Identification of Surface Reactivity Descriptor for Transition Metal Oxides in Oxygen Evolution Reaction
Top Cited Papers
- 1 August 2016
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 138 (31), 9978-9985
- https://doi.org/10.1021/jacs.6b05398
Abstract
A number of important reactions such as the oxygen evolution reaction (OER) are catalyzed by transition metal oxides (TMOs), the surface reactivity of which is rather elusive. Therefore, rationally tailoring adsorption energy of intermediates on TMOs to achieve desirable catalytic performance still remains a great challenge. Here we show the identification of a general and tunable surface structure, coordinatively unsaturated metal cation (MCUS), as a good surface reactivity descriptor for TMOs in OER. Surface reactivity of a given TMO increases monotonically with the density of MCUS, and thus the increase in MCUS improves the catalytic activity for weak-binding TMOs but impairs that for strong-binding ones. The electronic origin of the surface reactivity can be well explained by a new model proposed in this work, wherein the energy of the highest-occupied d-states relative to the Fermi level determines the intermediates’ bonding strength by affecting the filling of the antibonding states. Our model for the first time well describes the reactivity trends among TMOs, and would initiate viable design principles for, but not limited to, OER catalysts.Funding Information
- Agency for Science, Technology and Research (M4070232.120)
- Ministry of Science and Technology of the People's Republic of China (2012CB932800)
- Ministry of Education - Singapore (RG111/15)
- National Research Foundation-Prime Minister's office, Republic of Singapore
- Nanyang Technological University (M4080977.120)
This publication has 44 references indexed in Scilit:
- Valence band electronic structure characterization of the rutile TiO2 (110)-(1×2) reconstructed surfaceSurface Science, 2013
- Enhancing Electrocatalytic Oxygen Reduction on MnO2 with VacanciesAngewandte Chemie-International Edition, 2013
- Number of outer electrons as descriptor for adsorption processes on transition metals and their oxidesChemical Science, 2013
- Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysisJournal of Electroanalytical Chemistry, 2011
- Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteriesNature Chemistry, 2011
- Density functional theory in surface chemistry and catalysisProceedings of the National Academy of Sciences of the United States of America, 2011
- Electron traps and their effect on the surface chemistry of TiO 2 (110)Proceedings of the National Academy of Sciences of the United States of America, 2010
- Growth of Oriented Single-Crystalline Rutile TiO2 Nanorods on Transparent Conducting Substrates for Dye-Sensitized Solar CellsJournal of the American Chemical Society, 2009
- Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfacesNature Materials, 2007
- Efficiency of Splitting Water with Semiconducting PhotoelectrodesJournal of the Electrochemical Society, 1984