Buonsanti, RaffaellaTileli, VasilikiVávra, Jan2022-05-132022-05-13202210.5075/epfl-thesis-9556https://infoscience.epfl.ch/handle/20.500.14299/187852Electrochemical reduction of carbon dioxide is a promising approach to decrease the amount of anthropogenic CO2 being released into the atmosphere, provided that a surplus of renewable electrical energy is available. Copper based materials are at the center of attention as a catalyst to this reaction. The exact atomic arrangement of the Cu surface determines the selectivity and activity of the electrochemical reaction. However, recent evidence reports morphology changes of the Cu catalyst surface during the course the reaction. This thesis investigates the operational stability of Cu catalysts with various in-situ techniques, particularly liquid cell TEM, which was adapted to electrochemical CO2 reduction reaction so that it provides morphological and structural information on the catalyst in real-time. Two distinct stages contributing to the reconstruction of Cu catalysts are identified. In the first stage, the catalyst dissolves and spontaneously oxidizes during its contact with the reaction environment. As the reducing potential is applied, the initially dissolved Cu deposits back onto the working electrode. In the second stage, during the catalyst operation at reducing potentials, the dissolution/redeposition continues in the close vicinity of the catalyst surface. Formation of transient [CuCO]+ complexes is identified as the major process responsible for the operational dissolution of Cu catalysts. The provided mechanistic understanding of Cu catalyst (in)stability during electrochemical reduction of CO2 rationalizes the efforts in designing catalysts and electrolyzers with long-term stable operation and motivates further investigation on how to control the operational redeposition of Cu to continuously refresh the active surface motives.enCO2RRin-situ TEMcatalystcopperstabilitythesis::doctoral thesis