Valorization of waste oyster shells via thermal and acid activation for Congo red dye adsorption from aqueous media

Abstract

A scalable route to valorize waste oyster shells into an effective adsorbent for Congo red removal is reported. Sequential thermal calcination (500 °C) and H₃PO₄ activation convert the CaCO₃ matrix into Ca–phosphate-rich surfaces (XRD, FTIR) bearing abundant –OH/PO₄ groups. Despite a moderate BET area (MOS: 22.15 m² g⁻¹), the modified oyster shell achieves rapid uptake (>80–90% removal within 10 min; near-complete by 60 min), broad pH tolerance with optimal performance below pH_pzc ≈ 8.06, and high capacity (q_max = 50.89 mg g⁻¹). Kinetics follow a pseudo-second-order model (R² = 0.994; k₂ = 0.0127 g mg⁻¹ min⁻¹) and equilibrium data fit both Freundlich (R² = 0.997; K_F = 37.19; n = 2.97) and Langmuir (K_L = 4.21 L mg⁻¹) models, indicating chemisorptive affinity on an energetically heterogeneous surface. MOS is durable and regenerable (∼95% removal after five cycles). Density functional theory calculations corroborate strong dye-phosphate site interactions. The combined thermal-acid treatment thus yields a low-cost, reusable adsorbent suitable for practical dye-laden wastewater treatment.