A Linear Response DFT+U Study of Trends in the Oxygen Evolution Activity of Transition Metal Rutile Dioxides

Zhongnan Xu, Jan Rossmeisl, John R. Kitchin

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

There are known errors in oxidation energies of transition metal oxides caused by an improper treatment of their d-electrons. The Hubbard U is the cornputationally cheapest addition one can use to capture correct reaction energies, but the specific Hubbard U oftentimes m-uSt.be empirically determined only when suitable experimental data exist. We evaluated the effect of addling a calculated, linear response U on the predicted adsorption energies, scaling relationships, and activity trends with respect to the oxygen evolution reaction for a set of transition metal dioxides. We find that applying a U greater than zero always causes adsorption energies to be more endothermic. Furthermore, the addition of the Hubbard U greater than zero does not break scaling relationships established without the Hubbard U. The addition of the calculated linear response U value produces shifts of different systems along the activity volcano that results in improved activity trends when compared with experimental results.
Original languageEnglish
JournalThe Journal of Physical Chemistry Part C
Volume119
Issue number9
Pages (from-to)4827-4833
Number of pages7
ISSN1932-7447
DOIs
Publication statusPublished - 2015

Keywords

  • CHEMISTRY,
  • NANOSCIENCE
  • MATERIALS
  • DENSITY-FUNCTIONAL THEORY
  • WATER OXIDATION
  • OXIDE SURFACES
  • ELECTRONIC-STRUCTURE
  • CATALYSIS
  • ELECTROCATALYSIS
  • ELECTROLYSIS
  • UNIVERSALITY
  • PEROVSKITES
  • LIMITATIONS

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