Entropy‐Driven Ostwald Ripening Reversal Promotes the Formation of Low‐Platinum Intermetallic Fuel Cell Catalysts

Abstract Strain engineering has been widely used to optimize platinum‐based oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs). PtM ₃ (M is base metals), a well‐known high‐compressive‐strain intermetallic alloy, shows promise as a low platinum ORR catalyst due to high intrinsic activity. However, during the alloying of Pt with a threefold amount of M, a notable phase separation between Pt and M may occur, with M particles rapidly sintering while Pt particles grow slowly, posing a challenge in achieving a well‐defined PtM ₃ intermetallic alloy. Here, an entropy‐driven Ostwald ripening reversal phenomenon is discovered that enables the synthesis of small‐sized Pt(FeCoNiCu) ₃ intermetallic ORR catalysts. High entropy promotes the thermodynamic driving force for the alloying Pt with M, which triggers the Ostwald ripening reversal of sintered FeCoNiCu particles and facilitates the formation of uniform Pt(FeCoNiCu) ₃ intermetallic catalysts. The prepared Pt(FeCoNiCu) ₃ catalysts exhibit a high specific activity of 3.82 mA cm ⁻² , along with a power density of ≈1.3 W cm ⁻² at 0.67 V and 94 °C with a cathode Pt loading of 0.1 mg cm ⁻² in H ₂ –air fuel cell.