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Title: Insights into the (1x1)-to-(2x1) Phase Transition of the alpha-Fe2O3(012) Surface Using EELS, LEED and Water TPD

Abstract

The (1x1)-to-(2x1) surface reconstruction of alpha-Fe2O3(012) (also known as the R-cut or (011- 2) surface) was examined using low energy electron diffraction (LEED), electron energy loss spectroscopy (EELS) and temperature programmed desorption (TPD). The (1x1) surface is generated by heating in 5 x 10-7 torr O2 at 750 K, followed by cooling in O2. The surface prepared in this manner exhibits a p(1x1) LEED pattern consistent with a bulk-terminated structure. EELS analysis of this surface shows a 2 eV bandgap consistent with that of hematite and little or no evidence for Fe2+ surface sites. In contrast, a (2x1) LEED pattern is observed after annealing the (1x1) surface in UHV at 950 K. The EELS spectrum of the (2x1) surface exhibits a prominent loss feature at about 1 eV, which is consistent with Fe2+ sites. The (2x1) surface prepared by annealing at 950 K does not consist of a termination film of Fe3O4, as has been reported in the literature for the (001) surface, since the phonon spectrum remains consistent with that of alpha-Fe2O3. Both LEED and EELS detect the onset of the (1x1)-to-(2x1) reconstruction process to be at 700 K, whereas water TPD, which shows distinctively different desorption features formore » those two surface phases, detects the onset to occur at about 600 K. The (1x1)-to-(2x1) surface reconstruction process appears to be highly nucleated based on observations that the (2x1) LEED spots grow in during annealing without streaking and that coverage-dependent water TPD for a half (1x1) - half (2x1) surface shows simultaneous filling of both (1x1) and (2x1) binding sites. Given that the reconstruction process is accompanied by reduction of Fe3+ surface sites to Fe2+ sites, the preference for growth of existing (2x1) domains over initiation of new (2x1) domains implies that the kinetics for hematite reduction (i.e., Fe2+ formation) are more favorable in the vicinity of other Fe2+ sites than in regions rich in Fe3+.« less

Authors:
 [1]
  1. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab., Richland, WA (US)
Sponsoring Org.:
US Department of Energy (US)
OSTI Identifier:
15001628
Report Number(s):
PNNL-SA-36598
KC0201010; TRN: US200406%%92
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Journal Article
Journal Name:
Surface Science
Additional Journal Information:
Journal Volume: 515; Journal Issue: 1; Other Information: PBD: 1 Jan 2002
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; ANNEALING; DESORPTION; ELECTRON DIFFRACTION; ELECTRONS; ENERGY-LOSS SPECTROSCOPY; HEATING; HEMATITE; KINETICS; PHONONS; WATER; LEED; EELS; TPD; FE3+; FE2+

Citation Formats

Henderson, Michael A. Insights into the (1x1)-to-(2x1) Phase Transition of the alpha-Fe2O3(012) Surface Using EELS, LEED and Water TPD. United States: N. p., 2002. Web. doi:10.1016/S0039-6028(02)01917-9.
Henderson, Michael A. Insights into the (1x1)-to-(2x1) Phase Transition of the alpha-Fe2O3(012) Surface Using EELS, LEED and Water TPD. United States. doi:10.1016/S0039-6028(02)01917-9.
Henderson, Michael A. Tue . "Insights into the (1x1)-to-(2x1) Phase Transition of the alpha-Fe2O3(012) Surface Using EELS, LEED and Water TPD". United States. doi:10.1016/S0039-6028(02)01917-9.
@article{osti_15001628,
title = {Insights into the (1x1)-to-(2x1) Phase Transition of the alpha-Fe2O3(012) Surface Using EELS, LEED and Water TPD},
author = {Henderson, Michael A},
abstractNote = {The (1x1)-to-(2x1) surface reconstruction of alpha-Fe2O3(012) (also known as the R-cut or (011- 2) surface) was examined using low energy electron diffraction (LEED), electron energy loss spectroscopy (EELS) and temperature programmed desorption (TPD). The (1x1) surface is generated by heating in 5 x 10-7 torr O2 at 750 K, followed by cooling in O2. The surface prepared in this manner exhibits a p(1x1) LEED pattern consistent with a bulk-terminated structure. EELS analysis of this surface shows a 2 eV bandgap consistent with that of hematite and little or no evidence for Fe2+ surface sites. In contrast, a (2x1) LEED pattern is observed after annealing the (1x1) surface in UHV at 950 K. The EELS spectrum of the (2x1) surface exhibits a prominent loss feature at about 1 eV, which is consistent with Fe2+ sites. The (2x1) surface prepared by annealing at 950 K does not consist of a termination film of Fe3O4, as has been reported in the literature for the (001) surface, since the phonon spectrum remains consistent with that of alpha-Fe2O3. Both LEED and EELS detect the onset of the (1x1)-to-(2x1) reconstruction process to be at 700 K, whereas water TPD, which shows distinctively different desorption features for those two surface phases, detects the onset to occur at about 600 K. The (1x1)-to-(2x1) surface reconstruction process appears to be highly nucleated based on observations that the (2x1) LEED spots grow in during annealing without streaking and that coverage-dependent water TPD for a half (1x1) - half (2x1) surface shows simultaneous filling of both (1x1) and (2x1) binding sites. Given that the reconstruction process is accompanied by reduction of Fe3+ surface sites to Fe2+ sites, the preference for growth of existing (2x1) domains over initiation of new (2x1) domains implies that the kinetics for hematite reduction (i.e., Fe2+ formation) are more favorable in the vicinity of other Fe2+ sites than in regions rich in Fe3+.},
doi = {10.1016/S0039-6028(02)01917-9},
journal = {Surface Science},
number = 1,
volume = 515,
place = {United States},
year = {2002},
month = {1}
}