Unlocking synergy in bimetallic catalysts by core–shell design

Extending the toolbox from mono- to bimetallic catalysts is key in realizing efficient chemical processes1. Traditionally, the performance of bimetallic catalysts featuring one active and one selective metal is optimized by varying the metal composition1–3, often resulting in a compromise between the catalytic properties of the two metals4–6. Here we show that by designing the atomic distribution of bimetallic Au–Pd nanocatalysts, we obtain a synergistic catalytic performance in the industrially relevant selective hydrogenation of butadiene. Our single-crystalline Au-core Pd-shell nanorods were up to 50 times more active than their alloyed and monometallic counterparts, while retaining high selectivity. We find a shell-thickness-dependent catalytic activity, indicating that not only the nature of the surface but also several subsurface layers play a crucial role in the catalytic performance, and rationalize this finding using density functional theory calculations. Our results open up an alternative avenue for the structural design of bimetallic catalysts. Nanomaterials may present interesting catalytic properties, but well-defined model systems are rare. Here, a Au–Pd core–shell catalyst is investigated for selective hydrogenation of butadiene, with shell-thickness-dependent catalytic activity, high selectivity and activity 50 times greater than that of alloyed counterparts.