Depletable peroxidase-like activity of Fe3O4 nanozymes accompanied with separate migration of electrons and iron ions

Abstract

As pioneering Fe₃O₄ nanozymes, their explicit peroxidase (POD)-like catalytic mechanism remains elusive. Although many studies have proposed surface Fe²⁺-induced Fenton-like reactions accounting for their POD-like activity, few have focused on the internal atomic changes and their contribution to the catalytic reaction. Here we report that Fe²⁺ within Fe₃O₄ can transfer electrons to the surface via the Fe²⁺-O-Fe³⁺ chain, regenerating the surface Fe²⁺ and enabling a sustained POD-like catalytic reaction. This process usually occurs with the outward migration of excess oxidized Fe³⁺ from the lattice, which is a rate-limiting step. After prolonged catalysis, Fe₃O₄ nanozymes suffer the phase transformation to γ-Fe₂O₃ with depletable POD-like activity. This self-depleting characteristic of nanozymes with internal atoms involved in electron transfer and ion migration is well validated on lithium iron phosphate nanoparticles. We reveal a neglected issue concerning the necessity of considering both surface and internal atoms when designing, modulating, and applying nanozymes.