Kirkendall Effect Boosts Phosphorylated nZVI for Efficient Heavy Metal Wastewater Treatment

Removal of non-biodegradable heavy metals has been the top priority in wastewater treatment and the development of green technologies remains a significant challenge. We demonstrate that phosphorylated nanoscale zero-valent iron (nZVI) is promising for removal of heavy metals (Ni^II , Cu^II , Cr^VI , Hg^II ) via a boosted Kirkendall effect. Phosphorylation confines tensile hoop stress on the nZVI particles and "breaks" the structurally dense spherical nZVI to produce numerous radial nanocracks. Exemplified by Ni^II removal, the radial nanocracks favor the facile inward diffusion of Ni^II and the rapid outward transport of electrons and ferrous ions through the oxide shell for surface (Ni^II /electron) and boundary (Ni^II /Fe⁰ ) galvanic exchange. Accompanied by a pronounced hollowing phenomenon, phosphorylated nZVI can instantly reduce and immobilize Ni^II throughout the oxide shell with a high capacity (258 mg Ni g^-1  Fe). For real electroplating factory wastewater treatment, this novel nZVI performs simultaneous Ni^II and Cu^II removal, producing effluent of stable quality that meets local discharge regulations.