Strain and Shell Thickness Engineering in Pd₃Pb@Pt Bifunctional Electrocatalyst for Ethanol Upgrading Coupled with Hydrogen Production

The ethanol oxidation reaction (EOR) is an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen evolution cells. However, the development of high-performance bifunctional electrocatalysts for both EOR and hydrogen evolution reaction (HER) is a major challenge. Herein, the synthesis of Pd3Pb@Pt core-shell nanocubes with controlled shell thickness by Pt-seeded epitaxial growth on intermetallic Pd3Pb cores is reported. The lattice mismatch between the Pd3Pb core and the Pt shell leads to the expansion of the Pt lattice. The synergistic effects between the tensile strain and the core-shell structures result in excellent electrocatalytic performance of Pd3Pb@Pt catalysts for both EOR and HER. In particular, Pd3Pb@Pt with three Pt atomic layers shows a mass activity of 8.60 A mg(Pd+Pt)(-1) for ethanol upgrading to acetic acid and close to 100% of Faradic efficiency for HER. An EOR/HER electrolysis system is assembled using Pd3Pb@Pt for both the anode and cathode, and it is shown that low cell voltage of 0.75 V is required to reach a current density of 10 mA cm(-2). The present work offers a promising strategy for the development of bifunctional catalysts for hybrid electrocatalytic reactions and beyond.