Stabilizing Diluted Active Sites of Ultrasmall High‐Entropy Intermetallics for Efficient Formic Acid Electrooxidation

The poisoning of undesired intermediates or impurities greatly hinders the catalytic performances of noble metal-based catalysts. Herein, high-entropy intermetallics i-(PtPdIrRu)₂FeCu (HEI) are constructed to inhibit the strongly adsorbed carbon monoxide intermediates (CO*) during the formic acid oxidation reaction. As probed by multiple-scaled structural characterizations, HEI nanoparticles are featured with partially negative Pt oxidation states, diluted Pt/Pd/Ir/Ru atomic sites and ultrasmall average size less than 2 nm. Benefiting from the optimized structures, HEI nanoparticles deliver more than 10 times promotion in intrinsic activity than that of pure Pt, and well-enhanced mass activity/durability than that of ternary i-Pt₂FeCu intermetallics counterpart. In situ infrared spectroscopy manifests that both bridge and top CO* are favored on pure Pt but limited on HEI. Further theoretical elaboration indicates that HEI displayed a much weaker binding of CO* on Pt sites and sluggish diffusion of CO* among different sites, in contrast to pure Pt that CO* bound more strongly and was easy to diffuse on larger Pt atomic ensembles. This work verifies that HEIs are promising catalysts via integrating the merits of intermetallics and high-entropy alloys.