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Rational optimization of the OER activity of catalystsbased on LaNiO3 oxide is achieved by maximizing the presence of trivalent Ni in the surface structure. DFT investigations of the LaNiO3catalyst and surface structures related to it predict an improvement inthe OER activity for these materials to levels comparable with the topof the OER volcano if the La content is minimized while the oxidationstate of Ni is maintained. These theoretically predicted structures ofhigh intrinsic OER activity can be prepared by a templated spray-freeze freeze-drying synthesis followed by a simple postsynthesisexfoliation-like treatment in acidic media. These nanocrystallineLaNiO3-related materials confirm the theoretical predictions, showinga dramatic improvement in OER activity. The exfoliated surfacesremain stable in OER catalysis, as shown by an in-operando ICP-OESstudy. The unprecedented OER activation of the synthesized LaNiO3-based materials is related to a close juxtaposition of the theoretical conception of ideal structural motifs and the ability to engendersuch motifs using a unique synthetic procedure, both principally related to stabilization and pinning of the Ni oxidation state within the local coordination environment of the perovskite structure.

Developing new efficient catalyst materials for the oxygen evolution reaction (OER) is essential for widespread proton exchange membrane water electrolyzer use. Both RuO2(110) and IrO2(110) have been shown to be highly active OER catalysts, however DFT predictions have been unable to explain the high activity of RuO2. We propose that this discrepancy is due to RuO2 utilizing a different reaction pathway, as compared to the conventional IrO2 pathway. This hypothesis is supported by comparisons between experimental data, DFT data and the proposed reaction model.

Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups. Despite the substantial efforts, the driving force required for water oxidation is largely making the reaction inefficient. In the present work, we collected published studies involving DFT calculations for the OER, with the purpose to understand why the progress made so far, for lowering the overpotential of the reaction, is relatively small. The data revealed that the universal scaling relationship between HO* and HOO* intermediates is still present and robust, despite the variety in methods and structures used for calculating the binding energies of the intermediates. On the other hand, the data did not show a clear trend line regarding the O* binding. Our analysis suggested that trends in doped semiconducting oxides behave very differently from those in other oxides. This points towards a computational challenge in describing doped oxides in a realistic manner. We propose a way to overcome these computational challenges, which can be applied to simulations corresponding to doped semiconductors in general., Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups.