Fenton-like Reactivity on Fe3O4 Nanozymes Driven by Charge Transfer and Interfacial Water

Magnetite (Fe3O4) nanoparticles, widely recognized as inorganic nanozymes due to their enzyme-like catalytic activity, are emerging as effective heterogeneous catalysts for Fenton-like reactions, in which lattice iron activates hydrogen peroxide (H2O2) to generate reactive oxygen species. While hydr...

ver descrição completa

Detalhes bibliográficos
Autores: Sánchez, Verónica Muriel, Lima, Enio, Grassano, Juan Santiago, Lustemberg, Pablo G., Morales Ovalle, Marco Antonio, Vasquez Mansilla, Marcelo, Daneri, Juan, Estrin, Darío Ariel, Winkler, Elin Lilian, Ganduglia-Pirovano, M. V.
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2026
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/422501
Acesso em linha:http://hdl.handle.net/10261/422501
https://api.elsevier.com/content/abstract/scopus_id/105021985817
Access Level:Acceso aberto
Palavra-chave:density functional theory calculations
Fenton‐like catalysis
ferryl intermediate
magnetite nanoparticles
nanozymes
Descrição
Resumo:Magnetite (Fe3O4) nanoparticles, widely recognized as inorganic nanozymes due to their enzyme-like catalytic activity, are emerging as effective heterogeneous catalysts for Fenton-like reactions, in which lattice iron activates hydrogen peroxide (H2O2) to generate reactive oxygen species. While hydroxyl radicals (•OH) are generally considered the primary reactive species, the underlying mechanism-particularly the possible involvement of a high-valent ferryl intermediate (Fe4+═O)-remains under debate. Here, surface-specific spectroscopy with density functional theory (DFT) calculations is used to elucidate the mechanism of H2O2 activation on Fe3O4(001) surfaces. It is found that •OH production is driven by electron transfer from subsurface Fe2⁺ centers to adsorbed H2O2, accompanied by the transient formation of a ferryl species. Moreover, interfacial water plays an active role in modulating surface reactivity and stabilizing key reaction intermediates. These findings clarify the origin of radical formation in Fe3O4 nanozymes and offer mechanistic insight to guide the rational design of next-generation oxide-based catalysts for environmental and biomedical applications.