Atomic Structure Evolution of Pt-Co Binary Catalysts: Single Metal Sites versus Intermetallic Nanocrystals

Due to their exceptional catalytic properties for the oxygen reduction reaction (ORR) and other crucial electrochemical reactions, PtCo intermetallic nanoparticle (NP) and single atomic (SA) Pt metal site catalysts have received considerable attention. However, their formation mechanisms at the atomic level during high-temperature annealing processes remain elusive. Here, the thermally driven structure evolution of Pt-Co binary catalyst systems is investigated using advanced in situ electron microscopy, including PtCo intermetallic alloys and single Pt/Co metal sites. The pre-doping of CoN₄ sites in carbon supports and the initial Pt NP sizes play essential roles in forming either Pt₃ Co intermetallics or single Pt/Co metal sites. Importantly, the initial Pt NP loadings against the carbon support are critical to whether alloying to L1₂ -ordered Pt₃ Co NPs or atomizing to SA Pt sites at high temperatures. High Pt NP loadings (e.g., 20%) tend to lead to the formation of highly ordered Pt₃ Co intermetallic NPs with excellent activity and enhanced stability toward the ORR. In contrast, at a relatively low Pt loading (<6 wt%), the formation of single Pt sites in the form of PtC₃ N is thermodynamically favorable, in which a synergy between the PtC₃ N and the CoN₄ sites could enhance the catalytic activity for the ORR, but showing insufficient stability.