Strain in Core–Shell Spinel Nanocrystals Enhances ORR Activity

Strain engineering of electrocatalysts has been an extensively studied field in recent years, but there has been limited investigation of strain and ligand effects in the catalysts of heterostructured oxides. Such studies could have significant impacts as the localized changes in the electronic structure of metal oxide shells may induce enhanced catalytic activity, complementing those from the well-studied metallic systems. Here, we developed a colloidal synthesis route to monodisperse core–shell spinel oxide nanocrystals with tunable shell thickness for the oxygen reduction reaction (ORR) in alkaline media. We compare the activity of these heterostructured particles, finding a higher activity for smaller shell thicknesses. The smallest shell thickness aligns with the highest shell strain. The best-performing core–shell sample achieved a half-wave potential of 0.893 V versus RHE in 1.0 M KOH, making it one of the best-reported values for a spinel oxide electrocatalyst for alkaline ORR with a PGM-free catalyst. In addition, this value is within 11 mV of that of the Pt/C reference material. Though a Pt/C reference sample has an overall higher mass activity at 0.9 V vs RHE, when cost is considered, the strained spinel outperforms the Pt/C by over 600-fold at this potential. Our results provide an impetus for exploring the deliberate and controlled use of strain engineering in metal oxides as high-performance, low-cost electrocatalysts.