The central topic of this work has been synthesis, characterization and optimization of novel Ni-Ga based catalysts for hydrogenation of CO2 to methanol. The overall goal was to search for materials that could be used as a low temperature (and low pressure) methanol synthesis catalyst. This is required for small scale delocalized methanol production sites, where installation of energy demanding compression units should be avoided. The work was triggered by DFT calculations, which showed that certain bimetallic systems are active towards methanol synthesis from CO2 and H2 at ambient pressure. Among them, Ni-Ga has been chosen, primarily due to low price of constituent metals. After the preliminary optimization work, an optimal catalyst composition and preparation method has been suggested. Indeed, for an optimal catalyst, which is a SiO2 supported Ni-Ga prepared from a solution of nitrates containing 5:3 molar ratio of Ni:Ga, the intrinsic activity (methanol production rate per active surface area) is comparable to that of highly optimised Cu/ZnO/Al2O3. Formation of the catalyst was investigated with the aid of in-situ XRD and in-situ XAS techniques. The mechanism of alloying was proposed. It was found that the Ni-Ga nanoparticle formation always proceeds through a more Ni-rich phase. These studies were backed up with the electron microscopy, x-ray fluorescence, thermogravimetric analysis and mass spectroscopy. The catalyst was found to deactivate both at normal reaction conditions (presumably due to carbon formation) and under accelerated ageing conditions (due to dealloying). However, the initial activity could always be restored after treatment in hydrogen flow at elevated temperatures. The work in the direction of suppression of deactivation and by-product formation is still in progress.
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Chorkendorff, Ib, Dahl, Søren
Department of Physics, Technical University of Denmark, 2013