Spontaneous FeIII/FeII redox cycling in single-atom catalysts: Conjugation effect and electron delocalization

iScience. 2022 Dec 28;26(1):105902. doi: 10.1016/j.isci.2022.105902. eCollection 2023 Jan 20.

ABSTRACT

The mechanism of spontaneous FeIII/FeII redox cycling in iron-centered single-atom catalysts (I-SACs) is often overlooked. Consequently, pathways for continuous SO4 ·-/HO⋅ generation during peroxymonosulfate (PMS) activation by I-SACs remain unclear. Herein, the evolution of the iron center and ligand in I-SACs was comprehensively investigated. I-SACs could be considered as a coordination complex created by iron and a heteroatom N-doped carbonaceous ligand. The ligand-field theory could well explain the electronic behavior of the complex, whereby electrons delocalized by the conjugation effect of the ligand were confirmed to be responsible for the FeIII/FeII redox cycle. The possible pyridinic ligand in I-SACs was demonstrably weaker than the pyrrolic ligand in FeIII reduction due to its shielding effect on delocalized π orbitals by local lone-pair electrons. The results of this study significantly advance our understanding of the mechanism of spontaneous FeIII/FeII redox cycling and radical generation pathways in the I-SACs/PMS process.

PMID:36691626 | PMC:PMC9860487 | DOI:10.1016/j.isci.2022.105902

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