Issue 16, 2020

Trends in C–O and N–O bond scission on rutile oxides described using oxygen vacancy formation energies

Abstract

Reactivity trends on transition metals can generally be understood through the d-band model, but no analogous theory exists for transition metal oxides. This limits the generality of analyses in oxide-based catalysis and surface chemistry and has motivated the appearance of numerous descriptors. Here we show that oxygen vacancy formation energy (ΔEVac) is an inexpensive yet accurate and general descriptor for trends in transition-state energies, which are usually difficult to assess. For rutile-type oxides (MO2 with M = 3d metals from Ti to Ni), we show that ΔEVac captures the trends in C–O and N–O bond scission of CO2, CH3OH, N2O, and NH2OH at oxygen vacancies. The proportionality between ΔEVac and transition-state energies is rationalized by analyzing the oxygen–metal bonds, which change from ionic to covalent from TiO2 to NiO2. ΔEVac may be used to design oxide catalysts, in particular those where lattice oxygen and/or oxygen vacancies participate in the catalytic cycles.

Graphical abstract: Trends in C–O and N–O bond scission on rutile oxides described using oxygen vacancy formation energies

Supplementary files

Article information

Article type
Edge Article
Submitted
29 1 2020
Accepted
20 3 2020
First published
23 3 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 4119-4124

Trends in C–O and N–O bond scission on rutile oxides described using oxygen vacancy formation energies

H. Su, X. Ma, K. Sun, C. Sun, Y. Xu and F. Calle-Vallejo, Chem. Sci., 2020, 11, 4119 DOI: 10.1039/D0SC00534G

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