Three-dimension hierarchical composite via in-situ growth of Zn/Al layered double hydroxide plates onto polyaniline-wrapped carbon sphere for efficient naproxen removal.

In this work, a novel adsorbent, 3D hierarchical CS@PANI@ZnAl-LDH composite, has been successfully fabricated through the hydrothermal synthesis of the carbon sphere, oxidative polymerization of polyaniline, and in-site growth of ZnAl-layered double hydroxides, simultaneously applied for the naproxen removal from aqueous solutions. The dynamics and isotherms fit better with the pseudo-second-order and Langmuir model, demonstrating the chemisorption, monolayer, and endothermic process. In addition, the high uptake capacities of CS@PANI@ZnAl-LDH for naproxen was 545.5 mg/g at 298 K when the pH was 5.0, outperforming most previously reported materials. Moreover, after five adsorption-desorption cycles, the spent CS@PANI@ZnAl-LDH maintains high removal efficiency and structural composition, revealing excellent recyclability and stability. Furthermore, Fourier transformed infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) analyses indicate electrostatic interactions, π-π interactions, and hydrogen bonding between CS@APNI@ZnAl-LDH and naproxen. Quantitative analyses, Localized orbit locator (LOL)-π isosurface, and Independent Gradient Model further verify the adsorption mechanisms mentioned above, indicating the synergistic effects between PANI and ZnAl-LDH improve the elimination ability for naproxen. Significantly, Hirshfeld surface analyses reveal that naproxen behaves as the H-bond acceptor, and the ZnAl-LDH acts as the H-bond donor. This work provided a feasible way to design purification materials for wastewater treatment.