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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 formation of secondary phases in the porous electrodes is a severe mechanism affecting the lifetime of solid oxide fuel cells (SOFC). It can occur via various chemical mechanisms and it has a significant influence on cell performance due to pore clogging and deactivation of active surfaces and triple-phase boundary (TPB). We present a modeling and simulation study of nickel oxide formation (reoxidation) and carbon formation (coking) within the SOFC anode. We use a 2D continuum model based on a multi-phase framework [Neidhardt et al., J. Electrochem. Soc., 159, 9 (2012)] that allows the introduction of arbitrary solid phases (here: Ni, YSZ, NiO, Carbon) plus gas phase. Reactions between the bulk phases are modeled via interface-adsorbed species and are described by an elementary kinetic approach. Published experimental data are used for parameterization and validation. Simulations allow the prediction of cell performance under critical operation conditions, like (i) a non-fuel operation test, where NiO formation is taking place (Figure 1a), or (ii) an open circuit voltage (OCV) stability test under hydrocarbon atmosphere, where solid carbon is formed (Figure 1b). Results are applied for enhanced interpretation of experimental data and for prediction of safe operation conditions.
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.
The following contribution deals with the growth of cracks in low-cycle fatigue (LCF) and thermomechanical fatigue (TMF) tested specimens of Inconel 718 measured by using the replica method. The specimens are loaded with different strain rates. The material shows a significantly higher crack growth rate if the strain rate is decreased. Electron backscatter diffraction (EBSD) is adopted to identify the failure mechanism and the misorientation relationship of failed grain boundaries in secondary cracks. The analyzed cracks propagated mainly transgranular but also intergranular failure can be observed in some areas. It is found that grain boundaries with coincidence site lattice (CSL) boundary structure are generally less susceptible for intergranular failure than grain boundaries with random misorientation. For modeling the experimentally identified crack behavior an existing model for fatigue crack growth based on the mechanism of time dependent elastic–plastic crack tip blunting is enhanced to describe environmental effects based on the mechanism of oxygen diffusion at the crack tip. For the diffusion process the temperature dependent parabolic diffusion law is assumed. As a result, the time dependent cyclic crack tip opening displacement (DCTOD) is used as representative value to describe both mechanisms. Thus, most
of the included model parameters characterize the deformation behavior of the material and can be determined by independent material tests. With the determined material properties, the proposed model describes the experimentally measured crack growth curves very well. The model is validated based on predictions of the number of cycles to failure of LCF as well as in-phase and out-of-phase TMF tests in the temperature range between room temperature and 650 °C.