Unravelling the role of dopants in the electrocatalytic activity of ceria towards CO₂ reduction in solid oxide electrolysis cells

CO₂ reduction in Solid Oxide Electrolysis Cells (SOECs) is a key-technology for the transition to a sustainable energy infrastructure and chemical industry. Ceria (CeO₂) holds great promise in developing highly efficient, cost-effective and durable fuel electrodes, due to its promising electrocatalytic properties, and proven ability to suppress carbon deposition and to tolerate high concentrations of impurities. In the present work, we investigate the intrinsic electrocatalytic activity of ceria towards CO₂ reduction by means of electrochemical impedance spectroscopy (EIS) on model systems with well-defined geometry, composition and surface area. Aiming at the optimization of the intrinsic catalytic properties of the material, we systematically study the effect of different dopants (Zr, Gd, Pr and Bi) on the reaction rate under varying operating conditions (temperature, gas composition and applied polarization) relevant for SOECs. The electrochemical measurements reveal the dominant role of the surface defect chemistry of the material in the reaction rate, with doping having only a mild effect on the rate and activation energy of the reaction. By analyzing the pO₂ and overpotential dependence of the reaction rate with a general micro-kinetic model, we are able to identify the second electron transfer as the rate limiting step of the process, highlighting the dominant role of surface polarons in the energy landscape. These insights on the correlation between the surface defects and the electrocatalytic activity of ceria open new directions for the development of highly performing ceria-based technological electrodes.