Phosphorous-functionalized PAMAM dendrimers supported on mesoporous silica for Zr(iv) and Hf(iv) separation

To overcome the urgency of zirconium and hafnium separation, a novel mesoporous silica sorbent (PS-G1.0-MSNs) modified with phosphorous-functionalized G1.0 PAMAM dendrimers was prepared. The adsorption and separation behaviors of PS-G1.0-MSNs adsorbent on Zr(iv) and Hf(iv) were perfromed as a function of acidity, contact time, temperature, and ion concentrations by batch sorption methods. The maximum adsorption capacities for Zr(iv) and Hf(iv) were 25.7 mg g-1 and 5.36 mg g-1 under optimal experimental conditions, respectively, and the separation factor βHf/Zr = 2.0 > 1 demonstrated that the prepared sorbent had preferential selectivity for Hf(iv) in rich Zr(iv) solution. Moreover, kinetic data indicated that the sorption process on Zr(iv) and Hf(iv) achieved equilibrium within 120 min, and followed the pseudo-first-order model with a rate-determining step. The adsorption amount increased as temperature raised from 283 K to 303 K and the isothermal data plotted with the Langmuir model was better than the Freundlich model with monolayer behavior. Thermodynamic data analysis indicated that the sorption process was spontaneous and endothermic. Furthermore, XPS analysis revealed that the metal ion adsorption was mainly induced by the chemical coordination of Zr(iv) and Hf(iv) ions with N, O, P atoms of amide and phosphate groups. The present work provides good guidelines on the design of high efficient sorbent for the separation of Hf(iv) from Zr(iv) solutions.