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Abstract

Interactions with their support, adsorbates and unique structural motifs are responsible for the many intriguing properties and potential applications of supported metal nanoparticles (NPs). At the same time, they complicate the interpretation of experimental data. In fact, the methods and approaches that work well for the ex situ analysis of bulk materials may be inaccurate or introduce artifacts in the in situ analysis of nanomaterials. Here we revisit the controversial topic of negative thermal expansion and anomalies in the Debye temperature reported for oxide-supported metal NPs. In situ X-ray absorption experimental data collected for Pt NPs in ultrahigh vacuum and an advanced data analysis approach based on an artificial neural network demonstrate that Pt NPs do not exhibit intrinsic negative thermal expansion. Similarly as for bulk materials, in the absence of adsorbates the bond lengths in metal NPs increase with temperature. The previously reported anomalies in particle size-dependent Debye temperatures can also be linked to the artifacts in the interpretation of conventional X-ray absorption data of disordered materials such as NPs.