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<p>Featuring excellent chemical stability and tunable pore aperture, zirconium-based metal-organic framework (Zr-MOF) represented by UiO-66 is promising for liquid molecular separation. Nevertheless, it is challenging to achieve high ion separation performance in UiO-66 membrane owing to the non-ideal pore environment. Here, we present a ligand engineering strategy to synergistically regulate pore size and functionality in Zr-MOF membrane for mono-/di-valent ions separation. This is achieved by positioning the amino group (-NH<sub>2</sub>) in the ligand of the UiO-66 framework. The influences of amino groups on the lattice defects and pore functionality, as well as the ion separation performance of MOF membranes, were investigated systematically. Benefiting the properly narrowed pore size and enhanced repulsive force towards divalent ions, the optimized Zr-MOF membrane displayed excellent mono-/di-valent ions separation performance with monovalent ions permeation rate of 0.36–0.55 mol m<sup>−2</sup> h<sup>−1</sup> and mono-/di-valent ions selectivities of 64–98, far beyond the separation performance of state-of-the-arts membranes. This work provides a facile approach to precisely construct a nanosized space in crystalline membranes for molecular separation, energy conversion, and storage.</p>

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Synergistically regulating pore size and functionality in Zr-MOF membrane for precise ion sieving

  • 期刊论文

  • 发表日期：

    2025年7月30日

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  • Zhixu Chen,
  • Binyu Mo,
  • Xufan Zhou,
  • Lianhao Li,
  • Wenqi Ji,
  • Guozhen Liu,
  • Gongping Liu,
  • Wanqin Jin

摘要

Featuring excellent chemical stability and tunable pore aperture, zirconium-based metal-organic framework (Zr-MOF) represented by UiO-66 is promising for liquid molecular separation. Nevertheless, it is challenging to achieve high ion separation performance in UiO-66 membrane owing to the non-ideal pore environment. Here, we present a ligand engineering strategy to synergistically regulate pore size and functionality in Zr-MOF membrane for mono-/di-valent ions separation. This is achieved by positioning the amino group (-NH2) in the ligand of the UiO-66 framework. The influences of amino groups on the lattice defects and pore functionality, as well as the ion separation performance of MOF membranes, were investigated systematically. Benefiting the properly narrowed pore size and enhanced repulsive force towards divalent ions, the optimized Zr-MOF membrane displayed excellent mono-/di-valent ions separation performance with monovalent ions permeation rate of 0.36–0.55 mol m−2 h−1 and mono-/di-valent ions selectivities of 64–98, far beyond the separation performance of state-of-the-arts membranes. This work provides a facile approach to precisely construct a nanosized space in crystalline membranes for molecular separation, energy conversion, and storage.