Perovskite gas sensor : prepared by High Energy Ball Milling

Authors: Ghasdi Manghootaee, Mohammad
Advisor: Darvishi Alamdari, Houshang
Abstract: The aim of this project is to explore the possibility of exploitation of nanostructured mixed oxides obtained by HEBM technique in development of high efficient gas sensors in terms of performance and cost. LaFeO3 and LaCoO3 formulations were chosen as perovskite-based materials, based on their intrinsic sensing properties reported on the literature, to investigate the effect of synthesis parameters on their gas sensing performance. In the first step, synthesis parameters were optimized to obtain nanocrystalline LaCoO3 perovskite-oxide. A coating method was then developed in order to coat the sensing material in powder form on an electrically resistant substrate and to provide a sensing device. This coating method consisted of a simple wash-coating process where the nanocrystalline powder is put in suspension in an aqueous solution with an accurately adjusted pH and the substrate is dipped in until a continuous and homogeneous thick sensing layer is formed. The samples were then dried and conditioned and the sensing properties were evaluated basically by measuring electrical resistance behaviour of the device in different gas compositions. In order to compare the ball milling (BM) method with other synthesis methods, the same formulation was also obtained using sol-gel (SG) and solid-state reaction (SSR) methods. The effect of crystallite size on CO sensing performance of synthesized LaCoO3 was studied. Compared to the other methods, HEBM resulted in lowest crystallite size of 11 nm while the SG and SSR gave a crystallite size of 20 nm and 1 µm, respectively. While the specific surface area of all samples remained similar, the maximum response ratio was increased from 7% for SSR samples to 17% and 26% for SG and BM samples, respectively. In the second step, specific surface area (SSA) of milled materials was increased using a second milling process. The new synthesis process was called Activated Reactive Synthesis (ARS). The effect of surface area on gas sensing performance and oxygen mobility as well as oxygen desorption capacity of synthesized materials was investigated. Synthesized materials were characterized using XRD, TPD-O2 and BET. Gas sensing results revealed a positive effect of low crystallite size and high surface area on gas sensing performance of milled materials. Specific surface area of the BM sample was successfully increased from 4 m2/g to an optimum value of 66 m2/g by an ARS step. Improved BM material showed the highest response ratio of up to 75% for 100 ppm CO in dry air at 125°C, which is four and ten times higher than those obtained by sol-gel and solid-state reaction methods, respectively. The gas sensing performance of LaCoO3 samples with a crystallite size of 11 nm and a specific surface of 66 m2/g was set as a benchmark for further improvements. In the third step, the potential of ARS method in providing the doped formulations was explored by synthesizing La1-xCexCoO3 series doped with different amounts of cerium. The effect of cerium doping on perovskite structure and its gas sensing properties was then evaluated. Ce-doped formulations showed a saturation point at 10 at.% in the perovskite structure. The optimum CO sensing temperature for doped formulation was found to be 100°C compared to 130°C for pure perovskite. Among the Ce-doped formulations, La0.9Ce0.1CoO3 showed the best response ratio (240%) with respect to 100 ppm CO that was four times higher than the response ratio of pure LaCoO3. TPD-O2, TPD-CO and XPS were performed to find the relation between sensing performance and physical and chemical properties of synthesized samples. Further addition of Ce resulted in segregation of cerium oxide as a second phase (impurity) and deteriorated the sensing performance of the doped materials. Nanostructured LaFeO3 perovskite was also synthesized using ARS method. This formulation was chosen for its intrinsic hydrogen and CO sensing properties. The sensing properties of this formulation with respect to methane were improved by Pd doping. Pd oxide was impregnated on the surface of nanostructured and high surface of LaFeO3 to further enhance its methane sensing performance. Different amounts of palladium oxide were used to find the optimum level of doping. Doped formulations showed a good sensitivity to methane at very low temperature (< 150°C) while pure LaFeO3 did definitely not show any sensing property with respect to methane at the same temperature range. LaFeO3 with 2 wt.% Pd with a crystallite size of 14 nm and a high specific surface area of 46 m2/g showed maximum response ratio of 600% with respect to 300 ppm CH4 in air. Methane storage capacity of doped formulation was evaluated to investigate the effect of doping element on adsorption capacity and its relation with the sensing performance of synthesized samples. No catalytic activity was observed for doped formulations.
Document Type: Thèse de doctorat
Issue Date: 2013
Open Access Date: 19 April 2018
Grantor: Université Laval
Collection:Thèses et mémoires

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