Leveraging Hard–Soft Acid–Base Interactions for Effective Palladium Capture in Acidic Solutions
Anastasia D. Pournara, Jun-Hao Tang, Yang Lu, Jia-Ting Liu, Xiao‐Ying Huang, Mei‐Ling Feng, Mercouri G. Kanatzidis
Abstract
Demand for palladium is increasing as it is a precious metal with great industrial applications. In order to meet the potential challenges posed by limited terrestrial Pd resources, it is necessary to develop low-cost and efficient Pd enrichment materials and methods. Palladium is found in significant quantities in spent fuel as a fission product, making it highly valuable for recycling. However, the selective capture of Pd 2+ ions from highly acidic radioactive liquid wastes, with complex compositions generated from spent fuel reprocessing, remains a challenge. Leveraging the intrinsic bonding selectivities associated with hard–soft acid–base (HSAB) theory we present, the rapid and highly selective capture of Pd 2+ ions from strongly acidic solutions has been achieved by the layered potassium thiostannate K 2 x Sn 4– x S 8– x ( KTS-3 ). The maximum sorption capacity was calculated to be 397 and 162 mg of Pd 2+ /g of KTS-3 in 1 and 3 M HNO 3 solutions, respectively. In 1 M HNO 3 solutions with initial Pd 2+ concentrations of 1.02 and 260 mg/L, the sorption of Pd 2+ by KTS-3 reaches equilibrium within 2 and 30 min, respectively, with removal rates of more than 99.9%. KTS-3 can effectively and selectively remove Pd 2+ from mixtures containing Ag + or Pt 2+, although they also represent soft Lewis acids and pose strong competition with Pd 2+ for binding to the soft base S 2– sites of the framework. Moreover, KTS-3 can effectively separate Pd 2+ /M n + (M n + = Na +, Cs +, Sr 2+, Eu 3+, Zr 4+, Ni 2+, and Co 2+ ) in acidic solutions and shows excellent selective capture of Pd 2+ even in simulated high-level liquid wastes. The outstanding Pd 2+ sorption by KTS-3, showcasing a record-breaking capacity and selectivity, is attributed to the synergistic effect of the easily exchangeable K + cations and the strong HSAB affinity of the S 2– active sites for Pd 2+ ions. This is achieved under extremely acidic conditions, which coupled with its structural integrity and effectiveness even post γ-irradiation, positions it as a promising material for palladium capture and recovery, especially in the treatment of radioactive waste.