Skip to main content
banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The full text of this article is not currently available.
J. Suntivich, K. J. May, H. A. Gasteiger, J.B. Goodenough, and Y. Shao-Horn, “A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles,” Science 334, 1383 (2011).
W. T. Hong et al., “Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis,” Energy Environ. Sci. 8, 1404 (2015).
J. Suntivich et al., “Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries,” Nat. Chem. 3, 546 (2011).
M. Risch et al., “La0.8Sr0.2MnO3-δdecorated with Ba0.5Sr0.5Co0.8Fe0.2O3-δ: a bifunctional surface for oxygen electrocatalysis with enhanced stability and activity,” J. Am. Chem. Soc. 136, 5229 (2014).
K. Zhang et al., “Nanostructured Mn-based oxides for electrochemical energy storage and conversion,” Chem. Soc. Rev. 44, 699 (2015).
J. Kim, X. Yin, K. C. Tsao, S. Fang, and H. Yang, “Ca2Mn2O5 as oxygen-deficient perovskite electrocatalyst for oxygen evolution reaction,” J. Am. Chem. Soc. 136, 14646 (2014).
B. Hammer and J. K. Nørskov, “Theoretical surface science and catalysis—Calculations and concepts,” Adv. Catal. 45, 71 (2000).
J. O. Bockris and T. Otagawa, “The electrocatalysis of oxygen evolution on perovskites,” J. Electrochem. Soc. 131, 290 (1984).
J. Rossmeisl, Z. W. Qu, H. Zhu, G. J. Kroes, and J. K. Nørskov, “Electrolysis of water on oxide surfaces,” J. Electroanal. Chem. 607, 83 (2007).
M. Imada, A. Fujimori, and Y. Tokura, “Metal-insulator transitions,” Reviews of Modern Physics 70, 1039 (1998).
G. Kresse and J. Furthmüller, “Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set,” Physical Review B 54, 11169 (1996).
G. Kresse and D. Joubert, “From ultrasoft pseudopotentials to the projector augmented-wave method,” Physical Review B 59, 1758 (1999).
P. E. Blöchl, “Projector augmented-wave method,” Physical Review B 50, 17953 (1994).
V. I. Anisimov, J. Zaanen, and O. K. Andersen, “Band theory and Mott insulators: Hubbard U instead of Stoner I,” Physical Review B 44, 943 (1991).
W. Metzner and D. Vollhardt, “Correlated lattice fermions ind=dimensions,” Physical Review Letters 62, 324 (1989).
A. Georges, G. Kotliar, W. Krauth, and M. J. Rozenberg, “Dynamical mean-field theory of strongly correlated fermion systems and the limit of infinite dimensions,” Reviews of Modern Physics 68, 13 (1996).
F. Lu, W.-H. Wang, and L.-J. Zou, “Metal-insulator transition in the half-filling two-orbital Hubbard model on the triangular lattice,” Physical Review B 77, 125117 (2008).
G. Kotliar et al., “Electronic structure calculations with dynamical mean-field theory,” Reviews of Modern Physics 78, 865 (2006).
X. Deng, L. Wang, X. Dai, and Z. Fang, “Local density approximation combined with Gutzwiller method for correlated electron systems: Formalism and applications,” Physical Review B 79, 075114 (2009).
F. Lu, J. Zhao, H. Weng, Z. Fang, and X. Dai, “Correlated topological insulators with mixed valence,” Physical Review Letters 110, 096401 (2013).
E. Gull et al., “Continuous-time Monte Carlo methods for quantum impurity models,” Reviews of Modern Physics 83, 349 (2011).
L. Huang et al., “iQIST: An open source continuous-time quantum Monte Carlo impurity solver toolkitsolver toolkit,” Computer Physics Communications 195, 140 (2015).
N. Marzari, A. A. Mostofi, J. R. Yates, I. Souza, and D. Vanderbilt, “Maximally localized Wannier functions: Theory and applications,” Reviews of Modern Physics 84, 1419 (2012).
J. Mravlje, M. Aichhorn, and A. Georges, “Origin of the high Néel temperature in SrTcO3,” Physical Review Letters 108, 197202 (2012).
C. Castellani, C. R. Natoli, and J. Ranninger, “Magnetic structure of V2O3 in the insulating phase,” Physical Review B 18, 4945 (1978).
D. Neagu, G. Tsekouras, D. N. Miller, H. Ménard, and J. T. Irvine, “In situ growth of nanoparticles through control of non-stoichiometry,” Nature Chemistry 5, 916923 (2013).
W. Zhang and W. T. Zheng, “Exsolution-mimic heterogeneous surfaces: Towards unlimited catalyst design,” ChemCatChem 7, 4850 (2015).

Data & Media loading...


Article metrics loading...



3-orbital filling in transition metal oxide is crucial to govern the catalytic activity in oxygen evolution reduction, nevertheless, it is not fundamentally accessible why specific orbital occupation produces a highest catalytic performance. Here, we utilize brownmillerite CaMnO to clarify the orbital selective catalytic behavior due to the crystal field splitting and on-site coulomb interactions. Within density functional theory plus dynamical mean field theory, CaMnO shows a paramagnetic Mott insulating behavior at room temperature, consistent with optical adsorption spectra and magnetic susceptibility. As the center of the orbital locates in the lower Hubbard sub-band, the unit occupation on orbital provides a moderate bonding with external O* species to cause a high catalytic activity of CaMnO with a square pyramid crystal field. Such concept of unit occupation of near Fermi level could be extended to other crystal fields for future design of oxide catalysts.


Full text loading...


Access Key

  • FFree Content
  • OAOpen Access Content
  • SSubscribed Content
  • TFree Trial Content
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd