Tetragonal-Like Phase in Core–Shell Iron Iron-Oxide Nanoclusters

Kaur, Maninder; McCloy, John S.; Kukkadapu, Ravi; Pearce, Carolyn; Tucek, Jiri; Bowden, Mark; Engelhard, Mark; Arenholz, Elke; Qiang, You

doi:10.1021/acs.jpcc.7b01469

Title: Tetragonal-Like Phase in Core–Shell Iron Iron-Oxide Nanoclusters

Journal Article · Fri May 05 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b01469· OSTI ID:1368113

^[1];

^[2]; Kukkadapu, Ravi ^[3]; Pearce, Carolyn ^[4];

^[5]; Bowden, Mark ^[3]; Engelhard, Mark ^[3]; Arenholz, Elke ^[6]; Qiang, You ^[1]

University of Idaho, Moscow, ID (United States)
Washington State University, Pullman, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Palacky University, Olomouc (Czech Republic)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Two sizes of iron/iron-oxide (Fe/Fe-oxide) nanoclusters (NCs) of 10 and 35 nm diameters were prepared using a cluster deposition technique. Both these NCs displayed X-ray diffraction (XRD) peaks due to body-centered cubic (BCC) Fe⁰ and magnetite-like phase. ⁵⁷Fe Mössbauer spectroscopy measurements confirmed (a) the core–shell nature of the NCs, (b) the Fe-oxide shell to be nanocrystalline and partially oxidized beyond magnetite, and (c) the Fe-oxide spins are significantly canted. In addition to the BCC Fe and magnetite-like phases, a phase similar to tetragonal σ-Fe-Cr (8% Cr) was clearly evident in the larger NC, based on XRD. The origin of the tetragonal-like phase in the larger NC could be due to significant distortion of the Fe⁰ core lattice planes; subtle peaks due to this phase were also apparent in the smaller NC. Unambiguous evidence for the presence of such a phase was not clear from X-ray photoelectron spectroscopy, vibrating sample magnetometry, X-ray magnetic circular dichroism, or transmission electron microscopy. ⁵⁷Fe Mössbauer spectroscopy, however, provided support for a non-BCC Fe⁰ phase in the strongest sixth and the first resonance lines of the Fe⁰ sextet. So to our knowledge, this is the first report of a tetragonal-like phase in the Fe/Fe-oxide core–shell systems.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Education, Youth and Sports of the Czech Republic

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830; FC07-08ID14926; FG02-07ER46386

OSTI ID:: 1368113

Report Number(s):: PNNL-SA-124063; 35204; KP1704020

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 21; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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