Effective functionalization of disordered oxide lattices on iron particle surfaces using mechanochemical reactions

Satoshi Motozuka, Motohiro Tagaya, Hiroshi Nishiyama, Masami Nishikawa, Toshiyuki Ikoma, Tomohiko Yoshioka, Sadaki Samitsu, Junzo Tanaka

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The mechanochemical surface functionalization of iron oxides with disordered lattices on bare iron (Fe) particles was investigated using simple milling processes to clarify the formation mechanism of the oxide layer and investigate the near-surface models with different states. The homogeneous α-Fe particles at the milling equilibrium were first prepared under an argon atmosphere. After the subsequent milling reaction of the particles with oxygen molecules, the surface analyses by X-ray diffraction and Raman and X-ray photoelectron spectroscopies revealed that the near-surface layers consisted of two iron oxide phases (α-Fe2O3 and Fe 3O4) through oxygen atom diffusion, and the α-Fe2O3 was dominantly grown on the near surface. During the initial reaction, the signals from an electron spin resonance suggested the dangling bond formation on α-Fe2O3. The oxygen atoms effectively induce disordered lattices in the local area to form oxidized Fe3+ clusters, and the geometric distortion formed the dangling bonds, which were theoretically supported by a molecular orbital calculation to elucidate the increase in the unpaired electron sites on the α-Fe2O3. Therefore, the defective Fe3+ ions induced by the lattice mismatching between the clusters and bare α-Fe are found to form the disordered lattice that contains the oxygen atoms with unpaired electrons, which are successfully induced by the near-surface strain based on the simple mechanochemical reactions. The patterns of surface activation of the Fe particle surfaces by oxidization will be capable of novel chemical reactions by selective oxygen insertion as well as deep oxidation.

Original languageEnglish
Pages (from-to)9908-9919
Number of pages12
JournalJournal of Physical Chemistry C
Volume117
Issue number19
DOIs
Publication statusPublished - May 16 2013
Externally publishedYes

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Oxides
Iron
iron
oxides
Oxygen
oxygen atoms
Dangling bonds
iron oxides
Iron oxides
Atoms
Orbital calculations
oxygen
Electrons
Argon
Molecular orbitals
insertion
chemical reactions
surface layers
molecular orbitals
electron paramagnetic resonance

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Effective functionalization of disordered oxide lattices on iron particle surfaces using mechanochemical reactions. / Motozuka, Satoshi; Tagaya, Motohiro; Nishiyama, Hiroshi; Nishikawa, Masami; Ikoma, Toshiyuki; Yoshioka, Tomohiko; Samitsu, Sadaki; Tanaka, Junzo.

In: Journal of Physical Chemistry C, Vol. 117, No. 19, 16.05.2013, p. 9908-9919.

Research output: Contribution to journalArticle

Motozuka, S, Tagaya, M, Nishiyama, H, Nishikawa, M, Ikoma, T, Yoshioka, T, Samitsu, S & Tanaka, J 2013, 'Effective functionalization of disordered oxide lattices on iron particle surfaces using mechanochemical reactions', Journal of Physical Chemistry C, vol. 117, no. 19, pp. 9908-9919. https://doi.org/10.1021/jp401655m
Motozuka, Satoshi ; Tagaya, Motohiro ; Nishiyama, Hiroshi ; Nishikawa, Masami ; Ikoma, Toshiyuki ; Yoshioka, Tomohiko ; Samitsu, Sadaki ; Tanaka, Junzo. / Effective functionalization of disordered oxide lattices on iron particle surfaces using mechanochemical reactions. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 19. pp. 9908-9919.
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