Adsorption of phosphate in water by La/Al bimetallic-organic frameworks-chitosan composite with wide adaptable pH range

Abstract

The limited metal sites of monometallic MOFs and the high influence of pH limit their adsorption capacity. To solve these problems, La/Al bimetallic MOFs/chitosan composite was prepared by hydrothermal synthesis and impregnation methods and then characterized by XRD, FTIR, SEM, BET and XPS techniques. The doping of La has no obvious effect on the structure of Al-MOFs, but chitosan has greatly changed the structure of La/Al bimetallic MOFs. The phosphate adsorption of the composite was affected by La/Al molar ratio, chitosan/bimetallic MOFs mass ratio, temperature, phosphate initial concentration, adsorbent dosage, pH, and coexisting ions. The optimum molar ratio of La/Al and mass ratio of chitosan/bimetallic MOFs are 0.5:1 and 5.0%, respectively. The addition of La and chitosan can provide additional adsorption active sites, inhibit metal leaching, and enhance the phosphate adsorption performance, stability, and acid-alkali resistance of the composite. Its maximum adsorption capacity was 264.48 mg·g⁻¹. Its phosphate removal efficiency is above 90% at pH= 3.0–9.0. The actual phosphorus-containing wastewater with 7.064 mg·L⁻¹ PO₄^3- and initial pH 7.4 can be treated to meet Chinese first-class effluent quality standard. La, Al, amino groups, and hydroxyl groups play an important role in the adsorption process of phosphate. When pH < pH_pzc (4.99), phosphate is adsorbed by electrostatic gravitation between it and protonated positively charged amino and hydroxyl groups on La and Al, while when pH > pH_pzc, phosphate is removed by ligand exchange between it and hydroxyl groups on La and Al. A stable, low-cost, and efficient bimetallic MOFs-based phosphate adsorbent was designed and prepared in this paper, and the results can provide reference for researchers in environmental chemical engineering.