Electrochemical Activation Applied to Perovskite Titanate Fibers to Yield Supported Alloy Nanoparticles for Electrocatalytic Application

Active bi-metallic nanoparticles are of key importance in catalysis and renewable energy. Here, the in situ formation of bi-metallic nanoparticles is investigated by exsolution on 200 nm diameter perovskite fibers. The B-site co-doped perovskite fibers display a high degree of exsolution, decorated with NiCo or Ni₃ Fe bi-metallic nanoparticles with average diameter about 29 and 35 nm, respectively. The perovskite fibers are utilized as cathode materials in pure CO₂ electrolysis cells due to their redox stability in the CO/CO₂ atmosphere. After in situ electrochemical switching, the nanoparticles exsolved from the perovskite fiber demonstrate an enhanced performance in pure CO₂ electrolysis. At 900 °C, the current density of solid oxide electrolysis cell (SOEC) with 200 µm YSZ electrolyte supported NiFe doped perovskite fiber anode reaches 0.75 Acm^-2 at 1.6 V superior to the NiCo doped perovskite fiber anode (about 1.5 times) in pure CO₂ . According to DFT calculations (PBE-D3 level) the superior CO₂ conversion on NiFe compared to NiCo bi-metallic species is related to an enhanced driving force for C-O cleavage under formation of CO chemisorbed on the nanoparticle and a reduced binding energy of CO required to release this product.