The thermal treatment of bimetallic nanocatalysts plays an important role in determining their catalytic performance. Here tuning the surface oxidized metal species of bimetallic Pd–Fe electrocatalysts for the formic acid (FA) oxidation reaction is reported and a correlation between the surface oxidized metal species of the Pd–Fe nanoparticles and their catalytic activities is proposed. The structural details of the Pd–Fe/C catalysts are characterized by X-ray diffraction, X-ray photoelectron spectroscopy and high-sensitivity low-energy ion scattering (HS-LEIS). Cyclic voltammetry measurements demonstrated that the mass activity of the Pd–Fe nanoparticles with a molar ratio of Pd/Fe = 1/15 is about 7.4 times higher than that of Pd/C. This enhancement could be attributed to the synergistic effect between Pd(0) and Pd oxidized species on the surface of the Pd–Fe/C treated sample and electronic effects. This finding demonstrates the importance of surface oxidized metal species at the nanoscale in harnessing the true electrocatalytic potential of bimetallic nanoparticles and opens up strategies for the development of highly active bimetallic nanoparticles for electrochemical energy conversion.
