Circumstances of La, Eu, Dy, and Yb Cations Intercalated via Ion Exchange in γ-Zirconium Phosphate

Abstract

Both α- and γ-zirconium phosphate were examined for use as ion exchangers for recovery of rare earth elements. Trivalent rare earth elements can be partially substituted for protons in the interlayer space, and γ-zirconium phosphate shows a much better ion exchange competency than α-zirconium phosphate. The exchanged cation of the rare earth elements might be related to different amounts of oxygen from P–OH and H2O, and these rare earth elements were thus positioned at a different separations from the zirconium phosphate layer. The radial structure function (RSF) curve from extended X-ray absorption fine structure data implied that the calibrated M–O distance and coordination number changed with the ionic radius. The calibrated M–O distances from RSF were 2.52, 2.42, 2.38, and 2.28 for La, Eu, Dy, and Yb, respectively. The coordination numbers of oxygen for Yb were approximately 7 and greater than 10 for La and Eu, respectively. These smaller coordination numbers for smaller cations may result from the strong interaction between the cations and the zirconium phosphate layer. The Debye–Waller factor also increased with an increase in the ionic radius. These factors show a strong relation to the coordination state of rare earth elements in the unit cell of the γ-zirconium phosphate and to the interaction strength.