Dual-engineered defect-rich molecularly imprinted zirconium metal organic framework platform for selective adsorption...

Metal-Organic Frameworks (MOFs) are recognized as ideal platforms owing to their highly tunable pore structures and tailorable functional sites. Nevertheless, their real-world applications are hindered by inadequate binding affinity and slow mass transport toward target molecules. Herein, A dual-engineered molecularly imprinted-defective zirconium metal-organic framework MI-d-Zr-MOF platform was pioneered via one-step synthesis, combining porogen and template strategies. Flexible ligand L-aspartic acid enabled size-adaptive regulation and functional alternariol (AOH) adsorption via dicarboxylic/amino groups, while trifluoroacetic acid porogen modulated crystallization, increasing specific surface area from 14.5 m²·g⁻¹ to 443 m²·g⁻¹ . Driven by the synergistic effects of surface imprinting, hydrogen bonding and electrostatic interactions, the MI-d-Zr-MOF achieved a maximum adsorption capacity of 456 mg·g⁻¹ . MI-d-Zr-MOF was used as an adsorbent for dispersed solid-phase extraction and combined to determine trace AOH in six cereal samples. The developed method has high selectivity and sensitivity, with a detection limit and recovery rate of 0.01-0.03 μg·kg⁻¹ and 86-112%, respectively. This dual-engineering strategy provides a versatile blueprint for advanced MOF-based adsorbents, enabling precise customization for diverse targets such as AOH and its validated, selective quantification in complex cereal matrices, demonstrating significant potential for safety monitoring.