Electronic and lattice strain dual tailoring for boosting Pd electrocatalysis in oxygen reduction reaction

Abstract

SummaryDeliberately optimizing the d-band position of an active component via electronic and lattice strain tuning is an effective way to boost its catalytic performance. We herein demonstrate this concept by constructing core-shell Au@NiPd nanoparticles with NiPd alloy shells of only three atomic layers through combining an Au catalysis with the galvanic replacement reaction. The Au core with larger electronegativity modulates the Pd electronic configuration, while the Ni atoms alloyed in the ultrathin shells neutralize the lattice stretching in Pd shells exerted by Au cores, equipping the active Pd metal with a favorable d-band position for electrochemical oxygen reduction reaction in an alkaline medium, for which core-shell Au@NiPd nanoparticles with a Ni/Pd atomic ratio of 3/7 exhibit a half-wave potential of 0.92 V, specific activity of 3.7 mA cm−2, and mass activity of 0.65 A mg−1 at 0.9 V, much better than most of the recently reported Pd-even Pt-based electrocatalysts.