Interfacial Atom Rearrangement Drives Potential‐Adaptive Electrocatalytic Olefin Hydrogenation

Dynamic rearrangement of metal atoms at heterointerfaces by chemical bond conversion drives high efficiency electrocatalytic processes. It is of great significance to explore transformative catalytic systems that directly control the interfacial structure and function of atomic composition. As an emerging 2D carbon allotrope, graphdiyne (GDY) offers unprecedented advantages for heterointerface engineering. In particular, the uneven surface charge distribution, high distribution of active sites and customizable electronic structures of GDY provide unprecedented opportunities for developing new‐generation catalytic systems. Here, we report a new idea to directly control the cooperative growth and drive metal atomic rearrangement on the interface of GDY/NiPd/GDY. Experimental results revealed two unique interfacial phenomena: (i) GDY‐induced massive dislocation formation within NiPd nanoalloys and (ii) rearrangement of surface metal atoms from (111) to (200) facets. Detailed spectroscopic analysis further demonstrated the composition‐dependent evolution of elemental valence states and stoichiometric ratios. This atomic‐level restructuring establishes a charge‐redistribution network featuring non‐integer charge transfer, which improves the overall conductivity and intrinsic activity. What is even more encouraging is that this electrocatalytic olefin hydrogenation is carried out in an aqueous solution. The GDY/NiPd/GDY heterostructure achieves exceptional activity (turnover frequency: 6.8 s‐1), stability (>5 cycles), and chemo‐selectivity (~100%), which is superior to traditional catalysts.