Enhanced CO₂ Electrolysis Through Mn Substitution Coupled with Ni Exsolution in Lanthanum Calcium Titanate Electrodes

In this study, perovskite oxides La0.3Ca0.6Ni0.05MnxTi0.95-xO3-gamma (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 - 3% H2O. The performance of La0.3Ca0.6Ni0.05Ti0.95O3-gamma is notably improved by co-doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO(3)) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133 h of high-temperature operation, suggesting a reliable cathode material for CO2 electrolysis.