Mesostructured Intermetallic Compounds of Platinum and Non-Transition Metals for Enhanced Electrocatalysis of Oxygen Reduction Reaction

Alloying techniques show genuine potential to develop more effective catalysts than Pt for oxygen reduction reaction (ORR), which is the key challenge in many important electrochemical energy conversion and storage devices, such as fuel cells and metal‐air batteries. Tremendous efforts have been made to improve ORR activity by designing bimetallic nanocatalysts, which have been limited to only alloys of platinum and transition metals (TMs). The Pt‐TM alloys suffer from critical durability in acid‐media fuel cells. Here a new class of mesostructured Pt–Al catalysts is reported, consisting of atomic‐layer‐thick Pt skin and Pt3Al or Pt5Al intermetallic compound skeletons for the enhanced ORR performance. As a result of strong Pt–Al bonds that inhibit the evolution of Pt skin and produce ligand and compressive strain effects, the Pt3Al and Pt5Al mesoporous catalysts are exceptionally durable and ≈6.3‐ and ≈5.0‐fold more active than the state‐of‐the‐art Pt/C catalyst at 0.90 V, respectively. The high performance makes them promising candidates as cathode nanocatalysts in next‐generation fuel cells. A mesostructured ordered intermetallic of PtAl is developed by a facilely and cost‐effectively alloying/dealloying approach for the high‐performance ORR. The extremely strong covalent bonds between Pt and Al not only give rise to excellent kinetic stability, but also result in remarkable catalytic activity duo to the downshift of d‐band center.