Thermal Air Oxidation-Mediated Synchronous Coordination and Carbonation of Lanthanum on Biochar toward Phosphorus Adsorption from Wastewater

Biochar has attracted increasing attention as the sustainable and structure-tunable carrier for lanthanum (La) species for diverse applications. Carbonated La species possesses a higher biocompatibility and a lower leaching potential than other commonly used La species, while less attention is paid on the application of carbonated La in phosphorus (P) adsorption. Herein, thermal air oxidation (TAO) was applied as a novel strategy for synchronously tuning the coordination environment and chemical species of La on biochar surface. The results demonstrated that TAO induced the coordination of La with oxidation-generated oxygenated functional groups (OFGs) and carbonation of La species by the oxidation-generated CO2 on the biochar surface. The batch adsorption results showed that the Qm of resultant biochar remarkably increased from 68.92 to 132.49 mg/g at 1 g/L dosage. It also showed a robust adsorption stability in pH 2-6, a strong resistance to the co-existing Cl-, SO42-, NO3-, CO32-, or HCO3-, a stable adsorption recyclability, and an ultralow La leaching potential. The P adsorption was dominated by ligand exchange-induced inner-sphere complexation. In practical swine wastewater, the resultant biochar composite (1 g/L) removed 99.87% of P from 92.3 to 0.12 mg/L at a practical pH of 7.12. The density functional theory calculation further revealed the significant role of the binding of carbonated La by the biochar surface OFGs in reducing the P adsorption energies, indicating the synergism between the oxygenated biochar carrier and the carbonated La in P adsorption. Finally, this study provided a novel route to synchronously tune the coordination environment and chemical species of La on biochar via a facile TAO process for high-efficient P adsorption from wastewater.