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Crystal structures of two metal–organic frameworks (MFU‐1 and MFU‐2) are presented, both of which contain redox‐active CoII centres coordinated by linear 1,4‐bis[(3,5‐dimethyl)pyrazol‐4‐yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert‐butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU‐1, MFU‐2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure–reactivity relationships in the future design of redox‐active metal–organic frameworks. Mechanistic details for oxidation reactions employing tert‐butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K‐edge X‐ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O2 were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature‐programmed oxidation (TPO). Solution impregnation of MFU‐1 with a co‐catalyst (N‐hydroxyphthalimide) led to NHPI@MFU‐1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed.
The lifetime and performance of solid-oxide fuel cells (SOFC) and electrolyzer cells (SOEC) can be significantly degraded by oxidation of nickel within the electrode and support structures. This paper documents a detailed computational model describing nickel oxide (NiO) formation as a growing film layer on top of the nickel phase in Ni/YSZ composite electrodes. The model assumes that the oxidation rate is controlled by transport of ions across the film (Wagner's theory). The computational model, which is implemented in a two-dimensional continuum framework, facilitates the investigation of alternative chemical reaction and transport mechanisms. Model predictions agree well with a literature experimental measurement of oxidation-layer growth. In addition to providing insight in interpreting experimental observations, the model provides a quantitative predictive capability for improving electrode design and controlling operating conditions.