Prelithiation-derived hierarchical TiO2 sieve with metal-organic framework gate for selective lithium recovery.

• A novel hierarchical cubic Li x TiO 2 -based hollow Li-ion sieve was constructed. • A prelithiation concept at a mild temperature is proposed to engineer active Li+ sites. • ZIF-8 with unique 6-ring window is employed as Li+ channel for selective recovery. • The hollow TiO 2 -based core–shell hybrid yields high Li+ capture capacity against competing ions. Sustainable lithium supply significantly matters the healthy development of electric vehicles markets. Selective adsorption plays an important role in aqueous lithium recovery due to low energy consumption and easy processing. We here report a prelithiation concept to generate active Li+ sites in TiO 2 forming Li x TiO 2 at a mild temperature for lithium recovery. A hollow protonated Li x TiO 2 matrix with nanosheets surface was built to provide abundant active sites for specific Li+ capture with fast matter transfer. And a biomimetic metal–organic framework (ZIF-8) gate layer, acting as Li+ channel, was engineered to regulate cation solvation structure for selective transport of Li+. Consequently, the resultant TiO 2 -based hybrid lithium-ion sieve demonstrates fast and homogenous Li+ chemisorption with a high Li+ uptake capacity (∼14 mg g−1 for 24 h at pH = 12), high Li+ selectivity against competing cations in both simulated and natural brine, and acceptable reusability in simulated brine, indicating further application potential. [ABSTRACT FROM AUTHOR]