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

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 *NH₂ to *NH dehydrogenation, compounded by the facile deactivation by *N on the Pt surface. In this work, a unique catalyst, Pt₄Ir@AlOOH/NGr i.e., Pt₄Ir/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 Pt₄Ir/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 Pt₄Ir (100) facilitates the conversion of the *NH₂ to *NH with minimal energy barriers. Finally, testing of DAFC at the system level using a membrane electrode assembly (MEA) with Pt₄Ir/ANGr as the anode catalyst, demonstrating the suitability of the catalyst for its practical applications. This study thus uncovers the potential of the Pt₄Ir catalyst in synergy with ANGr, largely addressing the challenges in hydrogen transportation, storage, and safety within DAFCs.