Breaking the Pt Electron Symmetry and OH Spillover towards PtIr Active Center for Performance Modulation in Direct Ammonia Fuel Cell

Abstract The growing interest in low‐temperature direct ammonia fuel cells (DAFCs) arises from the utilization of a carbon‐neutral ammonia source; however, DAFCs encounter significant electrode overpotentials due to the substantial energy barrier of the *NH ₂ to *NH dehydrogenation, compounded by the facile deactivation by *N on the Pt surface. In this work, a unique catalyst, Pt ₄ Ir@AlOOH/NGr i.e., Pt ₄ Ir/ANGr, is introduced composed of PtIr alloy nanoparticles controllably decorated on the pseudo‐boehmite phase of AlOOH‐supported nitrogen‐doped reduced graphene (AlOOH/NGr) composite, synthesized via the polyol reduction method. The detailed studies on the structural and electronic properties of the catalyst by XAS and VB‐XPS reveal the possible electronic modulations. The optimized Pt ₄ Ir/ANGr composition exhibits a significantly improved onset potential and mass activity for AOR. The DFT study confirms the OH _ad species spillover by AlOOH and Pt ₄ Ir (100) facilitates the conversion of the *NH ₂ to *NH with minimal energy barriers. Finally, testing of DAFC at the system level using a membrane electrode assembly (MEA) with Pt ₄ Ir/ANGr as the anode catalyst, demonstrating the suitability of the catalyst for its practical applications. This study thus uncovers the potential of the Pt ₄ Ir catalyst in synergy with ANGr, largely addressing the challenges in hydrogen transportation, storage, and safety within DAFCs.