Copper Removal from Water by Citrate-Stabilized Amorphous Calcium Phosphate Nanoparticles: Adsorption Performance and Mechanisms

Amorphous calcium phosphate (ACP), a key calcium-phosphorus compound, has been widely applied in fields such as dentistry, orthopedics, and biomedicine. However, its potential for removing copper ions from aqueous solutions remains largely unexplored. In this study, sodium citrate-stabilized amorphous calcium phosphate (Cit-ACP) and its calcined derivatives at various temperatures were successfully synthesized as adsorbents for copper ions. The adsorption behavior of Cit-ACP was best described by the Langmuir isotherm, with kinetics following a pseudo-second-order model. Under conditions of pH 5.5 and an initial copper ion concentration of 200 mg/L, Cit-ACP exhibited a maximum adsorption capacity of 323.96 mg/g. Thermodynamic analysis confirmed that the adsorption process was spontaneous and endothermic. Comprehensive characterization via XRD, XPS, and zeta potential measurements before and after adsorption revealed a two-stage adsorption mechanism. At low initial copper concentrations, adsorption occurred predominantly through surface complexation between copper ions and sodium citrate molecules on Cit-ACP nanoparticles. At higher concentrations, the mechanism extended to include co-precipitation of copper ions with hydroxyl groups, which promoted the transformation of Cit-ACP into copper-substituted calcium phosphate phases, such as copper-containing hydroxyapatite. Owing to its straightforward synthesis, high adsorption capacity, and inherent biocompatibility, Cit-ACP presents a promising, cost-effective, and efficient adsorbent for the removal of copper ions from aqueous environments.