Surface Polarization Matters: Enhancing the Hydrogen‐Evolution Reaction by Shrinking Pt Shells in Pt–Pd–Graphene Stack Structures

Surface charge state plays an important role in tuning the catalytic performance of nanocrystals in various reactions. Herein, we report a synthetic approach to unique Pt-Pd-graphene stack structures with controllable Pt shell thickness. These unique hybrid structures allow us to correlate the Pt thickness with performance in the hydrogen-evolution reaction (HER). The HER activity increases with a decrease in the Pt thickness, which is well explained by surface polarization mechanism as suggested by first-principles simulations. In this hybrid system, the difference in work functions of Pt and Pd results in surface polarization on the Pt surface, tuning its charge state for hydrogen reduction. Meanwhile, the supporting graphene provides two-dimensional channels for efficient charge transport, improving the HER activities. This work opens up possibilities of reducing Pt usage while achieving high HER performance.