Intermetallics with sp-d orbital hybridisation: morphologies, stabilities and work functions of In-Pd particles at the nanoscale.

The field of intermetallic catalysts, alloying a p-block and a transition metal to form a pM-TM bimetallic alloy, is experiencing robust growth, emerging as a vibrant frontier in catalysis research. Although such materials are increasingly used in the form of nanoparticles, a precise description of their atomic arrangements at the nanoscale remains scarce. Based on the In-Pd binary as a typical pM-TM system, we performed density functional theory calculations to investigate the morphologies, relative stabilities and electronic properties of 24 Å and 36 Å nanoparticles built from the In 3 Pd 2 , InPd and InPd 3 compounds. Wulff equilibrium structures are compared to other ordered and disordered structures. Surface energies are computed to discuss their thermodynamic stability, while work functions are calculated to examine their electronic structures. For any compound, increasing the size leads to the stabilisation of Wulff polyhedra, which are found to offer smaller surface energies than non-crystalline and chemically disordered structures. Disordered In 3 Pd 2 and InPd nanoparticles show a tendency towards amorphisation, owing to repulsive short In-In bonds. Tuning nanoparticles' work functions can be achieved through the control of the surface structure and composition, by virtue of the roughly linear correlation found between the surface composition and the work function which nevertheless includes a certain number of outliers. This work paves the way to rationalisation of both structural and electronic properties of pM-TM nanoparticles.