Engineering the Near‐Surface of PtRu3 Nanoparticles to Improve Hydrogen Oxidation Activity in Alkaline Electrolyte

Tailoring the near-surface composition of Pt-based alloy can optimize the surface chemical properties of a nanocatalyst and further improve the sluggish H₂ electrooxidation performance in an alkaline electrolyte. However, the construction of alloy nanomaterials with a precise near-surface composition and smaller particle size still needs to overcome huge obstacles. Herein, ultra-small PtRu₃ binary nanoparticles (<2 nm) evenly distributed on porous carbon (PtRu₃ /PC), with different near-surface atomic compositions (Pt-increased and Ru-increased), are successfully synthesized. XPS characterizations and electrochemical test confirm the transformation of a near-surface atomic composition after annealing PtRu₃ /PC-300 alloy; when annealing in CO atmosphere, forming the Pt-increased near-surface structure (500 °C), while the Ru-increased near-surface structure appears in an Ar heat treatment process (700 °C). Furthermore, three PtRu₃ /PC nanocatalysts all weaken the hydrogen binding strength relative to the Pt/PC. Remarkably, the Ru-increased nanocatalyst exhibits up to 38.8-fold and 9.2-fold HOR improvement in mass activity and exchange current density, compared with the Pt/PC counterpart, respectively. CO-stripping voltammetry tests demonstrate the anti-CO poisoning ability of nanocatalysts, in the sequence of Ru-increased ≥ PtRu₃ /PC-300 > Pt-increased > Pt/PC. From the perspective of engineering a near-surface structure, this study may open up a new route for the development of high-efficiency electrocatalysts with a strong electronic effect and oxophilic effect.