Carbon-carbon bond formation on model titanium oxide surfaces

identification of surface reaction intermediates by high-resolution electron energy loss spectroscopy

Hengshan Qiu, Hicham Idriss, Yuemin Wang, Christof Woell

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

The interaction of CH2O with perfect and defective TiO2(110) surfaces (produced by overannealing and Ar ion sputtering methods) was studied by thermal desorption spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT) calculations. Exposing the perfect TiO2(110) surface to CH2O at 100 K leads to the formation of physisorbed CH2O and to polymerization of CH2O, yielding paraformaldehyde. The latter is bound to the 5-fold coordinated surface Ti atoms and is found to decompose and release CH2O at about 270 K. On the defective TiO2(110) surface, CH2O adsorbs more strongly on oxygen vacancy sites, ultimately forming a diolate (-OCH2CH2O-) species, as demonstrated by HREELS. The assignment of the vibrational frequencies was aided by theoretical calculations on the DFT-B3LYP level. Upon heating to higher temperatures, this species undergoes deoxygenation, resulting in ethylene formation.

Original languageEnglish
Pages (from-to)9828-9834
Number of pages7
JournalThe Journal of Physical Chemistry C
Volume112
Issue number26
Early online date10 Jun 2008
DOIs
Publication statusPublished - 3 Jul 2008

Keywords

  • single-crystal surfaces
  • RUO2(110) surfaces
  • TIO2(110) surface
  • RU(1120) surface
  • McMurry reaction
  • active-sites
  • adsorption
  • oxidation
  • oxygen
  • formaldehyde

Cite this

Carbon-carbon bond formation on model titanium oxide surfaces : identification of surface reaction intermediates by high-resolution electron energy loss spectroscopy. / Qiu, Hengshan; Idriss, Hicham; Wang, Yuemin; Woell, Christof.

In: The Journal of Physical Chemistry C, Vol. 112, No. 26, 03.07.2008, p. 9828-9834.

Research output: Contribution to journalArticle

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title = "Carbon-carbon bond formation on model titanium oxide surfaces: identification of surface reaction intermediates by high-resolution electron energy loss spectroscopy",
abstract = "The interaction of CH2O with perfect and defective TiO2(110) surfaces (produced by overannealing and Ar ion sputtering methods) was studied by thermal desorption spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT) calculations. Exposing the perfect TiO2(110) surface to CH2O at 100 K leads to the formation of physisorbed CH2O and to polymerization of CH2O, yielding paraformaldehyde. The latter is bound to the 5-fold coordinated surface Ti atoms and is found to decompose and release CH2O at about 270 K. On the defective TiO2(110) surface, CH2O adsorbs more strongly on oxygen vacancy sites, ultimately forming a diolate (-OCH2CH2O-) species, as demonstrated by HREELS. The assignment of the vibrational frequencies was aided by theoretical calculations on the DFT-B3LYP level. Upon heating to higher temperatures, this species undergoes deoxygenation, resulting in ethylene formation.",
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T2 - identification of surface reaction intermediates by high-resolution electron energy loss spectroscopy

AU - Qiu, Hengshan

AU - Idriss, Hicham

AU - Wang, Yuemin

AU - Woell, Christof

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N2 - The interaction of CH2O with perfect and defective TiO2(110) surfaces (produced by overannealing and Ar ion sputtering methods) was studied by thermal desorption spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT) calculations. Exposing the perfect TiO2(110) surface to CH2O at 100 K leads to the formation of physisorbed CH2O and to polymerization of CH2O, yielding paraformaldehyde. The latter is bound to the 5-fold coordinated surface Ti atoms and is found to decompose and release CH2O at about 270 K. On the defective TiO2(110) surface, CH2O adsorbs more strongly on oxygen vacancy sites, ultimately forming a diolate (-OCH2CH2O-) species, as demonstrated by HREELS. The assignment of the vibrational frequencies was aided by theoretical calculations on the DFT-B3LYP level. Upon heating to higher temperatures, this species undergoes deoxygenation, resulting in ethylene formation.

AB - The interaction of CH2O with perfect and defective TiO2(110) surfaces (produced by overannealing and Ar ion sputtering methods) was studied by thermal desorption spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT) calculations. Exposing the perfect TiO2(110) surface to CH2O at 100 K leads to the formation of physisorbed CH2O and to polymerization of CH2O, yielding paraformaldehyde. The latter is bound to the 5-fold coordinated surface Ti atoms and is found to decompose and release CH2O at about 270 K. On the defective TiO2(110) surface, CH2O adsorbs more strongly on oxygen vacancy sites, ultimately forming a diolate (-OCH2CH2O-) species, as demonstrated by HREELS. The assignment of the vibrational frequencies was aided by theoretical calculations on the DFT-B3LYP level. Upon heating to higher temperatures, this species undergoes deoxygenation, resulting in ethylene formation.

KW - single-crystal surfaces

KW - RUO2(110) surfaces

KW - TIO2(110) surface

KW - RU(1120) surface

KW - McMurry reaction

KW - active-sites

KW - adsorption

KW - oxidation

KW - oxygen

KW - formaldehyde

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JO - The Journal of Physical Chemistry C

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