A study of platinum-coated nanoparticles shows how energy balance controls crystal growth
Many catalysts are made using core-shell nanoparticles, in which the core is a structurally important or inexpensive material and the thin shell surrounding it is an expensive metal such as platinum. Since catalytic reactions occur on the surface, this helps to reduce the amount of platinum required and therefore lowers costs. Crystal structures are described based on the smallest repeating unit of the crystal (the unit cell) using the Bravais lattice system. Three important crystal structures are face-centred cubic (fcc, atoms at the corners and faces of a cube), body-centred cubic (bcc, atoms at the corners and centre of a cube), and hexagonal close-packed (hcp, a hexagonal arrangement of atoms).
Different materials have different crystal structures; for example, platinum is fcc, many alloys are bcc, and magnesium and zinc are hcp. In core–shell nanoparticles, differences between the crystal structures of the core and shell mean that the atoms do not line up perfectly. This mismatch creates strain, which can significantly affect catalytic performance. In this work, the researchers explored how a platinum shell grows on a different crystal structure in a process known as heteroepitaxy.
They studied platinum shells (Pt, fcc) grown on cores made of ruthenium (Ru, hcp), palladium–copper (PdCu, bcc), and specially synthesised ruthenium with an fcc structure. It was found that each system accommodates the atomic mismatch differently. In hcp/fcc particles, some areas lined up coherently while others contained defects called dislocations, which formed networks in particles smaller than 10 nm. In bcc/fcc particles, both the core and shell stretched or compressed to fit together. In fcc/fcc particles, the matching crystal structures aligned more readily, but twin defects formed in which one region mirrored another.
Overall, this study shows that the way a Pt shell grows on a nanoparticle core is determined by a balance between the energies of the interface, shell, and core, with the system naturally adopting the lowest-energy configuration. These findings could help scientists achieve atomic-precision interfacial engineering, controlling the catalytic, mechanical, and electrical properties of core-shell nanoparticles.
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PLP-Logo-2.png, find out more. Single metal nanoparticles: optical detection, spectroscopy and applications by P Zijlstra and M Orrit (2011)