Metal-organic frameworks (MOFs) show great promise in heavy metal removal; however, their applications are restricted by the poor separability and water instability. Herein, granular Zr-based MOF-polymer composite beads (MPCB(Zr)) (mean diameter ∼ 1.74 mm) were synthesized using a facile dropping method, and applied on efficient lead ions (Pb(II)) removal. The as-prepared MPCB(Zr) demonstrated deep Pb(II) removal capability by reducing its concentration to ∼ 0.002 mg L-1 after adsorption equilibrium at 360 min. The distribution coefficient for Pb(II) reached 8.0 × 106 mL g-1, and the theoretical adsorption capacity for Pb(II) was 144.5 mg g-1 (0.70 mmol g-1, 30 °C). The resulting MPCB(Zr) was highly selective for Pb(II), with the selectivity coefficient up to ∼ 1.0-3.6 × 103 for the background cations (Na(I), K(I), Ca(II), and Mg(II)). Moreover, the MPCB(Zr) exhibited a broad working pH range (3.0-6.0) and satisfactory anti-interference to dissolved organic matters (humic acid and fuvic acid). Notably, the MPCB(Zr) also demonstrated excellent reusability with the Pb(II) removal efficiency over 99.0% after 20 cycles. Combined physicochemical characterizations unveiled that the thiol and oxygen-containing groups (e.g., hydroxyl, carboxylate) were responsible for the effective Pb(II) removal. To provide guidance for engineering application, the full-scale performance of the MPCB(Zr) under varying operation conditions was systematically evaluated via the validated pore surface diffusion model. This work provides an effective methodology to construct macroscopic MOF-polymer beads for effective Pb(II) removal, and promote the actual application of MOFs in water treatment.
Keywords: Adsorption mechanism; Fixed bed; Heavy metal removal; Macroscopic adsorbent; Model.
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