3D atomic-scale imaging of mixed Co-Fe spinel oxide nanoparticles during oxygen evolution reaction
Weikai Xiang, Nating Yang, Xiaopeng Li, Julia Linnemann, Ulrich Hagemann, Olaf Ruediger, Markus Heidelmann, Tobias Falk, Matteo Aramini, Serena DeBeer, Martin Muhler, Kristina Tschulik, Tong Li
Abstract
Abstract The three-dimensional (3D) distribution of individual atoms on the surface of catalyst nanoparticles plays a vital role in their activity and stability. Optimising the performance of electrocatalysts requires atomic-scale information, but it is difficult to obtain. Here, we use atom probe tomography to elucidate the 3D structure of 10 nm sized Co 2 FeO 4 and CoFe 2 O 4 nanoparticles during oxygen evolution reaction (OER). We reveal nanoscale spinodal decomposition in pristine Co 2 FeO 4 . The interfaces of Co-rich and Fe-rich nanodomains of Co 2 FeO 4 become trapping sites for hydroxyl groups, contributing to a higher OER activity compared to that of CoFe 2 O 4 . However, the activity of Co 2 FeO 4 drops considerably due to concurrent irreversible transformation towards Co IV O 2 and pronounced Fe dissolution. In contrast, there is negligible elemental redistribution for CoFe 2 O 4 after OER, except for surface structural transformation towards (Fe III , Co III ) 2 O 3 . Overall, our study provides a unique 3D compositional distribution of mixed Co-Fe spinel oxides, which gives atomic-scale insights into active sites and the deactivation of electrocatalysts during OER.