Yuhuan Su

Phosphate pollution caused by human activities has become a pressing environmental issue, leading to eutrophication and severe ecological risks. In this study, artificial humic acid (HA) and fulvic acid (FA) were synthesized from tung fruit and glucose, respectively, and further composited with ferrihydrite (Fh) to prepare HA/Fh and FA/Fh adsorbents for phosphate removal. The structural and morphological characteristics of the composites were confirmed by SEM, XRD, FTIR, and XPS analyses, which indicated successful complexation of HA or FA with Fh through ligand exchange and surface interactions. Batch adsorption experiments revealed that HA/Fh and FA/Fh exhibited significantly enhanced adsorption capacities compared to pristine Fh, with maximum Langmuir adsorption capacities of 33.67 mg g⁻¹ and 37.06 mg g⁻¹, respectively. The adsorption behavior was well described by the pseudo-second-order kinetic model and the Langmuir isotherm, suggesting a chemisorption-dominated process involving ligand exchange between surface –OH groups of Fh and phosphate ions, supplemented by electrostatic attraction. Coexisting ion studies demonstrated that Cl⁻ and SO₄²⁻ slightly promoted phosphate adsorption, while NO₃⁻ and CO₃²⁻ strongly inhibited it, highlighting the competition of multivalent anions with phosphate for Fe³⁺ active sites. Importantly, the phosphate-enriched adsorbents can be directly recycled as phosphorus fertilizers, providing a sustainable pathway for both environmental remediation and phosphorus resource recovery.

Fe–Ce-MOFs with a rice-grain-like morphology were successfully obtained via hydrothermal synthesis, where ferric chloride (FeCl₃) and cerium nitrate [Ce(NO₃)₃] served as the metal precursors and terephthalic acid (PTA) acted as the organic coordinating ligand. The effects of the Fe:Ce molar ratio, (Fe/Ce):PTA ratio, reaction duration, and synthesis temperature on adsorption performance of the Fe–Ce-MOFs were systematically studied. A comprehensive evaluation was conducted on the removal of fluoride and phosphate ions from aqueous solution. Under optimized conditions, the maximum adsorption capacities of Fe–Ce-MOFs for fluoride and phosphate reached 183.82 mg g⁻¹ and 110.74 mg g⁻¹, respectively. Adsorption data correlated strongly with the Langmuir isotherm, were best represented by the pseudo-second-order kinetic model, and were identified as a spontaneous and endothermic reaction. After three regeneration cycles, the adsorbent still maintained high removal efficiencies for fluoride (85.17%) and phosphate (47.34%) removal. In practical wastewater treatment, removal efficiencies of 92.04% for fluoride and 93.87% for phosphate were achieved. Mechanistic studies revealed that fluoride removal was dominated by electrostatic attraction and hydroxyl–fluoride ion exchange, whereas phosphate removal was attributed to the generation of inner-sphere complexes involving PO₄³⁻ and Fe/Ce active sites. This study not only elucidates the synergistic mechanism of fluoride and phosphate elimination by Fe–Ce-MOFs but also provides theoretical guidance and application prospects for the development of highly efficient and stable bimetallic MOF-based adsorbents for environmental remediation.