Incorporating Two Crown Ether Struts into the Backbone of Robust Zirconium‐Based Metal–Organic Frameworks as Custom‐Designed Efficient Collectors for Radioactive Metal Ions

TL;DR

Scientists created new zirconium-based materials with crown ether structures that efficiently capture radioactive metal ions like strontium and cesium.

Contribution

The first stable zirconium-based MOFs with crown ether struts in their backbone, enabling efficient capture of radioactive ions.

Findings

ZJU-X100 and ZJU-X102 showed high porosity and stability under harsh conditions.

The MOFs exhibited fast sorption kinetics and high adsorption capacities for Sr2+ and Cs+.

The structures of Sr2+ and Cs+ adsorption were confirmed using crystallography.

Abstract

The incorporation of crown ether into metal‐organic frameworks (MOFs) is garnered significant attention because these macrocyclic units can fine‐tune the inherent properties of the frameworks. However, the synthesis of flexible crown ethers with precise structures as the fundamental building blocks of crystalline MOFs remains a challenging endeavor, with only a limited number of transition metal examples existing to date. Herein, 18‐crown‐6 and 24‐crown‐8 struts are successfully incorporated into the skeleton of zirconium‐based MOFs to obtain two new and stable crown ether‐based MOFs, denoted as ZJU‐X100 and ZJU‐X102. These newly developed MOFs displayed high porosity and remarkable stability when exposed to various solvents, boiling water, pH values, and even concentrated HCl conditions. Thanks to their highly ordered porous structure and high‐density embedding of specific binding sites within tubular channels, these two MOFs exhibited extremely fast sorption kinetics and demonstrated outstanding performance in the uptake of strontium and cesium ions, respectively. Furthermore, the structures of Sr‐adsorbed ZJU‐X100 and Cs‐adsorbed ZJU‐X102 are solved and confirmed the precise location of Sr2+/Cs+ in the cavity of 18‐crown‐6/24‐crown‐8. This makes modular mosaic of different crown ethers into the skeleton of stable zirconium‐based MOFs possible and promote such materials have broad applications in sorption, sensing, and catalysis.

Two new stable zirconium‐based metal–organic frameworks decorated with crown ether struts in the backbone are first fabricated. Due to the high‐density of embedding crown ether units and regular channels, ZJU‐X100 and ZJU‐X102 exhibited rapid adsorption kinetics and high adsorption capacities for Sr2+ and Cs+, respectively.

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