Synergistic Sorption of Gallium(III) and Scandium(III) Ions by the Interpolymer System of Poly(Acrylic Acid)/Poly(4-vinylpyr-idine) Hydrogels: Kinetics, Selectivity, and Mechanism.

Selective recovery of critical metals such as gallium and scandium from dilute, multicomponent process streams remains challenging due to their low concentrations and complex matrices. Here we investigate a remotely interacting intergel system based on crosslinked poly(acrylic acid) (hPAA) and poly(4-vinylpyridine) (hP4VP) hydrogels across seven mass ratios (6:0-0:6) for sorption of Ga(III) and Sc(III) from binary sulfate solutions. Inductively coupled plasma optical emission spectroscopy shows that mutual activation of the weak polyacid/polybase pair markedly enhances metal uptake, with maximum sorption degrees of 73.17% for Ga(III) at hPAA:hP4VP = 3:3 and 56.00% for Sc(III) at 2:4, corresponding to distribution coefficients up to 2726.7 mL g-1 and Ga/Sc selectivity factors β up to 6.41. Sorption is well described by Langmuir-type isotherms, and desorption with 2 wt.% HNO3 reveals an inverse sorption-release relationship, indicating stronger binding at compositions of maximal mutual activation. FTIR spectroscopy evidences inner-sphere complexation through bidentate carboxylate coordination in hPAA and M←N dative bonding in hP4VP, while TGA/DSC shows that metal-loaded hydrogels retain their structural integrity up to approximately 320-340 °C, with the onset of significant decomposition occurring at ~350 °C for hP4VP-containing samples. The composition-dependent magnitude of Ga(III)-over-Sc(III) preferential uptake-with selectivity coefficients β = Kd(Ga)/Kd(Sc) remaining greater than 1 across all seven compositions studied-is rationalized using Hard-Soft Acid-Base considerations and demonstrates that hPAA:hP4VP intergels constitute a composition-tunable platform for enhancing Ga(III) recovery and partial Ga/Sc separation from simplified sulfate media, motivating future validation in real hydrometallurgical liquors and in the presence of competing multivalent cations.