DFF study of carboxylic acids modes of adsorption on rutile TiO2(011) surfaces

P. R. McGill, Hicham Idriss

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Plane wave density functional theory (PWDFT) has been employed to study the energy and structure of formic and acetic acids dissociative adsorption on rutile TiO2(011) surfaces. Both the bulk terminated (1 x 1) and reconstructed (2 x 1) surfaces were considered. On both surfaces the bridging (bidentate) configuration was found more stable than the monodentate configuration for formate species by 2540 kJ mol(-1). The difference in stability between the bridging and monodentate species is more pronounced in the case of acetates on the 2 x 1 reconstructed surface where the former adsorption was found equal to 162 kJ mol(-1) while the latter dropped to 100 kJ mol(-1). The decrease in stability of the monodentate configuration in the case of acetate species is attributed to the considerable repulsion between the methyl group and terminal Ti=O groups. Analyses of the density of states indicated that while the dissociated adsorption of formic acid on the 2 x I reconstructed surface appears complete with a clear formation of surface hydroxyl that on the 1 x 1 surface may still involve electron sharing between surface hydroxyls and the formate species, The chelating mode, whereby the two oxygen atoms of the carboxylate species are in close proximity with one surface Ti atoms was found unstable for both acids and on both surfaces. Comparison with experimental TPD results of carboxylic acids over the rutile TiO2 (011) surface is presented and discussed. (C) 2008 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)3688-3695
Number of pages8
JournalSurface Science Reports
Volume602
Issue number24
Early online date17 Oct 2008
DOIs
Publication statusPublished - 15 Dec 2008

Keywords

  • TiO2(011) surface
  • Formic acid
  • Acetic acid
  • Density functional theory (OFT)
  • Adsorption energy
  • Bidentate
  • Density of state (DOS)
  • Lowdin population analysis
  • Single-crystal surfaces
  • Formic-acid
  • TIO2(110) surface
  • Photocatalytic reactions
  • Dissociative adsorption
  • Reaction pathways
  • Acetic-Acid
  • TIO2
  • Decomposition
  • 1st-principles

Cite this

DFF study of carboxylic acids modes of adsorption on rutile TiO2(011) surfaces. / McGill, P. R.; Idriss, Hicham.

In: Surface Science Reports, Vol. 602, No. 24, 15.12.2008, p. 3688-3695.

Research output: Contribution to journalArticle

McGill, P. R. ; Idriss, Hicham. / DFF study of carboxylic acids modes of adsorption on rutile TiO2(011) surfaces. In: Surface Science Reports. 2008 ; Vol. 602, No. 24. pp. 3688-3695.
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N2 - Plane wave density functional theory (PWDFT) has been employed to study the energy and structure of formic and acetic acids dissociative adsorption on rutile TiO2(011) surfaces. Both the bulk terminated (1 x 1) and reconstructed (2 x 1) surfaces were considered. On both surfaces the bridging (bidentate) configuration was found more stable than the monodentate configuration for formate species by 2540 kJ mol(-1). The difference in stability between the bridging and monodentate species is more pronounced in the case of acetates on the 2 x 1 reconstructed surface where the former adsorption was found equal to 162 kJ mol(-1) while the latter dropped to 100 kJ mol(-1). The decrease in stability of the monodentate configuration in the case of acetate species is attributed to the considerable repulsion between the methyl group and terminal Ti=O groups. Analyses of the density of states indicated that while the dissociated adsorption of formic acid on the 2 x I reconstructed surface appears complete with a clear formation of surface hydroxyl that on the 1 x 1 surface may still involve electron sharing between surface hydroxyls and the formate species, The chelating mode, whereby the two oxygen atoms of the carboxylate species are in close proximity with one surface Ti atoms was found unstable for both acids and on both surfaces. Comparison with experimental TPD results of carboxylic acids over the rutile TiO2 (011) surface is presented and discussed. (C) 2008 Elsevier B.V. All rights reserved.

AB - Plane wave density functional theory (PWDFT) has been employed to study the energy and structure of formic and acetic acids dissociative adsorption on rutile TiO2(011) surfaces. Both the bulk terminated (1 x 1) and reconstructed (2 x 1) surfaces were considered. On both surfaces the bridging (bidentate) configuration was found more stable than the monodentate configuration for formate species by 2540 kJ mol(-1). The difference in stability between the bridging and monodentate species is more pronounced in the case of acetates on the 2 x 1 reconstructed surface where the former adsorption was found equal to 162 kJ mol(-1) while the latter dropped to 100 kJ mol(-1). The decrease in stability of the monodentate configuration in the case of acetate species is attributed to the considerable repulsion between the methyl group and terminal Ti=O groups. Analyses of the density of states indicated that while the dissociated adsorption of formic acid on the 2 x I reconstructed surface appears complete with a clear formation of surface hydroxyl that on the 1 x 1 surface may still involve electron sharing between surface hydroxyls and the formate species, The chelating mode, whereby the two oxygen atoms of the carboxylate species are in close proximity with one surface Ti atoms was found unstable for both acids and on both surfaces. Comparison with experimental TPD results of carboxylic acids over the rutile TiO2 (011) surface is presented and discussed. (C) 2008 Elsevier B.V. All rights reserved.

KW - TiO2(011) surface

KW - Formic acid

KW - Acetic acid

KW - Density functional theory (OFT)

KW - Adsorption energy

KW - Bidentate

KW - Density of state (DOS)

KW - Lowdin population analysis

KW - Single-crystal surfaces

KW - Formic-acid

KW - TIO2(110) surface

KW - Photocatalytic reactions

KW - Dissociative adsorption

KW - Reaction pathways

KW - Acetic-Acid

KW - TIO2

KW - Decomposition

KW - 1st-principles

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DO - 10.1016/j.susc.2008.10.010

M3 - Article

VL - 602

SP - 3688

EP - 3695

JO - Surface Science Reports

JF - Surface Science Reports

SN - 0167-5729

IS - 24

ER -