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A study of microwave plasma-assisted CO2 conversion by plasma catalysis

par Chen, Guoxing
Président du jury Godet, Stéphane
Promoteur Delplancke, Marie-Paule
Co-Promoteur Snyders, Rony
Publication Non publié, 2017-06-21

Thèse de doctorat

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Résumé :

Climate change and global warming caused by the increasing greenhouse gases emissions (such as CO2) in the atmosphere recently attract the attention of the scientific community. These large emissions have been correlated to the Global Warming effect which has many consequences across the globe, including glacial retraction, ocean acidification and increased severity of weather events. With green technologies still in the infancy stage, it can be expected that CO2 emissions will stay this way for a long time to come. It is necessary to find an alternative way to get rid of the resulting environmentally harmful emissions. A promising solution is the use of CO2-free electrical energy produced, for example, by renewable or nuclear sources, for dissociation of CO2 or other greenhouse gases, followed by their conversion into easily storable fuels. In this context, the CO2 re-utilization to synthesize syngas, fuels or chemical compounds as well as pure CO2 dissociation into CO and O2, is of a special interest. Among the different methods to convert CO2 into added-value products (thermolysis, thermochemical cycles, electrolysis, photocatalysis, etc), the discharges sustained by microwave radiation combining high electron and low gas temperature have already demonstrated huge potential for plasma-assisted CO2 conversion. The present research work is targeted to the systematic investigation of the microwave-assisted conversion of various CO2-based gas mixtures being especially focused on plasma catalysis. The different physical effects affecting the efficiency of plasma catalysis are considered, for a better understanding of the synergistic effects between plasma and catalyst. The characterization of microwave discharges is performed by various plasma diagnostics methods, including optical spectroscopy and gas chromatography. In addition, the catalysts have been characterized by the state of art material characterization techniques, such as Transmission electron microscopy (TEM), Raman spectroscopy, etc. Such a combined characterization of both plasma and catalysts is performed for the sake of better understanding of the plasma-catalytic processes.In the first part of this study, the different dissociation pathways of the studied molecule as a function of different plasma parameters are considered by evaluating the composition with different plasma diagnostic techniques. A simple increase of Specific Energy Input (SEI) is not a promising solution since in this case the energy efficiency drops. The beneficial effects of lowering the pulse frequency for increasing CO2 conversion efficiency are observed and discussed. The obtained results are explained by the relation between the plasma pulse parameters and the rates of the relevant energy transfer mechanisms in the discharge. Simultaneous dissociation of CO2 and H2O has been investigated as well. It was clearly demonstrated that both H2 and CO productions are strongly affected by the different plasma parameters. The second part of this study deals with the effects of catalyst preparation method, nature of plasma activation gas, gas admixture, as well as NiO content and their influences on the CO2 conversion and energy efficiencies in microwave plasma. It was found throughout this work that the catalyst preparation method has a significant effect on the chemical and physical properties of the catalysts, which in turn strongly influences CO2 conversion and energy efficiencies of this process. In particular Ar plasma treatment results in a higher density of oxygen vacancies and a very favorable distribution of nickel oxide on the TiO2 surface. It is concluded that, the oxygen vacancies are the key factor explaining high catalytic activity in CO2 decomposition. The dissociative electron attachment of CO2 at the catalyst surface enhanced by the oxygen vacancies and plasma electrons can explain the observed increase of CO2 conversion efficiency as well as the energy efficiency. A mechanism explaining the observed plasma–catalyst synergy is proposed. The overall aim is to establish a model describing the interaction between highly reactive species produced in plasma discharge and supported catalyst for the conversion of CO2 into useful compounds.