The reduction of CO2 is a promising route for the synthesis of renewable energy carriers and the removal of CO2 from the atmosphere to limit global warming. These negative emission technologies (NETs) require the conversion of carbon dioxide into a stable and easily storable form[1]. However, despite its potential, the development of suitable CO2 reduction catalysts is still in its infancy. Indeed state of the art catalysts suffer from high overpotentials, a low selectivity between possible products and a generally low yield of post CO products with two or more carbon atoms. Catalysts which even allow for the electrochemical polymerization of CO2 and thus, the direct formation of hard carbon were completely absent until the work of Esrafilzadeh et al.[2]. Using a liquid electrocatalyst consisting of Ga, In, Sn and Ce in a n,n-dimethylformamide (DMF) electrolyte they were able to polymerize CO2 electrochemically to a carbonaceous material. They hypothesized that the active catalyst consists of a cerium oxide which is reduced to metallic Ce in the process. However, no direct proof for this hypothesis was provided. Also a possible mechanism which could lead to the reported products is so far unknown.In this contribution we will explore the reaction mechanisms for the electrochemical polymerization of CO2 using density functional theory (DFT) modelling. In the initial step, the most likely active sites at Ce oxide are identified. This is then followed by a detailed analysis of the reaction route which is based on well known mechanisms in organic chemistry. We find that an oxygen defect rich CeO2(110) surface is most likely present under reaction conditions. [3] The reaction over this surface is initialized at oxygen defect sites. Chain propagation is then achieved through an electrochemical aldol condensation type mechanism (Figure 1). [3] References 1 J. Hilaire, J. C. Minx et al., Climatic Change, 2019, 157, 189.2 D. Esrafilzadeh, A. Zavabeti et al., Nature. Commun., 2019, 10, 865.3 F. Keller, J. Döhn, A. Groß, M. Busch, in preparation. Figure 1
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