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

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...

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Bibliographic Details
Published in:Nature communications 2022-09, Vol.13 (1), p.5365-11, Article 5365
Main Authors: Dong, Haijiao, Du, Wei, Dong, Jian, Che, Renchao, Kong, Fei, Cheng, Wenlong, Ma, Ming, Gu, Ning, Zhang, Yu
Format: Article
Language:English
Subjects:
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Catalysis
Depletion
Electron transfer
Electrons
Engineering
Enzymes
Ferric ions
Ferric oxide
Ferrous ions
Humanities and Social Sciences
Ion migration
Ions
Iron oxides
Iron phosphates
Laboratories
Lithium
multidisciplinary
Nanoparticles
Oxidation
Peroxidase
Phase transitions
Science
Science (multidisciplinary)
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Summary: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.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-022-33098-y