The progress of dealloying, an electrochemical synthesis method capable of producing nanoporous structures with bulk outer dimensions, is studied by in situ resistometry. The resistance increases by three orders of magnitude while nanoporous gold or platinum is formed. Simultaneous monitoring of charge flow and electrical resistance increase proves to be an ideal combination for analyzing the etching progress, which in accordance with recent studies can be demonstrated to occur in two steps referred to as 'primary (or bulk) dealloying' and 'secondary (or ligament) dealloying'. A model is developed, which describes the resistance increase during etching as governed by the reduction of the master alloy backbone in favor of the nanoporous structure. This new approach allows an evaluation of the etching front propagation (primary dealloying) as well as the status of the already porous structure (secondary dealloying).
Nanoporous gold (np-Au), produced by dealloying in silver nitrate solution exhibits extraordinary high surface-to-volume ratios of more than 20 m 2 /g which represents an excellent prerequisite for property tuning by surface charging. Upon electrochemical charging in aqueous KOH solution, the electrical resistance is observed to vary reversibly by up to 88%. The charge coefficient, thus the sensitivity of the resistance toward the imposed charge per mol, is however significantly smaller compared to conventionally prepared np-Au, etched in nitric acid solution. While the strong resistance variation observed in the present work can directly be related to the high charge transfer due to extraordinary fine porosity, the charge coefficients can be understood with regards to the matrix resistance of the respective materials, which is strongly influenced by dealloying residuals.
Wastewater contains high amounts of unused energy in the form of dissolved ammonia, which can easily be converted into gaseous humidified ammonia via membrane distillation, thus providing a potential fuel for solid oxide fuel cells. This study presents comprehensive investigations of the use of humidified ammonia as the primary fuel component in high-fuel utilization conditions. For these investigations, large planar anode-and electrolyte-supported solid oxide single cells were operated at the respective appropriate temperatures, 800°C and 850°C. Fueled with ammonia, both cells exhibited excellent ammonia conversion (>99.5%) in addition to excellent performance output and fuel utilization. In 100 h stability tests performed at 80% fuel utilization, the cells exhibited stable performance, despite scanning electron microscopy analyzes revealing partial impairments to the nickel parts of both cells due to the formation and subsequent decomposition of nickel nitride. This study also demonstrates that methane is a perfect additional fuel component for humidified ammonia streams, as steam supports the internal reforming of methane. Alternating and direct current as well as electrochemical impedance measurements with a variety of ammonia/steam/methane/nitrogen fuel mixtures were used to evaluate the performance potential of the cells, and proved their stability over 48 h in highly polarized conditions.
In the course of this study the direct utilization of ammonia in different types of solid oxide fuel cells (SOFCs), such as anode- and electrolyte-supported SOFC, is investigated. Experiments in low fuel utilization, exhibited excellent performance of ammonia in SOFCs, although the power outputs of equivalent hydrogen/nitrogen fuels were not attained due to the incomplete endothermic ammonia decomposition. Next, the single cells were operated under high fuel utilization conditions and methane was added to the humidified ammonia stream, where they showed excellent ammonia- and methane conversions. The stability of the cells used was proven over a period of at least 48 hours with a variety of fuel mixtures. Post mortem scanning electron microscopy analysis of the anode micro-structures indicated nitriding effects of nickel, as microscopic pores and enlargements of the metallic parts occurred. Finally, a long-term test over 1,000 hours was carried out using a ten-layer stack consisting of electrolyte-supported cells.
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