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WIREs Comput Mol Sci
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Structure and water oxidation activity of 3d metal oxides

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Water splitting driven by solar energy is regarded as the candidate for the next generation of power source. The reaction is however kinetically hindered by the oxygen evolution reaction (OER) involving four proton–electron transfer steps. The ideal OER catalyst should avoid using precious elements, such as Ir, Ru, and Pt, and have a long‐term stability under positive bias potential. Recent experiments have shown that most 3d oxides are OER active catalysts, while some can even achieve comparable activities to commercial Ir/Ru catalysts in lab condition. In this article, we review the recent theoretical progress for characterizing the structure of 3d oxides and understanding the photo‐electrocatalytic water splitting mechanism over these catalysts. The methodology for global structure exploration, including evolutionary algorithm and stochastic surface walking method, is first introduced together with their applications in exploring the potential energy surface of TiO2 and NiOx systems. The current theoretical approaches to investigate the thermodynamics and kinetics of photo‐/electrochemical reactions are discussed and the latest understanding for OER reactions are summarized. WIREs Comput Mol Sci 2016, 6:47–64. doi: 10.1002/wcms.1236 This article is categorized under: Structure and Mechanism > Computational Materials Science Computer and Information Science > Computer Algorithms and Programming Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics
Energetically favorable NiO6 octahedral frameworks for β‐NiOOH. 3: pyrolusite (rutile), 4: nsutite, 5: ramsdellite‐/pyrolusite‐type intergrowth, 6: lepidocrocite, 7–8: 1 × 3 tunnel/pyrolusite‐type intergrowth, 9: ramsdellite. (Reprinted with permission from Ref . Copyright 2014 American Chemical Society)
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(a) DFT‐optimized bulk phase structure identified from SSW‐crystal global optimization. Gray and red spheres represent Ti and O atoms, respectively. (b) The DFT lowest energy connectivity map of the major phases at zero pressure. The energy unit is eV per Ti4O8 cell. The energy of rutile is set to zero. *lepidocrocite typed layered structure (Pmmn, #59). (Reprinted with permission from Ref . Copyright 2015 Institute of Physics.
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(a) Proton‐transfer energy profiles in the surface‐hole (A, B) and water‐hole (C, D) states for a selected configurations along the first principles MD trajectory of an anatase TiO2 (1 0 1) slab in contact with liquid water. (b) Spin density (0.01 a.u. contour) of the water‐hole and surface‐hole states before and after the proton transfer. (Reprinted with permission from Ref . Copyright 2013 American Chemical Society)
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(a) The optimized structures of the intermediate states of OER on anatase (1 0 1); (b) free energy profiles of OER on (1 0 1) (black), (0 0 1) (green), and (1 0 2) (red) surfaces at an overpotential of 0.7 V (1.93 V vs SHE) Ti, gray; O, red; H, white. (Reprinted with permission from Ref . Copyright 2010 American Chemical Society)
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The illustration of (a) the SSW method in 1D PES and (b) homogenous crystal phase transition. The phase transition can be divided into two steps: (1) the lattice rotation and (2) the lattice deformation. (Reprinted with permission from Ref . Copyright 2014 The Royal Society of Chemistry)
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(a) DFT energy profile and key structures for the anatase (1 1 2) reconstruction that leads to the formation of TiO2‐II and brookite phases. Blue: Ti after reconstruction; gray: Ti before reconstruction; yellow: O after reconstruction; and red: O before reconstruction. All views are looking down from anatase [1 1 0]. (Reprinted with permission from Ref . Copyright 2015 American Chemical Society)
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(a) DFT lowest energy transition pathway from TiO2(B) to anatase bulk crystal (structures viewed down from the b axis). The blue lines indicate the habit plane of the phase transition. (b) The atomic structure of the TiO2(B)/anatase phase junction with orientationrelation()B//(1 0 3)A+[0 1 0]B//[0 1 0]A as predicted from theory. From left to the right are the top‐views of (1 0 3)A and ((2 ) 0 1)B, and two side‐views of the junction showing the (1 0 0)B together with (0 0 1)A (theoretical dihedral angle 11.0 degrees), and (0 1 0)B//(0 1 0)A. Ti: gray; O: red. (Reprinted with permission from Ref . Copyright 2014 American Chemical Society)
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Structure and Mechanism > Computational Materials Science
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