Effect of Mn2+/Zn2+/Fe3+ Oxy(Hydroxide) Nanoparticles Doping onto Mg-Al-LDH on the Phosphate Removal Capacity from Simulated Wastewater

Abstract

A parent Mg-Al-LDH was upgraded in its adsorption properties due to the incorporation of tri-metal species oxy(hydroxide) nanoparticles obtaining Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH composite for the phosphate recovery from simulated urban treated wastewater. The physicochemical properties of the synthesized Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH make promising for real application without being environmentally harmful. The performance of Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH composite was evaluated through batch adsorption assays. The support of iron, manganese, and zinc (oxy)hydroxide nanoparticles onto the parent Mg-Al-LDH structure was performed by precipitation, isomorphic substitution, and complexation reactions. The main improvement of the Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH composite was the highest phosphate adsorption capacity (82.3 mg∙g^-1) in comparison to the parent Mg-Al-LDH (65.3 mg∙g^-1), in a broad range of concentrations and the effective phosphate adsorption at neutral pH (7.5) near to the real wastewater effluents conditions in comparison to the conventional limitations of other adsorbents. The effectiveness of Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH composite was higher than the conventional metal LDHs materials synthesized in a single co-precipitation step. The phosphate adsorption onto Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH composite was described to be governed by both physical and chemical interactions. The support of Mn²⁺/Zn²⁺/Fe³⁺ oxy(hydroxide) nanoparticles over the parent Mg-Al-LDH was a determinant for the improvement of the phosphate adsorption that was governed by complexation, hydrogen bonding, precipitation, and anion exchange. The intra-particular diffusion also described well the phosphate adsorption onto the Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH composite. Three specific stages of adsorption were determined during the phosphate immobilization with an initial fast rate, followed by the diffusion through the internal pores and the final equilibrium stage, reaching 80% of removal and the equilibrium within 1 h. The Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH was strongly selective towards phosphate adsorption in presence of competing ions reducing the adsorption capacity at 20%. The Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH has limited reusability, only 51% of the adsorbed phosphate could be recovered in the second cycle of the adsorption-desorption process. Around 14% of phosphate was loosely-bond to Mn²⁺/Zn²⁺/Fe³⁺/Mg-Al-LDH which brings the opportunity to be a new source of phosphorus. The use of eluted concentrates and the final disposal of the exhausted adsorbent for soil amendment applications can be an integral nutrient system (P, Mn, Zn, Fe) for agriculture purposes.

Keywords: Mg-Al-LDH; Mn2+/Zn2+/Fe3+; composite; equilibrium; kinetic; phosphate; thermodynamics.