Electron Tomography Reveals Porosity Degradation Spatially on Individual Pt-Based Nanocatalysts

Probing porosity evolution is essential to understand the degradation mechanism of electrocatalytic activity. However, spatially dependent degradation pathways for porous catalysts remain elusive. Here, we reveal the multiple degradation behaviors of individual PtCu₃ nanocatalysts spatially by three-dimensional (3D) electron tomography. We demonstrate that the surface area-volume ratio (SVR) of cycled porous particles decreases linearly rather than reciprocally with particle size. Additionally, an improved SVR (about 3-fold enhancement) results in increased oxygen reduction reaction (ORR) efficiency at the early stage. However, in the subsequent cycles, the degradation of catalytic activity is due to the excessive growth of pores, the reduction of reaction sites, and the chemical segregation of Cu atoms. The spatial porosity evolution model of nanocatalysts is applicable for a wide range of catalytic reactions, providing a critical insight into the degradation of catalyst activity.