The reactions of water vapour on the surfaces of stoichiometric and reduced uranium dioxide: A high resolution XPS study

S. D. Senanayake, G. I. N. Waterhouse, A. S. Y. Chan, T. E. Madey, D. R. Mullins, Hicham Idriss

Research output: Contribution to journalArticle

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Abstract

The reaction of water with stoichiometric and O-defective UO2 thin film surfaces is studied by high-resolution photoelectron spectroscopy using synchrotron X-rays radiation. The decomposition of D2O molecules and the oxidative healing of defects on the reduced surfaces was observed and quantified. D2O adsorption on the stoichiometric UO2 surface at 300 K showed small amounts of OD species (ca. 532 eV) probably formed on trace amounts of surface defects, while at 95 K D2O ice (533.5 eV) was the main surface species. On the contrary, a large signal of OD species was seen on the 300 K-Ar+-sputtered (reduced) surface, UO2-x. This was concomitant with a rapid healing of surface defects as monitored by their U4f signal. Quantitative analysis of the OD signal with increasing temperature showed their disappearance by 550 K. The disappearance of these species while hydrogen molecules are still desorbing from the surface as monitored by TPD [S.D. Senanayake, H. Idriss, Surf. Sci. 563 (1-3) (2004) 135; S.D. Senanayake, R. Rousseau, D. Colegrave, H. Idriss, J. Nucl. Mater. 342 (2005) 179] is shedding light on the re-combinative desorption mechanism from dissociatively adsorbed water molecules on the surfaces of this defective metal oxide. (c) 2006 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)151-157
Number of pages7
JournalCatalysis Today
Volume120
Issue number2
Early online date22 Aug 2006
DOIs
Publication statusPublished - 15 Feb 2007

Keywords

  • uranium oxides
  • synchrotron radiation
  • XPS
  • TPXPS
  • UO2-x
  • UO2
  • U4f
  • O1s
  • argon-ions sputtering
  • D2O
  • surface hydroxyls
  • UO2(111) single-crystal
  • polycrystalline UO2
  • monoxide
  • adsorption
  • oxidation

Cite this

Senanayake, S. D., Waterhouse, G. I. N., Chan, A. S. Y., Madey, T. E., Mullins, D. R., & Idriss, H. (2007). The reactions of water vapour on the surfaces of stoichiometric and reduced uranium dioxide: A high resolution XPS study. Catalysis Today, 120(2), 151-157. https://doi.org/10.1016/j.cattod.2006.07.040

The reactions of water vapour on the surfaces of stoichiometric and reduced uranium dioxide : A high resolution XPS study. / Senanayake, S. D.; Waterhouse, G. I. N.; Chan, A. S. Y.; Madey, T. E.; Mullins, D. R.; Idriss, Hicham.

In: Catalysis Today, Vol. 120, No. 2, 15.02.2007, p. 151-157.

Research output: Contribution to journalArticle

Senanayake, SD, Waterhouse, GIN, Chan, ASY, Madey, TE, Mullins, DR & Idriss, H 2007, 'The reactions of water vapour on the surfaces of stoichiometric and reduced uranium dioxide: A high resolution XPS study' Catalysis Today, vol. 120, no. 2, pp. 151-157. https://doi.org/10.1016/j.cattod.2006.07.040
Senanayake, S. D. ; Waterhouse, G. I. N. ; Chan, A. S. Y. ; Madey, T. E. ; Mullins, D. R. ; Idriss, Hicham. / The reactions of water vapour on the surfaces of stoichiometric and reduced uranium dioxide : A high resolution XPS study. In: Catalysis Today. 2007 ; Vol. 120, No. 2. pp. 151-157.
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T2 - A high resolution XPS study

AU - Senanayake, S. D.

AU - Waterhouse, G. I. N.

AU - Chan, A. S. Y.

AU - Madey, T. E.

AU - Mullins, D. R.

AU - Idriss, Hicham

PY - 2007/2/15

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N2 - The reaction of water with stoichiometric and O-defective UO2 thin film surfaces is studied by high-resolution photoelectron spectroscopy using synchrotron X-rays radiation. The decomposition of D2O molecules and the oxidative healing of defects on the reduced surfaces was observed and quantified. D2O adsorption on the stoichiometric UO2 surface at 300 K showed small amounts of OD species (ca. 532 eV) probably formed on trace amounts of surface defects, while at 95 K D2O ice (533.5 eV) was the main surface species. On the contrary, a large signal of OD species was seen on the 300 K-Ar+-sputtered (reduced) surface, UO2-x. This was concomitant with a rapid healing of surface defects as monitored by their U4f signal. Quantitative analysis of the OD signal with increasing temperature showed their disappearance by 550 K. The disappearance of these species while hydrogen molecules are still desorbing from the surface as monitored by TPD [S.D. Senanayake, H. Idriss, Surf. Sci. 563 (1-3) (2004) 135; S.D. Senanayake, R. Rousseau, D. Colegrave, H. Idriss, J. Nucl. Mater. 342 (2005) 179] is shedding light on the re-combinative desorption mechanism from dissociatively adsorbed water molecules on the surfaces of this defective metal oxide. (c) 2006 Elsevier B.V. All rights reserved.

AB - The reaction of water with stoichiometric and O-defective UO2 thin film surfaces is studied by high-resolution photoelectron spectroscopy using synchrotron X-rays radiation. The decomposition of D2O molecules and the oxidative healing of defects on the reduced surfaces was observed and quantified. D2O adsorption on the stoichiometric UO2 surface at 300 K showed small amounts of OD species (ca. 532 eV) probably formed on trace amounts of surface defects, while at 95 K D2O ice (533.5 eV) was the main surface species. On the contrary, a large signal of OD species was seen on the 300 K-Ar+-sputtered (reduced) surface, UO2-x. This was concomitant with a rapid healing of surface defects as monitored by their U4f signal. Quantitative analysis of the OD signal with increasing temperature showed their disappearance by 550 K. The disappearance of these species while hydrogen molecules are still desorbing from the surface as monitored by TPD [S.D. Senanayake, H. Idriss, Surf. Sci. 563 (1-3) (2004) 135; S.D. Senanayake, R. Rousseau, D. Colegrave, H. Idriss, J. Nucl. Mater. 342 (2005) 179] is shedding light on the re-combinative desorption mechanism from dissociatively adsorbed water molecules on the surfaces of this defective metal oxide. (c) 2006 Elsevier B.V. All rights reserved.

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KW - UO2-x

KW - UO2

KW - U4f

KW - O1s

KW - argon-ions sputtering

KW - D2O

KW - surface hydroxyls

KW - UO2(111) single-crystal

KW - polycrystalline UO2

KW - monoxide

KW - adsorption

KW - oxidation

U2 - 10.1016/j.cattod.2006.07.040

DO - 10.1016/j.cattod.2006.07.040

M3 - Article

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SP - 151

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JO - Catalysis Today

JF - Catalysis Today

SN - 0920-5861

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ER -