Metastable nano-zirconium phosphate inside gel-type ion exchanger for enhanced removal of heavy metals

Nanotechnology has provided a new opportunity for water decontamination from trace heavy metals, yet the relatively poor acidic stability remains a major obstacle for the nano-adsorbents, given that acidic treatment is frequently used to regenerate the heavy metal-saturated adsorbents. Zirconium phosphate (ZrP) is very promising for water treatment due to its absolute insoluble nature, though it interacts with heavy metals mainly through the non-specific electrostatic attraction. Herein, we prepared the ultrafine ZrP (~3.9 nm) inside the commercially available gel-type cation exchanger (N001), i.e., the sulfonated poly(styrene-co-divinylbenzene) bead. The resultant nanocomposite ZrP@N001 contained the amorphous nanoparticles (NPs) with metastable γ-ZrP structure as the main phase, unlike the layered α-ZrP formed inside the macroporous cation exchanger D001 (referred to as ZrP@D001). As a result, ZrP@N001 could selectively adsorb heavy metals through inner-sphere coordination, possessing a much stronger adsorption affinity than ZrP@D001, as confirmed by XPS analysis. In both batch and column assays on the Pb(II)-polluted water, ZrP@N001 exhibited superior adsorption performance over ZrP@D001. After adsorption, the exhausted ZrP@N001 was fully refreshed by acidic treatment for a 5-cyclic adsorption-regeneration run with constant removal efficiencies. This study may open a door for the rational design of highly efficient water purifiers for heavy metal control.