Structural and Valence State Modification of Cobalt in CoPt Nanocatalysts in Redox Conditions

Platinum is the primary catalyst for many chemical reactions in the field of heterogeneous catalysis. However, platinum is both expensive and rare. Therefore, it is advantageous to combine Pt with another metal to reduce cost while also enhancing stability. To that end, Pt is often combined with Co to form Co-Pt nanocrystals. However, dynamical restructuring effects that occur during reaction in Co-Pt ensembles can impact catalytic properties. In this study, model Co₂Pt₃ nanoparticles supported on carbon were characterized during a redox cycle with two in situ approaches, namely, X-ray absorption spectroscopy (XAS) and scanning transmission electron microscopy (STEM) using a multimodal microreactor. The sample was exposed to temperatures up to 500 °C under H₂, and then to O₂ at 300 °C. Irreversible segregation of Co in the Co₂Pt₃ particles was seen during redox cycling, and substantial changes of the oxidation state of Co were observed. After H₂ treatment, a fraction of Co could not be fully reduced and incorporated into a mixed Co-Pt phase. Reoxidation of the sample increased Co segregation, and the segregated material had a different valence state than in the fresh, oxidized sample. This in situ study describes dynamical restructuring effects in CoPt nanocatalysts at the atomic scale that are crucial to understand in order to improve the design of catalysts used in major chemical processes.