Rapid separation of the low concentration Pd from Pd-Pt coexisting systems: Cyano-group’s monomer-specific affinity

Abstract

Rapid separation of low concentration palladium (Pd) from Pd-Platinum (Pt) coexisting systems remains a formidable challenge, primarily due to the undifferentiated substitution of ligands in Pd/Pt complexes by adsorption sites. The development of an adsorbent featuring monomer-specific affinity adsorption sites for Pd/Pt could mitigate this drawback. Herein, Manganese hexacyanoferrate (MnHCF) possessing the sensitivity and specificity to Pd ions (Pd(II)) was synthesized via the facile co-precipitation method. MnHCF could rapidly and selectively capture 90.30 % of Pd(II) from a 10 ppm Pd-Pt coexisting system within just 5 min. Spectroscopic analyses and density functional theory (DFT) calculations indicated that cyano-group (CN) in MnHCF exhibited the monomer-specific affinity for targeted capturing Pd via the direct and strong coordination interaction (Fe-CN-PdCl2), which was co-determined by the electron-losing of C (0.06 e) and N (0.07 e) atom. At the same time, CN could neither react directly with the fully coordinated [PtCl6]2− species nor substitute the Cl− ligand, both of which contributed to the non-adsorption of Pt, thus triggering the Pd-Pt separation. This study provides a promising candidate adsorbent for practical applications in platinum group metals recovery by the design of adsorption sites with monomer-specific affinity.