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Title: Reactivity Differences of Nanocrystals and Continuous Films of α-Fe2O3 on Au(111) Studied with In Situ X-ray Photoelectron Spectroscopy

Journal Article · · Journal of Physical Chemistry. C
DOI:https://doi.org/10.1021/jp1085697· OSTI ID:1015217
 [1];  [1];  [1];  [1];  [2];  [3]
  1. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Cukurova Univ., Adana (Turkey) Dept. of Physics
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The interaction of CO with nanocrystals and continuous films of α-Fe2O3 grown on Au(111) was investigated using in situ X-ray photoelectron spectroscopy (XPS) at near ambient pressure (200 mTorr) and scanning tunneling microscopy (STM). Adsorbed CO was detected by XPS when α-Fe2O3 nanocrystals (6-7 nm) grown on Au(111) were exposed to 200 mTorr of the gas at room temperature. Under a low H2O background, surface bound hydroxyl groups (adsorbed OH) were also noted on these α-Fe2O3 nanocrystals as a result of H2O dissociation on the edges of the particles. Adsorbed formate (HCOO-) was detected during heating to 373 K and believed to originate from the reaction of adsorbed CO with the OH groups. The adsorbed formate desorbed or decomposed above 473 K. Continuous α-Fe2O3 thin films on Au(111) were inert under the same conditions studied for nanocrystalline α-Fe2O3. Specifically, neither adsorbed CO nor OH groups were observed for the continuous films of α-Fe2O3. This reactivity difference can be explained by the presence of α-Fe2O3 crystal edges and the interface which exists between the α-Fe2O3 nanocrystals and the Au(111) substrate. These edges and interfaces are present for the nanocrystalline α-Fe2O3/Au(111) system but are not present in significant amounts for the continuous films of α-Fe2O3. The implications of these experimental results for the water-gas shift reaction will be also discussed.

Research Organization:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)
Sponsoring Organization:
USDOE Assistant Secretary for Fossil Energy (FE)
OSTI ID:
1015217
Report Number(s):
NETL-TPR-3182
Journal Information:
Journal of Physical Chemistry. C, Vol. 114, Issue 51; ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English