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由于结构和功能方面的诸多特点，金属有机框架(MOFs)材料的制备和应用研究引起了广泛关注。然而，特殊的化学结构导致很多MOFs的化学稳定性较差，在特定条件下易发生化学刻蚀而引起其三维孔道结构、化学构成以及形貌发生变化。基于这一特性，可控化学刻蚀被用来调控MOFs的化学组成和孔道结构，从而赋予原有MOFs所不具备的诸多特殊功能并拓展其应用范围。因此，MOFs的可控化学刻蚀及其应用成为近年来的研究热点。文章简要总结了目前已报道的MOFs化学刻蚀方法、刻蚀产物的形貌与化学组成及其应用等方面的研究成果。在可控化学刻蚀方法方面，主要介绍基于配体取代和配体切割的刻蚀方法；在刻蚀产物形貌与化学组成方面，重点关注具有表面或内部缺陷的MOFs、含有介孔或大孔的MOFs、中空或Yolk-shell结构的纳米粒子以及无定形无机材料或层状金属双氢氧化物(LDH)等结构。最后，文章简单介绍了MOFs可控化学刻蚀产物在催化、电化学、吸附分离、生物医药等领域的应用。
Abstract：Metal-organic frameworks(MOFs) have garnered significant attention in recent decades due to their versatile properties stemming from well-defined three-dimensional porous structures and diverse chemical functionalities. The unique chemical nature of these materials, based on coordination bonding, often renders them susceptible to chemical etching, which can alter their porous architecture, chemical composition, and original morphology. However, judiciously controlled chemical etching offers a powerful approach to fine-tune the hierarchical structure and chemical properties of MOFs, thereby imparting novel functionalities to the resulting materials. Consequently, the controlled chemical etching of MOFs and the exploration of applications for the derived products have become a focal point of research. This review provides a concise overview of three key aspects: strategies for achieving controlled etching, the resulting chemical structures and morphologies of the etched MOFs, and representative applications of these derived materials across several fields. Ligand replacement and scissoring will be highlighted as prominent methods for achieving well-controlled chemical etching. In discussing the chemical structures and morphologies of etched MOFs, we will focus on materials exhibiting meso-or macropores, hollow or yolk-shell structures, and those transformed into amorphous phases or layered double hydroxides(LDHs). Finally, the review will showcase applications of the etched materials in catalysis, electrochemistry, adsorption and separation, and biomedicine.
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基本信息:
DOI：10.16026/j.cnki.iea.2025050432
中图分类号:TB34;O641.4
引用信息:
[1]张剑铎,季修文,路之源,等.金属有机框架材料的可控化学刻蚀用于构建功能材料及其应用进展[J].离子交换与吸附,2025,41(05):432-449.DOI:10.16026/j.cnki.iea.2025050432.
基金信息:
国家自然科学基金面上项目(项目号52273022)