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[Display omitted] • Dynamic Ir electronic and geometric structural change with surface adsorption. • pH-dependent oxygenate adsorption and Ir dissolution pathway. • Unfavorable adsorption coincides with distorted Ir linkage and decreased Ir valence state. The interaction between catalyst surfaces and adsorbed oxygen intermediates is critical to catalytic performance for electrochemical water oxidation to oxygen. However, the relationship between adsorption energetics and electrocatalytic activity is primarily assessed for pristine catalyst materials, which leaves much unknown about the dynamics of these properties in relationship to catalyst performance during long-term operation. In this work, we experimentally assess OH and O adsorption on Ca 2 IrO 4 nanoparticles and monitor their evolution during extensive chronoamperometry tests at highly oxidizing potentials in a range of low pH electrolytes. In situ x-ray absorption spectroscopy reveals changes for surface adsorbate energetics and local iridium structures with applied potentials. Increasingly unfavorable adsorption of OH and formation of O intermediates after long-term operation is correlated with severe metal dissolution, distorted [IrO 6 ] octahedral linkages, and a decreased average Ir valence. This work establishes connections between surface adsorption energetics, Ir structure, OER kinetics, and material stability outcomes. [ABSTRACT FROM AUTHOR]

Abstract: We consider propagation of waves through a spatio-temporal doubly periodic material structure with rectangular microgeometry in one spatial dimension and time. Both spatial and temporal periods in this dynamic material are assumed to be the same order of magnitude. Mathematically the problem is governed by a standard wave equation with variable coefficients. We consider a checkerboard microgeometry where variables cannot be separated. The rectangles in a space–time checkerboard are assumed filled with materials differing in the values of phase velocities but having equal wave impedance . The difference between dynamic materials and classical static composites is that in the former case the design variables will also be time dependent. Within certain parameter ranges, the formation of distinct and stable limiting characteristic paths, i.e., limit cycles, was observed in [K.A. Lurie, S.L. Weekes, Wave propagation and energy exchange in a spatio-temporal material composite with rectangular microstructure, J. Math. Anal. Appl. 314 (2006) 286–310]; such paths attract neighboring characteristics after a few time periods. The average speed of propagation along the limit cycles remains the same throughout certain ranges of structural parameters, and this was called in [K.A. Lurie, S.L. Weekes, Wave propagation and energy exchange in a spatio-temporal material composite with rectangular microstructure, J. Math. Anal. Appl. 314 (2006) 286–310] a plateau effect. Based on numerical evidence, it was conjectured in [K.A. Lurie, S.L. Weekes, Wave propagation and energy exchange in a spatio-temporal material composite with rectangular microstructure, J. Math. Anal. Appl. 314 (2006) 286–310] that a checkerboard structure is on a plateau if and only if it yields stable limit cycles and that there may be energy concentrations over certain time intervals depending on material parameters. In the present work we give a more detailed analytic characterization of these phenomena and provide a set of sufficient conditions for the energy concentration that was predicted numerically in [K.A. Lurie, S.L. Weekes, Wave propagation and energy exchange in a spatio-temporal material composite with rectangular microstructure, J. Math. Anal. Appl. 314 (2006) 286–310]. [Copyright &y& Elsevier]

A temporal laminate is a material whose parameters are homogeneous in space but vary periodically and discontinuously in time. In this article, we consider wave propagation through a temporal laminate where the period of the disturbance moving through the media is large relative to ϵ the period of the lamination. It is worth noting that the constituent materials and the mixing coefficient can be chosen so that the effective speed in a temporal laminate is greater than the individual phase speeds. We show that the analytic problem admits stable long wave modes, but shorter wave modes grow as they pass through the laminate layers. Computing wave motion through this composite medium using the standard upwind, finite-difference method under the CFL condition for numerical wave propagation in the individual media will produce growing short wave modes. Numerical results are degraded since accuracy is quickly lost due to the growth of short waves which enter into the computation through truncation and round-off error. A new CFL constraint is derived for a finite-difference numerical scheme which will allow us to compute the stable long wave motion. Numerical results are given for the direct numerical simulation of the homogenization problem (ϵ→0). [Copyright &y& Elsevier]