Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid‐liquid extraction) for both primary sources and certain waste streams. In this work, 4‐phosphoryl pyrazolones are used in an efficient pH‐controlled stepwise separation of Li⁺ from Ca²⁺, Mg²⁺, Na⁺ and K⁺. The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co‐ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li⁺ at pH 6.0 was 94 % when Mg²⁺ and Ca²⁺ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.

The increasing concerns on uranium and rare earth metal ion pollution in the environment require sustainable strategies to remove them from wastewater. The present study reports an eco-friendly approach to convert a kind of protein-rich biomass, brewer's spent grain (BSG), into effective biosorbents for uranyl and rare earth metal ions. The employed method reduces the energy consumption by performing the hydrothermal treatment at a significantly lower temperature (150 °C) than conventional hydrothermal carbonization. In addition, with the aid of the Maillard reaction between carbohydrates and proteins forming melanoidins, further activation processes are not required. Treatment at 150 °C for 16 h results in an altered biosorbent (ABSG) with increased content of carboxyl groups (1.46 mmol g⁻¹) and a maximum adsorption capacity for La³⁺, Eu³⁺, Yb³⁺ (pH = 5.7) and UO₂ ²⁺ (pH = 4.7) of 38, 68, 46 and 221 mg g⁻¹, respectively. Various characterization methods such as FT-IR, ¹³C CP/MAS NMR, SEM-EDX and STA-GC-MS analysis were performed to characterize the obtained material and to disclose the adsorption mechanisms. Aside from oxygen-containing functional groups, nitrogen-containing functional groups also contribute to the adsorption. These results strongly indicate that mild hydrothermal treatment of BSG could be applied as a greener, low-cost method to produce effective adsorbents for uranyl and rare earth metal ion removal.

Effective receptors for the separation of Li⁺ from a mixture with other alkali metal ions under mild conditions remains an important challenge that could benefit from new approaches. In this study, it is demonstrated that the 4‐phosphoryl pyrazolones, HL²‐HL⁴, in the presence of the typical industrial organophosphorus co‐ligands tributylphosphine oxide (TBPO), tributylphosphate (TBP) and trioctylphosphine oxide (TOPO), are able to selectively recognise and extract lithium ions from aqueous solution. Structural investigations in solution as well as in the solid state reveal the existence of a series of multinuclear Li⁺ complexes that include dimers (TBPO, TBP) as well as rarely observed trimers (TOPO) and represent the first clear evidence for the synergistic role of the co‐ligands in the extraction process. Our findings are supported by detailed NMR, MS and extraction studies. Liquid‐liquid extraction in the presence of TOPO revealed an unprecedented high Li⁺ extraction efficiency (78 %) for HL⁴ compared to the use of the industrially employed acylpyrazolone HL¹ (15 %) and benzoyl‐1,1,1‐trifluoroacetone (52 %) extractants. In addition, a high selectivity for Li⁺ over Na⁺, K⁺ and Cs⁺ under mild conditions (pH ∼8.2) confirms that HL²‐HL⁴ represent a new class of ligands that are very effective extractants for use in lithium separation.