Detection and Selective Sorption of Copper Ions by a COF-Modified Melamine Sponge

Commercial melamine sponges were modified with a functional covalent organic framework (COF), and they were evaluated as adsorbents of divalent copper cations from aqueous solutions. A phosphazene unit successfully covered the surface of the melamine sponge, and the organic framework was subsequently formed through the nucleophilic substitution with 4,4' bipyridine. The covalent organic framework functionalized on the melamine sponge can detect and effectively adsorb copper compounds in aqueous solutions. Its selectivity toward the adsorption of copper was demonstrated through the presence of different metal salts. Four competitive metal cations, i.e., copper, nickel, iron, and calcium, were selected to confirm the preferential binding of copper on the COF-functionalized sponge. The outcome was determined through the studies of X-Ray Fluorescence elemental analysis, X-Ray Photoelectron Spectroscopy (XPS), and Electron Paramagnetic Resonance experiments. XRF reported a copper sorption capacity of 293 μg cm^-2, which is nearly nine times higher than the performance of the pristine sponge. Q-band EPR measurements demonstrated the presence of different coordination sites with different substituents for copper on the modified sponges, when the adsorption took place in an aqueous solution containing exclusively copper cations, while only one coordination, the favorable trigonal bipyramidal geometry, was obtained in the presence of additional metals.