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Depletable peroxidase-like activity of Fe3O4 nanozymes accompanied with separate migration of electrons and iron ions
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Depletable peroxidase-like activity of Fe3O4 nanozymes accompanied with separate migration of electrons and iron ions
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Journal Article
Depletable peroxidase-like activity of Fe3O4 nanozymes accompanied with separate migration of electrons and iron ions
2022
Overview
As pioneering Fe
3
O
4
nanozymes, their explicit peroxidase (POD)-like catalytic mechanism remains elusive. Although many studies have proposed surface Fe
2+
-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 Fe
2+
within Fe
3
O
4
can transfer electrons to the surface via the Fe
2+
-O-Fe
3+
chain, regenerating the surface Fe
2+
and enabling a sustained POD-like catalytic reaction. This process usually occurs with the outward migration of excess oxidized Fe
3+
from the lattice, which is a rate-limiting step. After prolonged catalysis, Fe
3
O
4
nanozymes suffer the phase transformation to γ-Fe
2
O
3
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.
The mechanism of peroxidase-like Fe
3
O
4
nanozymes remains elusive. Here, the authors show the electron transfer mechanism of Fe(II) ions to regenerate surface Fe(II) and the related phase transformation and depletion of activity.
