two n-octyl groups exhibited the highest Pd(II) extraction efficiency at acidity levels of 1-5 M HNO3 and outstanding selectivity over 13 coexisting competing metal ions. Results from UV-vis titration experiments and theoretical calculations suggested that the differentiated extraction abilities of the ligands could be because of their different hydrophilicity rather than electron-donating effects. Slope analyses and electrospray ionization-high resolution mass spectrometry (ESI-HRMS) experiments revealed the formation of both L/Pd 1:1 and 2:1 species during the extraction process. These stoichiometries were further confirmed by job plots and NMR titration experiments. The ligands were found to aggregate slightly, especially at higher concentrations, which could result from multiple intermolecular hydrogen bonds as illustrated by X-ray crystallography. The configurations of PdL and PdL2 were further elucidated by analysis of single crystal structure and density-functional theory (DFT) calculations, respectively, where the first coordination sphere of Pd(II) was surrounded by four nitrogen or oxygen atoms in a quadrangular manner. This study provides an alternative method to separate palladium from HLLW and brings a new understanding of the coordination and complexation behaviors of Pd(II) with tridentate nitrogen ligands.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
