Trends within the adsorption energy of alcohols over rutile TiO2(110) and (011) clusters

L Kieu, P Boyd, Hicham Idriss

Research output: Contribution to journalArticle

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Abstract

The non-dissociative adsorption energy of a series of alcohols over a rutile Ti8O29H26 cluster, representing the TiO2(0 1 1) surface, as well as over a rutile Ti11O42H40 cluster, representing the TiO2(1 1 0) surface, was computed by means of a semi-empirical PM3 method. Over TiO2 (0 1 1) Surface the non-dissociative adsorption energy of methanol, ethanol, n-propanol and i-propanol were 1.29, 1.46, 2.08, and 2.40 eV, respectively. This trend can reasonably be explained by gas phase acidity, as measured by their relative (to methanol) polarizability. On the other hand, the same series investigated over TiO2(1 1 0) gave the following adsorption energy values: 1.49, 1.60, 1.96, and 1.94 eV, respectively, The relatively low adsorption energy for i-propanol, shows a deviation from the expected correlation. The reason for that is most likely structural. While TiO2(1 1 0) surface contains Ti4+ cations five- and six-fold coordinated to oxygen, TiO2(0 1 1) surface contains Ti4+ all in a five-fold coordination environment. Thus, it appears that the alternating rows of bridging oxygen anions of the (I 10) surface exert a repulsive interaction over the two-methyl groups of i-propanol decreasing its adsorption energy. (C) 2002 Published by Elsevier Science B.V.

Original languageEnglish
Pages (from-to)153-161
Number of pages9
JournalJournal of Molecular Catalysis A: Chemical
Volume188
Issue number1-2
Publication statusPublished - 30 Sep 2002

Keywords

  • adsorption energy
  • rutile
  • adsorbates
  • ELECTRON-DIFFRACTION
  • TIO2(001) SURFACE
  • CRYSTAL-SURFACES
  • TIO2 SURFACES
  • FORMIC-ACID
  • FORMALDEHYDE
  • DISSOCIATION
  • MICROSCOPY
  • REDUCTION
  • PATHWAYS

Cite this

Trends within the adsorption energy of alcohols over rutile TiO2(110) and (011) clusters. / Kieu, L ; Boyd, P ; Idriss, Hicham.

In: Journal of Molecular Catalysis A: Chemical, Vol. 188, No. 1-2, 30.09.2002, p. 153-161.

Research output: Contribution to journalArticle

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N2 - The non-dissociative adsorption energy of a series of alcohols over a rutile Ti8O29H26 cluster, representing the TiO2(0 1 1) surface, as well as over a rutile Ti11O42H40 cluster, representing the TiO2(1 1 0) surface, was computed by means of a semi-empirical PM3 method. Over TiO2 (0 1 1) Surface the non-dissociative adsorption energy of methanol, ethanol, n-propanol and i-propanol were 1.29, 1.46, 2.08, and 2.40 eV, respectively. This trend can reasonably be explained by gas phase acidity, as measured by their relative (to methanol) polarizability. On the other hand, the same series investigated over TiO2(1 1 0) gave the following adsorption energy values: 1.49, 1.60, 1.96, and 1.94 eV, respectively, The relatively low adsorption energy for i-propanol, shows a deviation from the expected correlation. The reason for that is most likely structural. While TiO2(1 1 0) surface contains Ti4+ cations five- and six-fold coordinated to oxygen, TiO2(0 1 1) surface contains Ti4+ all in a five-fold coordination environment. Thus, it appears that the alternating rows of bridging oxygen anions of the (I 10) surface exert a repulsive interaction over the two-methyl groups of i-propanol decreasing its adsorption energy. (C) 2002 Published by Elsevier Science B.V.

AB - The non-dissociative adsorption energy of a series of alcohols over a rutile Ti8O29H26 cluster, representing the TiO2(0 1 1) surface, as well as over a rutile Ti11O42H40 cluster, representing the TiO2(1 1 0) surface, was computed by means of a semi-empirical PM3 method. Over TiO2 (0 1 1) Surface the non-dissociative adsorption energy of methanol, ethanol, n-propanol and i-propanol were 1.29, 1.46, 2.08, and 2.40 eV, respectively. This trend can reasonably be explained by gas phase acidity, as measured by their relative (to methanol) polarizability. On the other hand, the same series investigated over TiO2(1 1 0) gave the following adsorption energy values: 1.49, 1.60, 1.96, and 1.94 eV, respectively, The relatively low adsorption energy for i-propanol, shows a deviation from the expected correlation. The reason for that is most likely structural. While TiO2(1 1 0) surface contains Ti4+ cations five- and six-fold coordinated to oxygen, TiO2(0 1 1) surface contains Ti4+ all in a five-fold coordination environment. Thus, it appears that the alternating rows of bridging oxygen anions of the (I 10) surface exert a repulsive interaction over the two-methyl groups of i-propanol decreasing its adsorption energy. (C) 2002 Published by Elsevier Science B.V.

KW - adsorption energy

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KW - TIO2 SURFACES

KW - FORMIC-ACID

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KW - REDUCTION

KW - PATHWAYS

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