Mixed-conducting LSC/CGO and Ag/CGO composites for passive oxygen separation membranes

Dense ceramic oxygen separation membranes can pass oxygen perm-selectively at elevated temperature and have potential for improving the performance and reducing the cost of several industrial processes: such as the conversion of natural gas to syngas, or to separate oxygen from air for oxy-fuel combustion in electricity generation (to reduce NOx emissions and facilitate CO2 sequestration). These pressure-driven solid state membranes are based on fast oxygen-ion conducting ceramics, but also need a compensating flow of electrons. Dual-phase composites are attractive since they provide an extra degree of freedom, compared with single phase membranes, for optimising the overall membrane performance. In this study, composites containing gadolinia doped ceria (CGO, Ce0.9Gd0.1O2- ) and either strontium-doped lanthanum cobaltite (LSC, La0.9Sr0.1CoO3- or La0.6Sr0.4CoO3- ) or silver (Ag) were investigated for possible application as oxygen separation membranes in oxy-fuel combustion system. These should combine the high oxygen ion conductivity of CGO with the high electronic conductivity and fast oxygen surface exchange of LSC or silver. Dense mixed-conducting composite materials of LSC/CGO (prepared by powder mixing and sintering) and Ag/CGO composites (prepared by silver plus copper oxide infiltration method) showed high relative density (above 95%), low background gas leakage and also good electrical conduction. The percolation threshold of the electronic conducting component was determined to be approximately 20 vol.% for both LSC compositions and 14 vol.% for Ag. Isotopic exchange and depth profiling by secondary ion mass spectrometry was used to investigated the oxygen tracer diffusion (D*) and surface exchange coefficient (k*) of the composites. Composites just above the electronic percolation threshold exhibited high solid state oxygen diffusivity, fast surface exchange activity moderate thermal expansion and sufficient mechanical strength thus combining the benefits of their constituent materials. The preliminary work on oxygen permeation measurement showed that the reasonable magnitude of oxygen fluxes is possible to be achieved. This indicates that the composites of LSC/CGO and Ag/CGO are promising for further development as passive oxygen separation membranes

Tris(ethyl­enediamine)cobalt(II) sulfate

The structure of the title compound, [CoII(C2H8N2)3]SO4, the cobalt example of [M(C2H8N2)3]SO4, is reported. The Co and S atoms are located at the 2d and 2c Wyckoff sites (point symmetry 32), respectively. The Co atom is coordinated by six N atoms of three chelating ethyl­enediamine mol­ecules generated from half of the ethyl­enediamine mol­ecule in the asymmetric unit. The O atoms of the sulfate anion are disordered mostly over two crystallographic sites. The third disorder site of O (site symmetry 3) has a site occupancy approaching zero. The H atoms of the ethyl­enediamine mol­ecules inter­act with the sulfate anions via inter­molecular N—H⋯O hydrogen-bonding inter­actions

Mixed-conducting LSC/CGO and Ag/CGO composites for passive oxygen separation membranes

Dense ceramic oxygen separation membranes can pass oxygen perm-selectively at elevated temperature and have potential for improving the performance and reducing the cost of several industrial processes: such as the conversion of natural gas to syngas, or to separate oxygen from air for oxy-fuel combustion in electricity generation (to reduce NOx emissions and facilitate CO2 sequestration). These pressure-driven solid state membranes are based on fast oxygen-ion conducting ceramics, but also need a compensating flow of electrons. Dual-phase composites are attractive since they provide an extra degree of freedom, compared with single phase membranes, for optimising the overall membrane performance. In this study, composites containing gadolinia doped ceria (CGO, Ce0.9Gd0.1O2- ) and either strontium-doped lanthanum cobaltite (LSC, La0.9Sr0.1CoO3- or La0.6Sr0.4CoO3- ) or silver (Ag) were investigated for possible application as oxygen separation membranes in oxy-fuel combustion system. These should combine the high oxygen ion conductivity of CGO with the high electronic conductivity and fast oxygen surface exchange of LSC or silver. Dense mixed-conducting composite materials of LSC/CGO (prepared by powder mixing and sintering) and Ag/CGO composites (prepared by silver plus copper oxide infiltration method) showed high relative density (above 95%), low background gas leakage and also good electrical conduction. The percolation threshold of the electronic conducting component was determined to be approximately 20 vol.% for both LSC compositions and 14 vol.% for Ag. Isotopic exchange and depth profiling by secondary ion mass spectrometry was used to investigated the oxygen tracer diffusion (D*) and surface exchange coefficient (k*) of the composites. Composites just above the electronic percolation threshold exhibited high solid state oxygen diffusivity, fast surface exchange activity moderate thermal expansion and sufficient mechanical strength thus combining the benefits of their constituent materials. The preliminary work on oxygen permeation measurement showed that the reasonable magnitude of oxygen fluxes is possible to be achieved. This indicates that the composites of LSC/CGO and Ag/CGO are promising for further development as passive oxygen separation membranes.EThOS - Electronic Theses Online ServiceRoyal Thai Government, Ministry of Science and Technology ScholarshipGBUnited Kingdo

Platelet Ceria Catalysts from Solution Combustion and Effect of Iron Doping for Synthesis of Dimethyl Carbonate from CO2

: Solution combustion (SC) remains among the most promising synthetic strategies for the production of crystalline nanopowders from an aqueous medium, due to its easiness, time and cost-effectiveness, scalability and eco-friendliness. In this work, this method was selected to obtain anisometric ceria-based nanoparticles applied as catalysts for the direct synthesis of dimethyl carbonate. The catalytic performances were studied for the ceria and Fe-doped ceria from SC (CeO2-SC, Ce0.9Fe0.1O2-SC) in comparison with the ceria nanorods (CeO2-HT, Ce0.9Fe0.1O2-HT) obtained by hydrothermal (HT) method, one of the most studied systems in the literature. Indeed, the ceria nanoparticles obtained by SC were found to be highly crystalline, platelet-shaped, arranged in a mosaic-like assembly and with smaller crystallite size (≈6 nm vs. ≈17 nm) and higher surface area (80 m2 g-1vs. 26 m2 g-1) for the undoped sample with respect to the Fe-doped counterpart. Although all samples exhibit an anisometric morphology that should favor the exposition of specific crystalline planes, HT-samples showed better performances due to higher oxygen vacancies concentration and lower amount of strong basic and acid sites