Zhang Xian, Xu Juan, Zhang Yanhui, Xiang Wenlong
College of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou, 363000, China.
College of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou, 363000, China; Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou, 363000, China; Fujian Provincial University Key Laboratory of Pollution Monitoring and Control, Minnan Normal University, Zhangzhou, 363000, China.
Environ Res. 2025 Sep 8;286(Pt 1):122804. doi: 10.1016/j.envres.2025.122804.
The derivation of defect-engineered metal-organic frameworks (MOFs) from industrial waste simultaneously mitigates environmental pollution, reduces MOF synthesis costs, and enhances adsorption performance. Herein, this study demonstrates a sustainable strategy for the resourceful synthesis of an iron-based MOF, s-MIL-100(Fe), using galvanizing pickling waste liquor (80.5 wt% Fe, 18.8 wt% Zn) as metal precursors. Although zinc ions do not incorporate into MOF frameworks, their coexistence induced the generation of coordinatively unsaturated metal sites (CUMS), enabling s-MIL-100(Fe) to achieve an ultra-high adsorption capacity of 721 mg g for doxycycline (DOX) at 303.15 K. In addition, Zn-mediated defect engineering increased the porosity of s-MIL-100(Fe), yielding optimized textural parameters (specific surface area: 733.4 m g; pore volume: 0.74 cm g), and outperformed commercial c-MIL-100(Fe) by 48.4 % in adsorption capacity with a shorter equilibrium time. Furthermore, s-MIL-100(Fe) exhibited robustness across a pH range of 2-10, in multi-ion matrices and under humic acid interference, while retaining 90 % capacity over four regeneration cycles. Synergistic mechanisms involve CUMS-driven coordination, π-π stacking, and pore confinement, supplemented by hydrogen bonding and electrostatic interactions. By transforming hazardous metallurgical waste into high-performance adsorbents, this work offers a sustainable approach that simultaneously addresses industrial waste management and advanced material synthesis. Notably, s-MIL-100(Fe) demonstrates >97 % DOX removal efficiency in real contaminated waters, including aquaculture effluents, municipal wastewater, and river systems, validating its practical utility in environmental remediation. The Zn-assisted defect modulation strategy provides new insights into the structure-property optimization of waste-derived MOFs, highlighting the untapped potential of impurity ions in functional material synthesis.
从工业废料中衍生出缺陷工程金属有机框架材料（MOF），既能减轻环境污染，降低MOF合成成本，又能提高吸附性能。在此，本研究展示了一种可持续策略，即以镀锌酸洗废液（铁含量80.5 wt%，锌含量18.8 wt%）为金属前驱体，资源丰富地合成铁基金属有机框架材料s-MIL-100(Fe)。虽然锌离子未纳入MOF框架，但其共存诱导了配位不饱和金属位点（CUMS）的产生，使s-MIL-100(Fe)在303.15 K下对多西环素（DOX）的吸附容量达到721 mg g的超高值。此外，锌介导的缺陷工程增加了s-MIL-100(Fe)的孔隙率，产生了优化的结构参数（比表面积：733.4 m g；孔体积：0.74 cm g），并在吸附容量上比市售的c-MIL-100(Fe)高出48.4%，且平衡时间更短。此外，s-MIL-100(Fe)在pH值为2至10的范围内、多离子基质中以及腐殖酸干扰下均表现出稳定性，在四个再生循环后仍保留90%的容量。协同机制包括CUMS驱动的配位、π-π堆积和孔道限制，辅以氢键和静电相互作用。通过将有害冶金废料转化为高性能吸附剂，这项工作提供了一种可持续方法，同时解决了工业废料管理和先进材料合成问题。值得注意的是，s-MIL-100(Fe)在包括水产养殖废水、城市污水和河流系统在内的实际污染水体中对DOX的去除效率超过97%，验证了其在环境修复中的实际效用。锌辅助的缺陷调制策略为源自废料的MOF的结构-性能优化提供了新见解，突出了杂质离子在功能材料合成中尚未开发的潜力。
