New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites

Fung, Victor N.; Wu, Zili; Jiang, De-en

doi:10.1021/acs.jpclett.8b02749

New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites

Journal Article · Wed Oct 17 00:00:00 EDT 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b02749· OSTI ID:1502543

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Univ. of California, Riverside, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

In this paper, a new model of bonding between radical adsorbates and lattice oxygens is proposed that considers both the adsorbate–oxygen bonding and the weakening of the metal–oxygen bonds. Density functional calculations of SrMO₃ perovskites for M being 3d, 4d, and 5d transition metals are used to correlate the bulk electronic structure with the surface-oxygen reactivity. Occupation of the metal–oxygen antibonding states, examined via the crystal orbital Hamilton population (COHP), is found to be a useful bulk descriptor that correlates with the vacancy formation energy of the lattice oxygen and its hydrogen adsorption energy. Analysis of density-of-states and COHP indicates that H adsorption energy is a combined result of formation of the O–H bond and the weakening of the surface metal–oxygen bond due to occupation of the metal–oxygen antibonding states by the electron from H. Lastly, this insight will be useful in understanding the trends in surface reactivity of perovskites and transition-metal oxides in general.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1502543

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 21 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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