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Bilayer Crown Ether-Engineered Nanofiltration Membranes with Dual Li+ Transport Channels for Ultra-high Mg2+/Li+ Separation from Saline Lake Brines
Water Research ( IF 11.4 ) Pub Date : 2025-05-28 , DOI: 10.1016/j.watres.2025.123924
Ke Liu, Yingjie Xia, Xi Chen, Xiaoke Li, Kun Zhou, Ying Zeng, Guangyong Zeng, Xiaojie Cheng, Zhangyang Luo, Shouliang Yi
Water Research ( IF 11.4 ) Pub Date : 2025-05-28 , DOI: 10.1016/j.watres.2025.123924
Ke Liu, Yingjie Xia, Xi Chen, Xiaoke Li, Kun Zhou, Ying Zeng, Guangyong Zeng, Xiaojie Cheng, Zhangyang Luo, Shouliang Yi
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The escalating demand for lithium necessitates the development of advanced separation technologies to efficiently extract and recover lithium from saline lake brines determined by high Mg2+/Li+ ratios. Herein, we report a dual interfacial polymerization strategy incorporating benzo-15-crown-5 (B15C5) ether to fabricate nanofiltration membranes with hierarchically structured Li+ transport channels. Systematic optimization of the secondary interfacial polymerization (SIP) parameters synergistically combined with B15C5 functionalization endowed the membrane with exceptional Mg2+ rejection (> 99%) while maintaining stable water permeance (8.2 L·m⁻2·h⁻1·bar⁻1). The membrane achieved ultra-high Mg2+/Li+ separation factors (SLi, Mg) of 57.2, outperforming most of the previously reported membranes. Practical validation using actual saline lake brine (Qarhan Salt Lake, China; initial Mg2+/Li+ ratio is 928.6) demonstrated a two-stage separation efficiency that reduced the Mg2+/Li+ ratio to 1.9 with 488.7-fold lithium enrichment. Density functional theory (DFT) calculations and static diffusion tests further revealed that the B15C5-modified membrane exhibited a strong binding affinity for Li+ and significantly enhanced Li+ permeation ability. Additionally, X-ray photoelectron spectroscopy (XPS) depth etching and Time-of-flight secondary ion mass spectrometry (TOF-SIMS) resolved the spatially graded bilayer architecture of the membrane. These findings established a molecular-scale design paradigm for ion-selective membranes, addressing critical challenges in energy-efficient lithium extraction from high Mg2+/Li+ ratio brines.
更新日期：2025-05-28
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