Citation: Yuanfei Liu, Wanjiao Wei, Xu Liu, Rui Hua, Yanjuan Liu, Yuefei Zhang, Wei Chen, Sheng Tang. Green and mild synthesis of Ca-MOF/COF functionalized silica microspheres in an acid-base tunable deep eutectic solvent for multi-mode chromatography[J]. Chinese Chemical Letters, ;2026, 37(1): 111186. doi: 10.1016/j.cclet.2025.111186 shu

Green and mild synthesis of Ca-MOF/COF functionalized silica microspheres in an acid-base tunable deep eutectic solvent for multi-mode chromatography

Yuanfei Liu ^a ,
Wanjiao Wei ^a ,
Xu Liu ^a ,
Rui Hua ^a ,
Yanjuan Liu ^b ,
Yuefei Zhang ^a ,
Wei Chen ^a ,
Sheng Tang ^{a, *,}

a.
School of Chemistry and Environmental Engineering, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Wuhan Institute of Technology, Wuhan 430205, China
b.
College of Medicine, Linyi University, Linyi 276000, China

stang@wit.edu.cn

Received Date: 23 September 2024
Revised Date: 12 February 2025
Accepted Date: 8 April 2025
Available Online: 8 April 2025

Figures(4)

Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO₂, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO₂ stationary phase. Firstly, COF@SiO₂ was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO₂. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO₂ can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO₂ is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
- Metal organic framework,
- Covalent organic framework,
- Deep eutectic solvent,
- Silica composites,
- Multi-mode chromatography
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