Hollow manganese phosphonate microspheres with hierarchical porosity for efficient adsorption and separation

Hollow manganese phosphonate microspheres of an inorganic-organic hybrid with hierarchically porous shells were prepared through a template-free hydrothermal method using ethylene diamine tetra(methylene phosphonic acid) as the coupling molecule. The hollow structures with hierarchical porosity were confirmed by SEM, TEM and N-2 sorption. FT-IR, XPS and TG-DSC measurements revealed that the organophosphonate linkers were homogeneously incorporated into the hybrid framework. The hierarchical manganese phosphonates could be used as efficient adsorbents for the removal of copper ions, showing fast binding kinetics due to the well-structured porosity. The adsorption process follows pseudo-second order reaction kinetics, as well as Langmuir isotherm, indicating that Cu2+ was monolayer adsorbed on the hybrid by chemical complexation. Furthermore, the synthesized manganese phosphonates with peculiar porosity exhibited excellent size selectivity for protein adsorption in a complex solution, presenting the promising potential as candidates for biomaterials.