New Complex-Forming Organomineral Support Based on Aluminum Oxyhydroxide Modified with Nitrilotris(methylene phosphonic) Acid

Abstract

A method for the surface chemical modification of aluminum oxyhydroxide (boehmite γ-AlO (OH)) by the nitrilotris(methylene phosphonic) acid (NTP) complexing ligand is proposed. The unmodified and NTP-modified boehmites are characterized using X-ray powder diffraction, XPS, and IR spectroscopy; the acid–base and complex-forming properties of surface-grafted NTP are studied. One of the three phosphonic groups of NTP is found to be involved in binding to the boehmite surface. The surface concentration and stepwise dissociation constants of grafted NTP are determined. A study of the nickel(II) sorption as a function of aqueous acidity shows that the modifying coating increases the sorption capacity of boehmite (causing рН50 to shift by one unit toward lower values). In terms of surface complexation theory, nickel(II) sorption from aqueous solutions may be described by models involving ≡Al–ONi+ and ≡Al–ONi(OH) complexes in the case of boehmite and ≡Al–LHi Nii–3 (i = 0, 1, 2, or 3) complexes in the case of NTP-modified boehmite (NTP-boehmite). NTP anchorage to the surface decreases the stability of nickel(II) complexes compared to their analogues in solutions. A mechanism of nickel(II) ion binding by NTP-boehmite is suggested. The prepared new organomineral support can be used to immobilize those metal ions that form stable complexes with phosphonic acids.