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Updated: Sep 9, 2025

Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Bromine-Functionalized Covalent Organic Frameworks Enhancing the Desorption Efficiency and Enabling Preconcentration
Yong Tian1, Ruijie Zhao2, Yanfeng Zhang3
1School of Environmental & Municipal Engineering, Qingdao University of Technology, Qingdao 266033, China.
Abstract:
Covalent organic frameworks (COFs) exhibit exceptional adsorption capacity but suffer from challenging desorption. In this study, a bromine-functionalized magnetic COF composite (Fe3O4@COF-Br) was synthesized via bromodimethylsulfonium bromide-mediated bromination of imine-linked COF on Fe3O4 nanospheres (Fe3O4@COF), where the COF framework was constructed by 1,3,5-tris(4-formylphenyl)benzene and 2,6-diamino-3,5-diethynylpyridine. Compared with pristine Fe3O4@COF, Fe3O4@COF-Br enhanced desorption efficiencies for brominated contaminants by about 30% while maintaining adsorption capacity. Systematic characterization and DFT simulations revealed reduced host-guest binding strengths in the brominated composite with interaction energies lowered by about 30 kcal mol-1. Employing Fe3O4@COF-Br as the magnetic solid-phase extraction (MSPE) adsorbent coupled with ESI-MS detection, the method achieved detection limits of 1.4-9.5 ng L-1 for tetrabromobisphenol A (TBBPA) and its derivatives (TBBPA-BHEE, TBBPA-BGE, TBBPA-BME, TBBPA-BAE, TBBPA-BDBPE), with coefficients of determination (R2) > 0.99 and precision (relative standard deviations) ≤ 8.4%. Validated in landfill leachate, soil, lake water, tap water, juice, soy sauce, and urine matrices, the method delivered 75-125% recoveries, demonstrating practicability and accuracy for complex environmental analysis.
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