Tuning the Structure of Pt Nanoparticles through Support Interactions: An in Situ Polarized X-ray Absorption Study Coupled with Atomistic Simulations

[Image: see text] Interactions of nanoparticles (NPs) with their environment may have a pronounced effect on their structure and shape as well as on their functionality in applications such as catalysis. It is therefore crucial to disentangle the particle–adsorbate and particle–support interaction effects on the particle shape, its local structure, atomic dynamics, and its possible anisotropies. In order to gain insight into the support effect, we carried out an X-ray absorption fine-structure spectroscopy (XAFS) investigation of adsorbate- and ligand-free size-selected Pt NPs deposited on two different supports in ultrahigh vacuum. Polarization-dependent XAFS measurements, neural network-based analysis of X-ray absorption near-edge structure data, and reverse Monte Carlo (RMC) simulations of extended X-ray absorption fine structure (EXAFS) were used to resolve the 3D shape of the NPs and details of their local structure. A synergetic combination of advanced in situ XAFS analysis with atomic force microscopy and scanning tunneling microscopy (STM) imaging provides uniquely detailed information about the particle–support interactions and the NP/support buried interface, not accessible to any experimental technique, when considered alone. In particular, our combined approach reveals differences in the structure of Pt NPs deposited on TiO(2)(110) and SiO(2)/Si(111). Pt NPs on SiO(2) assume a spherical-like 3D shape and weakly interact with the support. In contrast, the effective shape of analogously synthesized Pt NPs on TiO(2)(110) after annealing at 600 °C is found to be a truncated octahedron with (100) top and interfacial facets that are encapsulated by the TiO(2) support. Modeling disorder effects in these NPs using an RMC approach reveals differences in bond-length distributions for NPs on different supports and allows us to analyze their anisotropy, which may be crucial for the interpretation of support-dependent atomic dynamics and can have an impact on the understanding of the catalytic properties of these NPs.