Taking the commercial Pt/C catalyst as a baseline, we disclosed Fe-based catalyst prepared by controlled self-assembly can be used to catalyze hydrogen oxidation reaction (HOR) in the proton exchange membrane fuel cells (PEMFCs). Our electrochemical results clarified that the HOR kinetics is H-2 -> 2H(ad)-> 2H(+),which are determined by intermediate Had species and transfer impacts from H2 and H+. Specifically, the Fe-based catalyst can accelerate Had adsorption/desorption in low potential due to the Fe-Had reversibility of NPs, and the strengthened mass transfer as Well as recoverable active sites of PANI/Fe NPs (polyaniline/Fe NPs) interface in high potential, thus contributing intermittent HOR current in the HOR region. As HOR catalyst, our prototype fuel cell using Fe-based catalyst was demonstrated high E-ocp, mass power density and stability in 110 hrs, tolerance for C3H8 fuel, promising in replacing Pt-based catalysts in future. (C) 2017 Elsevier Ltd. All rights reserved.