Ultrasound-Assisted Synthesis of Fe3+/Zr4+-Modified Layered Double Hydroxides for RSM-Optimized Fluoride Remediation: Structural Insights and Evaluation in Groundwater

This study investigates the structure–performance relationship of Fe3+- and Zr4+-modified layered double hydroxides (LDHs) for fluoride removal from water. Mg–Al LDHs with different metal loadings (Zr0.05, Zr0.1, Fe0.8, and Fe1) were synthesized via ultrasound-assisted coprecipitation and characterized using XRD, SEM–EDS, FTIR, XPS, and N2 physisorption. Among the synthesized materials, Zr0.05-LDH exhibited the highest adsorption performance. Response surface methodology identified adsorbent dosage as the most influential parameter, achieving a maximum fluoride removal efficiency of 98.17% under optimal conditions (pH ≈ 5, adsorbent dose of 0.88 g/L, and initial fluoride concentration of 12.6 mg/L). Zr0.05-LDH showed the largest specific surface area (261 m2/g) and a maximum adsorption capacity of 137 mg/g, as described by the Langmuir isotherm model. Kinetic studies indicated rapid adsorption, with equilibrium reached at approximately 180 min. Fluoride removal was governed primarily by inner-sphere complexation at Zr4+ and Fe3+ sites, accompanied by anion exchange and electrostatic interactions. The adsorbent retained 89% of its capacity after five regeneration cycles. Groundwater tests from Durango, Mexico, demonstrated effective fluoride reduction below Mexican and WHO guideline limits despite competing anions. These results demonstrate the potential of modified LDHs for fluoride-contaminated groundwater treatment.