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Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water
Author NameAffiliationE-mail
XI Fugui Department of Chemistry, Xinzhou Normal University, Xinzhou, Shanxi 034000, China xifugui@163.com 
LI Du Department of Chemistry, Xinzhou Normal University, Xinzhou, Shanxi 034000, China  
YAN Zhourui Department of Chemistry, Xinzhou Normal University, Xinzhou, Shanxi 034000, China  
WANG Hui Department of Chemistry, Xinzhou Normal University, Xinzhou, Shanxi 034000, China  
XIANG Junyu Department of Chemistry, Xinzhou Normal University, Xinzhou, Shanxi 034000, China  
DONG Zhiyun Department of Chemistry, Xinzhou Normal University, Xinzhou, Shanxi 034000, China  
Abstract: In this study, UiO-66-CHO and UiO-66-CH=C(CN)2 were synthesized using pre-synthetic and postsynthetic modification methods, for the adsorption of tetracycline (TC) from aqueous solution. The powder X-ray diffraction patterns of these functional MOFs exhibit that they have the same frameworks with UiO-66 and good crystallinity. FTIR and 1H NMR spectroscopy powerfully suggested that the formyl and the cyano were successfully introduced to the frameworks. Compared to UiO-66, UiO-66-CHO and UiO-66-CH=C(CN)2 exhibit slightly diminished thermal stability in the thermogravimetric analysis and the absence of organic linkers. The Brunauer-Emmett-Teller (BET) specific surface area calculated from the N2 adsorption and desorption experiment data shows that all modified materials also preserve porousness. The three materials in the scanning electron microscope showed similar morphology at the microscopic level, and uniform particle size may be favorable for TC adsorption. A series of experiments were conducted on UiO-66-CHO and UiO-66-CH=C(CN)2 for the adsorption of TC in water. For the two functional MOFs, adsorption experiment data confirmed that the adsorption occurs via chemisorption on a monolayer, aligning with the pseudo-second-order kinetic and Langmuir isotherm models. UiO-66-CHO and UiO-66-CH=C (CN)2 exhibited a higher theoretical maximum adsorption capacity of 199.28 and 62.61 mg·g-1 at pH 9.0 than UiO-66 and shorter adsorption equilibrium time of about 150 min. Thermodynamic experiments have shown that the uptake of TC is both endothermic and spontaneous, leading to an increased disorder at the solid-solution interface. It is worth noting that UiO-66-CHO could preserve the 75% removal efficiency in the fifth adsorption cycle.
Keywords: tetracycline  metal-organic frameworks  UiO-66-CHO  cyano  adsorption
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XI Fugui,LI Du,YAN Zhourui,WANG Hui,XIANG Junyu,DONG Zhiyun.Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water[J].Chinese Journal of Inorganic Chemistry,2025,41(4):683-694.
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Chinese Journal of Inorganic Chemistry