Structure and water oxidation activity of 3d metal oxides

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 3 d 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 3 d 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 TiO 2 and NiO x 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