Development and test of a highly sensitive and selective hydrogen sensor system

A miniaturized field-applicable sensor system was developed for the measurement of hydrogen (H2) in air in the concentration range 0.2–200 ppmv. The sensor system is based on the application of an yttria-stabilized zirconia (YSZ) solid electrolyte cell (SEC) as a coulometric detector with gas chromatographic (GC) pre-separation. The main system components for injection, chromatographic separation, and the oxygen pumping cell were significantly miniaturized and tested separately to characterize important measurement properties like selectivity, lower limit of detection, repeatability, and signal-to-noise ratio. Measurements were conducted under varying GC parameters and detector operating conditions. While changing the detector temperature influences the hydrogen peak significantly due to diffusion processes at the electrode–electrolyte interface; different oxygen-partial pressures at the measuring electrode have no visible effect. The combination of two packed columns with 1 m length, one filled with a molecular sieve (13X) and the other one with silica gel, enabled highly reproducible and selective H2 measurements with more than 90 % analyte turnover compared to Faraday's law. The resulting insights were used to define appropriate system parameters, construction guidelines, and material properties for the final test prototype.

Redox Oxides-Based Solar Thermochemistry and Its Materialization to Reactor/Heat Exchanger Concepts for Efficient Solar Energy Harvesting, Transformation and Storage

Ca-Mn-based perovskites doped in their A- and B-site were synthesized and comparatively tested versus the Co3O4/CoO and (Mn,Fe)2O3/(Mn,Fe)3O4 redox pairs with respect to thermochemical storage and oxygen pumping capability, as a function of the kind and extent of dopant. The perovskites' induced heat effects measured via differential scanning calorimetry are substantially lower: the highest reaction enthalpy recorded by the CaMnO3–δ composition was only 14.84 kJ/kg compared to 461.1 kJ/kg for Co3O4/CoO and 161.0 kJ/kg for (Mn,Fe)2O3/(Mn,Fe)3O4. Doping of Ca with increasing content of Sr decreased these heat effects; more than 20 at % Sr eventually eliminated them. Perovskites with Sr instead of Ca in the A-site exhibited also negligible heat effects, irrespective of the kind of B site cation. On the contrary, perovskite compositions characterized by high oxygen release/uptake can operate as thermochemical oxygen pumps enhancing the performance of water/carbon dioxide splitting materials. Oxygen pumping via Ca0.9Sr0.1MnO3–δ and SrFeO3–δ doubled and tripled, respectively, the total oxygen absorbed by ceria during its re-oxidation versus that absorbed without their presence. Such effective pumping compositions exhibited practically no shrinkage during one heat-up/cool-down cycle. However, they demonstrated an increase of the coefficient of linear expansion due to the superposition of “chemical expansion” to thermal-only one, the effect of which on the long-term dimensional stability has to be further quantified through extended cyclic operation.