Zirconium-carboxylate metal–organic frameworks as stationary phases for chromatographic separation

Zirconium-based metal-organic frameworks (Zr-MOFs) have emerged as highly promising candidates for high-performance chromatographic stationary phases due to their exceptional stability, well-defined porous architectures, and excellent structural tunability. Due to the rich variety of carboxylate linkers and their strong adaptability to coordination flexibility and adjustable backbone rigidity, carboxylate-based Zr-MOFs have more flexible modifiability. The inherent flexibility in modulating both the pore structures and topology of Zr-MOFs enables directional engineering to meet specific application requirements. This includes precise control over porosity, pore environment, and framework stability, thereby achieving targeted and efficient separation of analytes. This review provides a systematic classification of Zr-MOFs and highlights representative examples. Furthermore, this review systematically analyzes the application of Zr-MOFs and Zr-MOF-based composites in various chromatographic separations, including gas chromatography (GC), high-performance liquid chromatography (HPLC), and capillary electrochromatography (CEC).