Redox Cycling for SOFC Accelerated Degradation

This work aims at development of Accelerated Stress Tests for SOFC via artificial aging of the fuel electrode applying chemical and electrochemical (hydrogen starvation) redox cycling. In principle the degradation processes follows that of calendar aging (Ni coarsening and migration), but in addition it can bring to irreversible damages caused by the development of cracks at the interface anode/electrolyte due to the expansion/shrinkage of the Ni network. The challenge is to introduce conditions which will prevent the formation of cracks which can be done by partial oxidation. The advantage of the proposed methodology is that a mild level of oxidation can be regulated by direct impedance monitoring of the Ni network resistance changes during oxidation/reduction. Once the redox cycling conditions are fixed on bare anode and checked on anode/electrolyte sample for eventual cracks, the procedure can be introduced for AST in full cell configuration. The developed methodology is evaluated by comparative impedance analysis of artificially aged and calendar aged button cells. The results for 20 redox cycles which can be performed for 24 hours are comparable with those obtained for about 1600 hours operation in standard conditions which ensures more than 50 times acceleration.

Exponential Amplification by Redox Cross-Catalysis and Unmasking of Doubly Protected Molecular Probes

The strength of autocatalytic reactions lies in their ability to provide a powerful means of molecular amplification, which can be very useful for improving the analytical performances of a multitude of analytical and bioanalytical methods. However, one of the major difficulties in designing an efficient autocatalytic amplification system is the requirement for reactants that are both highly reactive and chemically stable in order to avoid limitations imposed by undesirable background amplifications. In the present work, we devised a reaction network based on a redox cross-catalysis principle, in which two catalytic loops activate each other. The first loop, catalyzed by H2O2, involves the oxi-dative deprotection of a naphthylboronate ester probe into a redox-active naphthohydroquinone, which in turn catalyzes the production of H2O2 by redox cycling in the presence of a reducing enzyme/substrate couple. We present here a set of new molecular probes with improved reactivity and stability, resulting in particularly steep sigmoidal kinetic traces and enhanced discrimination between specific and nonspecific responses. This translates into the sensitive de-tection of H2O2 down to a few nM in less than 10 minutes or a redox cycling compound such as the 2-amino-3-chloro-1,4-naphthoquinone H2O2 down to 50 pM in less than 30 minutes. The critical reason leading to these remarkably good performances is the extended stability stemming from the double masking of the naphthohydroquinone core by two boronate groups, a counterintuitive strategy if we consider the need for two equivalents of H2O2 for full deprotection. An in-depth study of the mechanism and dynamics of this complex reaction network is conducted in order to better understand, predict and optimize its functioning. From this investigation, the time response as well as detection limit are found highly dependent on pH, nature of buffer, and concentration of the reducing enzyme.