Particle size governs the geometric and electronic structure of metal nanoparticles (NPs), shaping their catalytic performance. However, size-dependent entanglement in the geometric and electronic structures often leads to a trade-off between activity and selectivity, limiting the optimization of the overall catalytic performance. Based on this situation, a platinum monolayer on large gold NPs was precisely controlled synthesized to break the activity–selectivity trade-off on particle size in platinum-catalysed chemoselective hydrogenation of halonitrobenzenes, resulting in a remarkable activity, along with a 99% selectivity for haloanilines under mild conditions. The high activity results from upshift of the platinum 5<i>d</i>-band centre through platinum lattice expansion and ligand effect, whereas the high selectivity is caused by exposing more terrace sites on large particles. The geometric and electronic properties of bimetallic monolayer materials, distinct from monometallic NPs and alloys, constitute a promising platform for the rational design of metal catalysts with superior performance in hydrogenation reactions.

Bimetallic monolayer catalyst breaks the activity–selectivity trade-off on metal particle size for efficient chemoselective hydrogenations

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