Intermetallic PtFe Electrocatalysts for the Oxygen Reduction Reaction: Ordering Degree‐Dependent Performance

Platinum-based atomically ordered alloys (i.e., intermetallic compounds) have distinct advantages over disordered solid solution counterparts in boosting the cathodic oxygen-reduction reaction (ORR) in proton-exchange-membrane fuel cells. Nevertheless, the pivotal role of ordering degree of intermetallic catalysts in promoting ORR performance has been ignored heavily so far, probably owing to the lack of synthetic routes for controlling the ordering degree, especially for preparing highly ordered intermetallic catalysts. Herein, a family of intermetallic PtFe catalysts with similar particle size of 3-4 nm but varied ordering degree in a wide range of 10-70% are prepared. After constructing the PtFe/Pt core/shell structure with around 3 Pt-layer skin, a positive correlation between the ordering degree of the intermetallic catalysts and their ORR activity and durability is identified. Notably, the highly ordered PtFe/Pt catalyst exhibits a high mass activity of 0.92 A mgPt-1 at 0.9 ViR-corrected as cathode catalyst in H2 -O2 fuel cell, with only 24% loss after accelerated durability tests. The ordering degree-dependent performance can be ascribed to the compressive strain effect induced by the intermetallic PtFe core with smaller lattice parameters, and the more thermodynamically stable intermetallic structure compared to disordered alloys.