Covalency between the uranyl ion and dithiophosphinate by sulfur K-edge X-ray absorption spectroscopy and density functional theory

The dithiophosphinic acids (HS2PR 2) have been used for the selective separation of trivalent actinides (AnIII) from lanthanides (LnIII) over the past decades. The substituents on the dithiophosphinic acids dramatically impact the separation performance, but the mechanism is still open for debate. In this work, two dithiophosphinic acids with significantly different AnIII/LnIII separation performance, i.e. diphenyl dithiophosphinic acid (HS2PPh2) and bis(ortho-trifluoromethylphenyl) dithiophosphinic acid [HS2P(o-CF3C6H4)2], are employed to understand the substituent effect on the bonding covalency between the S2PR 2 − anions (R = Ph and o-CF3C6H4) and the uranyl ion by sulfur K-edge X-ray absorption spectroscopy (XAS) in combination with density functional theory calculations. The two UO2(S2PR 2)(EtOH) complexes display similar XAS spectra, in which the first pre-edge feature with an intensity of 0.16 is entirely attributed to the transitions from S 1s orbitals to the unoccupied molecular orbitals due to the mixing between U 5f and S 3p orbitals. The Mulliken population analysis indicates that the amount of \% S 3p character in these orbitals is essentially identical for the UO2(S2PPh2)2(EtOH) and UO2[S2P(o-CF3C6H4)2]2(EtOH) complexes, which is lower than that in the U 6d-based orbitals. The essentially identical covalency in U—S bonds for the two UO2(S2PR 2)2(EtOH) complexes are contradictory to the significantly different AnIII/LnIII separation performance of the two dithiophosphinic acids, thus the covalency seems to be unable to account for substituent effects in the AnIII/LnIII separation by the dithiophosphinic acids. The results in this work provide valuable insight into the understanding of the mechanism in the AnIII/LnIII separation by the dithiophosphinic acids.

Germanium Extraction from Sulfuric Acid Solutions in the Presence of Thiocyanate Ion

The extraction of Ge (IV) from sulfuric acid solutions in the presence of thiocyanate ion with various extractants (caprylic, poly(2-ethylhexyl)phosphonitrile, bis(2,4,4-trimethylpentyl) dithiophosphinic acids, trialkylmethylammonium thiocyanate, etc.) has been studied. In all cases, the thiocyanate ion increases germanium extraction as compared to the extraction from sulfuric acid solutions. During the germanium extraction with bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301, HR), a significant increase in the germanium extraction is due to the formation of a cationic intracomplex compound of the composition [Ge(OH)3-nRn]+[HSO4], where n = 1-3. Due to the large synergistic effect for the extraction of Ge, it is possible to use an extractant with a concentration of 0.1-0.15 mol/l. Trialkylmethylammonium thiocyanate (TAMAR), also shows a high efficiency of germanium extraction from sulfate thiocyanate solutions. For 5-6 stages of extraction with a 0.5 M solution of ТАМАР, the extraction of Ge was 99.5 %. The composition of the extracted complex supposedly corresponds to (R4N)2[Ge(CNS)6]. The use of extraction systems based on Cyanex 301 and ТАМАR in the presence of thiocyanate ion significantly reduces the concentration of extractants and is of undoubted practical interest for hydrometallurgical processes for the germanium extraction

From “S” to “O”: experimental and theoretical insights into the atmospheric degradation mechanism of dithiophosphinic acids

The oxidation behavior and mechanism of five typical DPAH ligands in the air was systematically studied through experimental and theoretical methods.