Kinetic control of oxygen interstitial interaction with TiO2(110) via the surface Fermi energy

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Atomically clean surfaces of semiconducting oxides efficiently mediate the interconversion of gas-phase O2 and solid-phase oxygen interstitial atoms (Oi). First-principles calculations together with mesoscale microkinetic modeling are employed for TiO2(110) to determine reaction pathways, assess appropriate rate expressions, and obtain corresponding activation energies and pre-exponential factors. The Fermi energy (EF) at the surface influences the rate-determining step for both injection and annihilation of Oi. The barriers range between 0.72−0.82 eV for injection and 0.60− 2.34 eV for annihilation and may be manipulated through intentional control of EF. At equilibrium, the microkinetic model and first-principles calculations indicate that interconversion of Oi species in the first and second sublayers limits the rate. The effective pre-exponential factors for injection and annihilation are surprisingly low, probably resulting from the use of simple Langmuir-like rate expressions to describe a complicated kinetic sequence.

Original languageEnglish (US)
Pages (from-to)12632-12648
Number of pages17
JournalLangmuir : the ACS journal of surfaces and colloids
Issue number42
Early online dateOct 16 2020
StatePublished - Oct 27 2020

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry


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