Efficient adsorption of phosphorus by macroscopic MOF/chitosan composites and preliminary investigation of subsequent phosphorus recovery through electrochemically-driven struvite precipitation.

The proper management of phosphorus (P) from wastewater is crucial for sustainable development consideration. Herein, we developed a strategy which combines adsorption via tailored adsorbents and electrochemically-driven struvite precipitation (ESP) for P recovery. Novel polydopamine-modified Ce-MOF/chitosan composite beads (PDA@Ce-MOF-CS) were prepared by a facile in situ growth of Ce-MOF crystals incorporated natural polymers and PDA coating. The physicochemical properties of PDA@Ce-MOF-CS were characterized. Both batch and fixed-bed column experiments were conducted to evaluate its adsorption performances. Representatively, PDA@Ce-MOF-CS performed good selectivity for P removal and exhibited a maximum adsorption capacity of 161.13 mg P/g at pH 3 and 318 K. Meanwhile, the developed adsorbent showed great reusability after ten regeneration cycles as well as good adsorption stability. The dominant mechanism for efficient P adsorption included electrostatic attraction, surface precipitation and ligand exchange. Interestingly, PDA@Ce-MOF-CS exhibited a remarkable adsorption capacity of 92.86 mg P/g by treating real P-rich electroplating wastewater, and the desorbed P in the eluate could be effectively recovered and converted into a solid fertilizer as struvite via ESP. Overall, this work provided a new research direction for P recovery from wastewater as struvite by combined technologies with the help of macroscopic MOF architectures.

Development of polyaminated chitosan-zirconium(IV) complex bead adsorbent for highly efficient removal and recovery of phosphorus in aqueous solutions.

The aim of this work is to examine the adsorption performance and mechanism of phosphorus (P) onto polyethyene polyamine (PEPA) grafted chitosan-zirconium(IV) composite beads (CS-Zr-PEPA) from aqueous solutions. The morphology, functional groups, and surface area of the CS-Zr-PEPA beads were characterized by SEM, FTIR, and BET analysis. Batch adsorption experiments were conducted via different operating parameters such as solution pH, initial phosphate concentration, co-existing anions and temperature. The adsorption kinetics, equilibrium isotherms and adsorption stability of the adsorbent were scrutinized. In comparison with other CS-based beads, the CS-Zr-PEPA had a greater affinity towards P and exhibited a maximum adsorption capacity of 103.96 mg-P/g predicted by Langmuir mode. The reusability studies of CS-Zr-PEPA beads were carried out. The CS-Zr-PEPA beads exhibit preferable sequestration of P through specific interactions, as further demonstrated by studying physicochemical characteristics of the virgin beads and P-adsorbed beads using X-ray photoelectron spectroscopy (XPS). The column performance of CS-Zr-PEPA beads was tested with P-containing wastewater. Results indicated that the developed CS-Zr-PEPA composite beads could be utilized as a promising adsorbent for effective removal and recovery of P from water and wastewater.

Phosphorus removal and recovery from water with macroporous bead adsorbent constituted of alginate-Zr4+ and PNIPAM-interpenetrated networks.

Currently, there is a growing trend in employing natural biomaterials (e.g., alginate) to prepare a novel bead adsorbent for phosphorus (P) elimination. However, the utilization of alginate beads to remove and recover P from effluents possesses limitations associated with its physical characteristics such as a dense gel layer, poor mechanical strength and low stability. To overcome the limitations and improve the adsorption performances, we synthesized a novel alginate-derived bead constituted of PNIPAM network interpenetrated in alginate-Zr4+ network (PNIPAM/SA-Zr) decorated with polyethylene glycol as a pore-forming agent, and then investigated its ability to remove and recover P from effluents. The morphology, functional groups, surface area, and mechanical strength of the beads were evaluated by SEM, FTIR, BET, and swelling analysis. The adsorption of P was investigated by varying various factors. The adsorption kinetics, isotherms, and thermodynamics were studied. Particularly, the P-loaded beads exhibited a faster desorption rate under thermal stimulus, and remained good desorption efficiency and reusability within five consecutive cycles. Zeta-potential and XPS results revealed that the adsorption mechanisms were related to electrostatic interactions, ligand exchange, and the formation of inner-sphere complexes. The beads possessed favorable fixed-bed column operation performances for P removal and recovery from real wastewater.