The historical development, current status and future prospects of chlor-alkali electrolysis with oxygen depolarized cathodes (ODCs) are summarized. Over the last decades, membrane chlor-alkali technology has been optimized to such an extent that no substantial reduction of the energy demand can be expected from further process modifications. However, replacement of the hydrogen evolving cathodes in the classical membrane cells by ODCs allows for reduction of the cell voltage and correspondingly the energy consumption of up to 30%. This replacement requires the development of appropriate cathode materials and novel electrolysis cell designs. Due to their superior long-term stability, ODCs based on silver catalysts are very promising for oxygen reduction in concentrated NaOH solutions. Finite-gap falling film cells appear to be the technically most mature design among the several ODC electrolysis cells that have been investigated.

Alkaline water electrolysis is a key technology for large-scale hydrogen production powered by renewable energy. As conventional electrolyzers are designed for operation at fixed process conditions, the implementation of fluctuating and highly intermittent renewable energy is challenging. This contribution shows the recent state of system descriptions for alkaline water electrolysis and renewable energies, such as solar and wind power. Each component of a hydrogen energy system needs to be optimized to increase the operation time and system efficiency. Only in this way can hydrogen produced by electrolysis processes be competitive with the conventional path based on fossil energy sources. Conventional alkaline water electrolyzers show a limited part-load range due to an increased gas impurity at low power availability. As explosive mixtures of hydrogen and oxygen must be prevented, a safety shutdown is performed when reaching specific gas contamination. Furthermore, the cell voltage should be optimized to maintain a high efficiency. While photovoltaic panels can be directly coupled to alkaline water electrolyzers, wind turbines require suitable converters with additional losses. By combining alkaline water electrolysis with hydrogen storage tanks and fuel cells, power grid stabilization can be performed. As a consequence, the conventional spinning reserve can be reduced, which additionally lowers the carbon dioxide emissions.

This study provides a direct comparison of hydrogen crossover in PEM (Nafion 117) and alkaline water electrolysis (Zirfon) at a temperature of 60 • C applying state-of-the-art separating unit materials. To this end, occurring crossover mechanisms are described first, before experimental data of the anodic hydrogen content are shown in dependence of current density, system pressure and process management strategy. The results suggest that permeation in PEM electrolyzers is mainly governed by diffusion due to a supersaturated concentration of dissolved hydrogen within the catalyst layer, showing a share of 98% of the total permeation flux at 1 A cm −2 and atmospheric pressure. Permeation in alkaline electrolyzers also exhibits a significant influence of supersaturation, but the overall crossover is mainly influenced by mixing the electrolyte cycles, which makes up a share of 90% at 0.7 A cm −2 and 1 bar. Generally it becomes evident that hydrogen permeation across the separating unit is more than one order of magnitude smaller in alkaline electrolysis, which is mainly a consequence of the significantly lower hydrogen solubility in concentrated KOH electrolyte. Finally, this study concludes with an assessment of the impact of separating unit thickness and provides mitigation strategies to reduce hydrogen crossover.

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Automatic mechanism generation is used to determine mechanisms for the CO 2 hydrogenation on Ni(111) in a two-stage process while considering the correlated uncertainty in DFT-based energetic parameters systematically. In a coarse stage, all the possible chemistry is explored with gas-phase products down to the ppb level, while a refined stage discovers the core methanation submechanism. Five thousand unique mechanisms were generated, which contain minor perturbations in all parameters. Global uncertainty assessment, global sensitivity analysis, and degree of rate control analysis are performed to study the effect of this parametric uncertainty on the microkinetic model predictions. Comparison of the model predictions with experimental data on a Ni/SiO 2 catalyst find a feasible set of microkinetic mechanisms within the correlated uncertainty space that are in quantitative agreement with the measured data, without relying on explicit parameter optimization. Global uncertainty and sensitivity analyses provide tools to determine the pathways and key factors that control the methanation activity within the parameter space. Together, these methods reveal that the degree of rate control approach can be misleading if parametric uncertainty is not considered. The procedure of considering uncertainties in the automated mechanism generation is not unique to CO 2 methanation and can be easily extended to other challenging heterogeneously catalyzed reactions.

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