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Description
In-situ environmental transmission electron microscopy (ETEM) is a powerful tool for following the evolution of supported metal nanoparticles under different reacting gas conditions at elevated temperatures. The ability to observe the events in real time under reacting gas conditions can provide significant information on the fundamental processes taking place in catalytic materials, from which the performance of the catalyst can be understood. The first part of this dissertation presents the application of in-situ ETEM studies in developing structure-activity relationship in supported metal nanoparticles. In-situ ETEM studies on nanostructures in parallel with ex-situ reactor studies of conversions and selectivities were performed for partial oxidation of methane (POM) to syngas (CO+H2) on Ni/SiO2, Ru/SiO2 and NiRu/SiO2 catalysts. During POM, the gas composition varies along the catalyst bed with increasing temperature. It is important to consider these variations in gas composition in order to design experiments for in-situ ETEM. In-situ ETEM experiments were performed under three different reacting gas conditions. First in the presence of H2, this represents the state of the fresh catalyst for the catalytic reaction. Later in the presence of CH4 and O2 in 2:1 ratio, this is the composition of the reacting gases for the POM reaction and this composition acts as an oxidizing environment. Finally in the presence of CH4, this is the reducing gas. Oxidation and reduction behavior of Ni, Ru and NiRu nanoparticles were followed in an in-situ ETEM under reacting gas conditions and the observations were correlated with the performance of the catalyst for POM. The later part of the dissertation presents a technique for determining the gas compositional analysis inside the in-situ ETEM using electron energy-loss spectroscopy. Techniques were developed to identify the gas composition using both inner-shell and low-loss spectroscopy of EELS. Using EELS, an "operando TEM" technique was successfully developed for detecting the gas phase catalysis inside the ETEM. Overall this research demonstrates the importance of in-situ ETEM studies in understanding the structure-activity relationship in supported-metal catalysts for heterogeneous catalysis application.
ContributorsChenna, Santhosh (Author) / Crozier, Peter A. (Thesis advisor) / Carpenter, Ray (Committee member) / Sieradzki, Karl (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2011
Description
One the major problems of this modern industrialized world is its dependence on fossil fuels for its energy needs. Burning of fossils fuels generates green-house gases which have adverse effects on global climate contributing to global warming. According to Environmental Protection Agency (EPA), carbon dioxide makes up 80 percent of green-house gases emitted in USA. Electrochemical reduction of carbon dioxide is an approach which uses CO2 emissions to produce other useful hydrocarbons which can be used in many ways.
In this study, primary focus was on optimizing the operating conditions, determining the better catalyst material, and analyzing the reaction products for the process of electrochemical reduction of carbon dioxide (ERC). Membrane electrode assemblies (MEA’s) are developed by air bushing the metal particles with a spray gun on to Nafion-212 which is a solid polymer based electrolyte (SPE), to support the electrodes in the electrochemical reactor gas diffusion layers (GDL) are developed using porous carbon paper. Anode was always made using the same material which is platinum but cathode material was changed as it is the working electrode.
The membrane electrode assembly (MEA) is then placed into the electrochemical reactor along with gas diffusion layer (GDL) to assess the performance of the catalyst material by techniques like linear sweep voltammetry and chronoamperometry. Performance of MEA was analyzed at 4 different potentials, 2 different temperatures and for 2 different cathode catalyst materials. The reaction products of the process are analyzed using gas chromatography (GC) which has thermal conductivity detector (TCD) used for detecting hydrogen (H2), carbon monoxide (CO) and flame ionization detector (FID) used for detecting hydrocarbons. The experiments performed at 40o C gave the better results when compared with the experiments performed at ambient temperature. Also results suggested that copper oxide cathode catalyst has better durability than platinum-carbon. Maximum faradaic efficiency for methane was 5.3% it was obtained at 2.25V using copper oxide catalyst. Furthermore, experiments must be carried out to make the electrochemical reactor more robust to withstand all the operating conditions like higher potentials and to make it a solar powered reactor.
In this study, primary focus was on optimizing the operating conditions, determining the better catalyst material, and analyzing the reaction products for the process of electrochemical reduction of carbon dioxide (ERC). Membrane electrode assemblies (MEA’s) are developed by air bushing the metal particles with a spray gun on to Nafion-212 which is a solid polymer based electrolyte (SPE), to support the electrodes in the electrochemical reactor gas diffusion layers (GDL) are developed using porous carbon paper. Anode was always made using the same material which is platinum but cathode material was changed as it is the working electrode.
The membrane electrode assembly (MEA) is then placed into the electrochemical reactor along with gas diffusion layer (GDL) to assess the performance of the catalyst material by techniques like linear sweep voltammetry and chronoamperometry. Performance of MEA was analyzed at 4 different potentials, 2 different temperatures and for 2 different cathode catalyst materials. The reaction products of the process are analyzed using gas chromatography (GC) which has thermal conductivity detector (TCD) used for detecting hydrogen (H2), carbon monoxide (CO) and flame ionization detector (FID) used for detecting hydrocarbons. The experiments performed at 40o C gave the better results when compared with the experiments performed at ambient temperature. Also results suggested that copper oxide cathode catalyst has better durability than platinum-carbon. Maximum faradaic efficiency for methane was 5.3% it was obtained at 2.25V using copper oxide catalyst. Furthermore, experiments must be carried out to make the electrochemical reactor more robust to withstand all the operating conditions like higher potentials and to make it a solar powered reactor.
ContributorsMudunur, Santosh shekar (Author) / Kannan, Arunachala (Thesis advisor) / Phelan, Patrick (Committee member) / Huang, Huei-Ping (Committee member) / Arizona State University (Publisher)
Created2017