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Title: Scanning Tunneling Microscopy and Theoretical Study of Water Adsorption on Fe3O4: Implications for Catalysis

Abstract

The reduced surface of a natural Hematite single crystal a-Fe2O3(0001) sample has multiple surface domains with di!erent terminations, Fe2O3(0001), FeO(111), and Fe3O4(111). The adsorption of water on this surface was investigated via Scanning Tunneling Microscopy (STM) and first-principle theoretical simulations. Water species are observed only on the Fe-terminated Fe3O4(111) surface at temperatures up to 235 K. Between 235 and 245 K we observed a change in the surface species from intact water molecules and hydroxyl groups bound to the surface to only hydroxyl groups atop the surface terminating FeIII cations. This indicates a low energy barrier for water dissociation on the surface of Fe3O4 that is supported by our theoretical computations. Our first principles simulations con"rm the identity of the surface species proposed from the STM images, finding that the most stable state of a water molecule is the dissociated one (OH + H), with OH atop surface terminating FeIII sites and H atop under-coordinated oxygen sites. Attempts to simulate reaction of the surface OH with coadsorbed CO fail because the only binding sites for CO are the surface FeIII atoms, which are blocked by the much more strongly bound OH. In order to promote this reaction we simulated amore » surface decorated with gold atoms. The Au adatoms are found to cap the under-coordinated oxygen sites and dosed CO is found to bind to the Au adatom. This newly created binding site for CO not only allows for coexistence of CO and OH on the surface of Fe3O4 but also provides colocation between the two species. These two factors are likely promoters of catalytic activity on Au/Fe3O4(111) surfaces.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1097963
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society, 134(46):18979−18985
Additional Journal Information:
Journal Name: Journal of the American Chemical Society, 134(46):18979−18985
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Rim, Kwang T., Eom, Daejin, Chan, Siu-Wai, Flytzani-Stephanopoulos, Maria, Flynn, George, Wen, Xiaodong, and Batista, Enrique R. Scanning Tunneling Microscopy and Theoretical Study of Water Adsorption on Fe3O4: Implications for Catalysis. United States: N. p., 2012. Web. doi:10.1021/ja305294x.
Rim, Kwang T., Eom, Daejin, Chan, Siu-Wai, Flytzani-Stephanopoulos, Maria, Flynn, George, Wen, Xiaodong, & Batista, Enrique R. Scanning Tunneling Microscopy and Theoretical Study of Water Adsorption on Fe3O4: Implications for Catalysis. United States. doi:10.1021/ja305294x.
Rim, Kwang T., Eom, Daejin, Chan, Siu-Wai, Flytzani-Stephanopoulos, Maria, Flynn, George, Wen, Xiaodong, and Batista, Enrique R. Tue . "Scanning Tunneling Microscopy and Theoretical Study of Water Adsorption on Fe3O4: Implications for Catalysis". United States. doi:10.1021/ja305294x.
@article{osti_1097963,
title = {Scanning Tunneling Microscopy and Theoretical Study of Water Adsorption on Fe3O4: Implications for Catalysis},
author = {Rim, Kwang T. and Eom, Daejin and Chan, Siu-Wai and Flytzani-Stephanopoulos, Maria and Flynn, George and Wen, Xiaodong and Batista, Enrique R.},
abstractNote = {The reduced surface of a natural Hematite single crystal a-Fe2O3(0001) sample has multiple surface domains with di!erent terminations, Fe2O3(0001), FeO(111), and Fe3O4(111). The adsorption of water on this surface was investigated via Scanning Tunneling Microscopy (STM) and first-principle theoretical simulations. Water species are observed only on the Fe-terminated Fe3O4(111) surface at temperatures up to 235 K. Between 235 and 245 K we observed a change in the surface species from intact water molecules and hydroxyl groups bound to the surface to only hydroxyl groups atop the surface terminating FeIII cations. This indicates a low energy barrier for water dissociation on the surface of Fe3O4 that is supported by our theoretical computations. Our first principles simulations con"rm the identity of the surface species proposed from the STM images, finding that the most stable state of a water molecule is the dissociated one (OH + H), with OH atop surface terminating FeIII sites and H atop under-coordinated oxygen sites. Attempts to simulate reaction of the surface OH with coadsorbed CO fail because the only binding sites for CO are the surface FeIII atoms, which are blocked by the much more strongly bound OH. In order to promote this reaction we simulated a surface decorated with gold atoms. The Au adatoms are found to cap the under-coordinated oxygen sites and dosed CO is found to bind to the Au adatom. This newly created binding site for CO not only allows for coexistence of CO and OH on the surface of Fe3O4 but also provides colocation between the two species. These two factors are likely promoters of catalytic activity on Au/Fe3O4(111) surfaces.},
doi = {10.1021/ja305294x},
journal = {Journal of the American Chemical Society, 134(46):18979−18985},
number = ,
volume = ,
place = {United States},
year = {2012},
month = {10}
}