The excessive thickness of the separation layer and the presence of cracks cause low water flux and poor lithium recovery in conventional forward osmosis (FO) membranes. According to the influence of the diffusion behavior of amine monomers in interfacial polymerization, the use of an interlayer optimizes the separation layer structure of traditional thin-film composite FO membrane. However, it is difficult to accurately control the separation layer structure by simply adjusting the amount of the interlayer material loaded. Herein, FO membranes with defect-containing metal–organic framework (MOF) interlayers were constructed. By adjusting the concentrations of competitive ligands, the MOFs showed different degrees of linker loss, which exposed the metal ions in the MOFs to different extents. The defective sites of the constructed MOFs increased the interaction between the interlayer and m-phenylenediamine (MPD), and density functional theory (DFT) simulations also revealed an increase in the binding energy of the two materials. Therefore, MPD attachment and diffusion were controlled by changing the proportion of defects in the MOFs, thereby finely regulating the separation layer structure. Additionally, tannic acid (TA) was predeposited to improve the stability of the interlayer. The prepared membrane exhibited water fluxes of 33.84 and 65.81 LMH and reverse salt fluxes of 0.58 and 2.38 gMH in the active layer facing feed solution (AL-FS) and active layer facing draw solution (AL-DS) modes, respectively. Excellent lithium ion recovery and fouling resistance was also demonstrated in battery wastewater treatment.
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