Synthesis of hierarchically porous zirconium-based metal-organic framework@silica core-shell stationary phase through etching strategy for liquid chromatography

Habib Ur Rehman; Chunyan Zhang; Xiangwei Liu; Yang Liu; Jiawei Liu; Changwei Tang; Quan Bai

doi:10.1016/j.chroma.2023.464377

Synthesis of hierarchically porous zirconium-based metal-organic framework@silica core-shell stationary phase through etching strategy for liquid chromatography

J Chromatogr A. 2023 Oct 25:1709:464377. doi: 10.1016/j.chroma.2023.464377. Epub 2023 Sep 12.

Authors

Habib Ur Rehman¹, Chunyan Zhang¹, Xiangwei Liu¹, Yang Liu¹, Jiawei Liu¹, Changwei Tang¹, Quan Bai²

Affiliations

¹ Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Key Laboratory of Modern Separation Science in Shaanxi Province, Institute of Modern Separation Science, Northwest University, Xi'an 710069, China.
² Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Key Laboratory of Modern Separation Science in Shaanxi Province, Institute of Modern Separation Science, Northwest University, Xi'an 710069, China. Electronic address: baiquan@nwu.edu.cn.

PMID: 37741224
DOI: 10.1016/j.chroma.2023.464377

Abstract

Metal organic frameworks (MOFs) show promise to be employed as stationary phase for high performance liquid chromatography (HPLC), however, the microporous structures of MOFs seriously restrict the diffusion and mass transfer of solute molecules, leading to a low column efficiency. In this paper, the fabrication of hierarchically porous UiO-66@SiO₂ (HP- UiO-66@SiO₂) core-shell microspheres via H₂O₂ etching has been proposed as a viable approach to enhance the separation performance of MOFs-based columns for HPLC. Through the direct treatment of the preliminary prepared UiO-66@SiO₂ microspheres with H₂O₂ etching, HP-UiO-66@SiO₂ core-shell microspheres were successfully synthesized with an enlarged pore size of up to 9 nm, facilitating efficient mass transfer in chromatographic separation. The prepared HP-UiO-66@SiO₂ core-shell microspheres were then explored as stationary phase in HPLC to separate the nonpolar alkyl benzene homologues, the polar aromatic alcohol homologues and the xylene isomers. The results indicated that the baseline separations of these solutes were achieved successfully with narrow peak width and higher resolution than the UiO-66@SiO₂ column. The HP-UiO-66@SiO₂ column exhibited superior separation performance, reaching a maximum plate number of 134,459/m for fluorene, and showing good reproducibility. As a result, this template-free approach suggests that the fabrication of hierarchically porous MOFs@silica core-shell microspheres is a successful approach to enhance the column efficiency of MOFs-based columns in HPLC.

Keywords: H(2)O(2) etching; HPLC; Hierarchical porous core-shell microspheres; Stationary phase; UiO-66.