Replacing
the kinetics sluggish oxygen evolution reaction with
thermodynamically favorable ethanol oxidation reaction (EOR) is a
prospective method to boost energy-efficient hydrogen production.
Surface regulation has achieved great success in enhancing catalytic
performance, but it has been rarely demonstrated for the coupled hydrogen
evolution reaction (HER)/EOR to date. Herein, the three-dimensional
PtCu nanoframe (NF) with high-index facets and multi-channels is designed
through a dealloying strategy to achieve bifunctional catalysis for
HER and EOR. The PtCu NF/C needs only 0.58 V to arrive at 10 mA cm–2 in the coupled HER/EOR, while 1.88 V is required
in water splitting. Moreover, ethanol can be oxidized by PtCu NF/C
to acetate with a high Faradaic efficiency of 92%. Mechanistic studies
reveal that the combination of the three-dimensional structure, Cu
introduction, and high-index facets endows the PtCu NF/C with enhanced
adsorption capacity for ethanol and H2O, as well as dissociation
capacity for C–H bonds of ethanol. This work is the icing on
the cake for bifunctional electrocatalysts and the further development
of energy-saving hydrogen evolution.