Ab initio study of surface acid-base reactions. The case of molecular and dissociative adsorption of ammonia on the (011) surface of rutile TiO2

P. R. McGill, Hicham Idriss

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The interaction of ammonia molecules with Lewis acid centers (Ti4+ metal ions) of the (011) surface of rutile TiO2 is investigated by density functional theory in order to understand, from first principle, the nature of acid-base reactions on solid surfaces. Unlike the rutile (110) surface that contains alternating rows of 5-fold and 6-fold Ti atoms, all Ti atoms of the (011) surface are 5-fold coordinated. This surface has shown considerable activity for numerous chemical reactions and is thus an ideal prototype. At -1/2 monolayer coverage, with respect to surface Ti atoms, the adsorption energy is found to be equal to 100 kJ mol(-1), and drops to 58 kJ mol(-1) at one monolayer coverage. Analysis of the electronic density of states (DOS) revealed information regarding the mode of adsorption. In particular, the nitrogen 3a(1) and 2a(1) orbitals appear to undergo significant changes upon adsorption, in agreement with photoelectron spectroscopy studies . Dissociative adsorption wa s also investigated on the same surface. Both NH2(Ti-s) + H(Os) and NH(Ti-s) + 2H(O-s,) modes of dissociative adsorption, where s stands for surface, are found to be less stable than the molecular (non dissociated) adsorption.

Original languageEnglish
Pages (from-to)97-104
Number of pages8
JournalLangmuir
Volume24
Issue number1
DOIs
Publication statusPublished - 1 Jan 2008

Keywords

  • single-crystal surfaces
  • density-functional theory
  • energy-loss spectroscopy
  • NH3 adsorption
  • electronic-structure
  • TIO2(110) surface
  • TIO2(001) surface
  • titanium-dioxide
  • desorption
  • PT(111)

Cite this

Ab initio study of surface acid-base reactions. The case of molecular and dissociative adsorption of ammonia on the (011) surface of rutile TiO2. / McGill, P. R.; Idriss, Hicham.

In: Langmuir, Vol. 24, No. 1, 01.01.2008, p. 97-104.

Research output: Contribution to journalArticle

@article{1de14f71043641d88adede268c6b4c25,
title = "Ab initio study of surface acid-base reactions. The case of molecular and dissociative adsorption of ammonia on the (011) surface of rutile TiO2",
abstract = "The interaction of ammonia molecules with Lewis acid centers (Ti4+ metal ions) of the (011) surface of rutile TiO2 is investigated by density functional theory in order to understand, from first principle, the nature of acid-base reactions on solid surfaces. Unlike the rutile (110) surface that contains alternating rows of 5-fold and 6-fold Ti atoms, all Ti atoms of the (011) surface are 5-fold coordinated. This surface has shown considerable activity for numerous chemical reactions and is thus an ideal prototype. At -1/2 monolayer coverage, with respect to surface Ti atoms, the adsorption energy is found to be equal to 100 kJ mol(-1), and drops to 58 kJ mol(-1) at one monolayer coverage. Analysis of the electronic density of states (DOS) revealed information regarding the mode of adsorption. In particular, the nitrogen 3a(1) and 2a(1) orbitals appear to undergo significant changes upon adsorption, in agreement with photoelectron spectroscopy studies . Dissociative adsorption wa s also investigated on the same surface. Both NH2(Ti-s) + H(Os) and NH(Ti-s) + 2H(O-s,) modes of dissociative adsorption, where s stands for surface, are found to be less stable than the molecular (non dissociated) adsorption.",
keywords = "single-crystal surfaces, density-functional theory, energy-loss spectroscopy, NH3 adsorption, electronic-structure, TIO2(110) surface, TIO2(001) surface, titanium-dioxide, desorption, PT(111)",
author = "McGill, {P. R.} and Hicham Idriss",
year = "2008",
month = "1",
day = "1",
doi = "10.1021/la701611p",
language = "English",
volume = "24",
pages = "97--104",
journal = "Langmuir",
issn = "0743-7463",
publisher = "AMER CHEMICAL SOC",
number = "1",

}

TY - JOUR

T1 - Ab initio study of surface acid-base reactions. The case of molecular and dissociative adsorption of ammonia on the (011) surface of rutile TiO2

AU - McGill, P. R.

AU - Idriss, Hicham

PY - 2008/1/1

Y1 - 2008/1/1

N2 - The interaction of ammonia molecules with Lewis acid centers (Ti4+ metal ions) of the (011) surface of rutile TiO2 is investigated by density functional theory in order to understand, from first principle, the nature of acid-base reactions on solid surfaces. Unlike the rutile (110) surface that contains alternating rows of 5-fold and 6-fold Ti atoms, all Ti atoms of the (011) surface are 5-fold coordinated. This surface has shown considerable activity for numerous chemical reactions and is thus an ideal prototype. At -1/2 monolayer coverage, with respect to surface Ti atoms, the adsorption energy is found to be equal to 100 kJ mol(-1), and drops to 58 kJ mol(-1) at one monolayer coverage. Analysis of the electronic density of states (DOS) revealed information regarding the mode of adsorption. In particular, the nitrogen 3a(1) and 2a(1) orbitals appear to undergo significant changes upon adsorption, in agreement with photoelectron spectroscopy studies . Dissociative adsorption wa s also investigated on the same surface. Both NH2(Ti-s) + H(Os) and NH(Ti-s) + 2H(O-s,) modes of dissociative adsorption, where s stands for surface, are found to be less stable than the molecular (non dissociated) adsorption.

AB - The interaction of ammonia molecules with Lewis acid centers (Ti4+ metal ions) of the (011) surface of rutile TiO2 is investigated by density functional theory in order to understand, from first principle, the nature of acid-base reactions on solid surfaces. Unlike the rutile (110) surface that contains alternating rows of 5-fold and 6-fold Ti atoms, all Ti atoms of the (011) surface are 5-fold coordinated. This surface has shown considerable activity for numerous chemical reactions and is thus an ideal prototype. At -1/2 monolayer coverage, with respect to surface Ti atoms, the adsorption energy is found to be equal to 100 kJ mol(-1), and drops to 58 kJ mol(-1) at one monolayer coverage. Analysis of the electronic density of states (DOS) revealed information regarding the mode of adsorption. In particular, the nitrogen 3a(1) and 2a(1) orbitals appear to undergo significant changes upon adsorption, in agreement with photoelectron spectroscopy studies . Dissociative adsorption wa s also investigated on the same surface. Both NH2(Ti-s) + H(Os) and NH(Ti-s) + 2H(O-s,) modes of dissociative adsorption, where s stands for surface, are found to be less stable than the molecular (non dissociated) adsorption.

KW - single-crystal surfaces

KW - density-functional theory

KW - energy-loss spectroscopy

KW - NH3 adsorption

KW - electronic-structure

KW - TIO2(110) surface

KW - TIO2(001) surface

KW - titanium-dioxide

KW - desorption

KW - PT(111)

U2 - 10.1021/la701611p

DO - 10.1021/la701611p

M3 - Article

VL - 24

SP - 97

EP - 104

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 1

ER -