Investigation of nanoscale zerovalent iron-based magnetic and thermal dual-responsive composite materials for the removal and detection of phenols.

In this study, well-defined magnetic and thermal dual-responsive nanomaterials were synthesized, which contained ultrafine core-shell Fe@SiO nanoparticles as magnetic core and poly(N-isopropylacrylamide) (PNIPAM) as thermosensitive outer shell. The fabricated nanoparticles were characterized and investigated for the adsorption of four phenolic compounds, including bisphenol A (BPA), tetrabromobisphenol A (TBBPA), 4-tert-octylphenol (4-OP) and 4-n-nonylphenol (4-NP). The experimental results demonstrated that the excellent adsorption rates were attributed to hydrophobic effect, hydrogen-bonding interaction, and electrostatic attraction. The adsorption process followed pseudo-second-order kinetics model and nonlinear isotherms, indicating heterogeneous adsorption process. The adsorption efficiency of 4-NP using Fe@SiO@PNIPAM was more than 90% under optimized condition within 2 h. The determined maximum adsorption amounts of BPA, TBBPA, 4-OP and 4-NP were 2.43, 6.83, 24.75, and 49.34 mg g, respectively. Meanwhile, a magnetic solid phase extraction (MSPE) method with Fe@SiO@PNIPAM was established to determine these four compounds simultaneously. Under the optimal conditions, the linearity ranges were in the range of 2-200, 2-300, 2-100 and 2-100 μg L for BPA, 4-OP, TBBPA, and 4-NP, respectively, and the detection limits were in the range of 0.58-0.76 μg L, respectively. The applicability of the proposed method was evaluated by analyzing three fresh water samples, and satisfactory spiked recoveries in the range 70.9-119.9% were achieved. It was proved that these adsorbents could be easily collected and recycled owing to the appropriate magnetism. The results also demonstrated that the as-prepared adsorbents had promising potential in the enrichment and analysis of detrimental organic pollutants from water.