Electronic interactions between metal nanoparticles and oxide supports control the functionality of nanomaterials, for example, the stability, the activity and the selectivity of catalysts. Such interactions involve electron transfer across the metal/support interface. In this work we quantify this charge transfer on a well-defined platinum/ceria catalyst at particle sizes relevant for heterogeneous catalysis. Combining synchrotron-radiation photoelectron spectroscopy, scanning tunnelling microscopy and density functional calculations we show that the charge transfer per Pt atom is largest for Pt particles of around 50 atoms. Here, approximately one electron is transferred per ten Pt atoms from the nanoparticle to the support. For larger particles, the charge transfer reaches its intrinsic limit set by the support. For smaller particles, charge transfer is partially suppressed by nucleation at defects. These mechanistic and quantitative insights into charge transfer will help to make better use of particle size effects and electronic metal-support interactions in metal/oxide nanomaterials.

Charles University Faculty of Mathematics and Physics Department of Surface and Plasma Science V Holešovičkách 2 18000 Prague 8 Czech Republic

CNR IOM DEMOCRITOS Istituto Officina dei Materiali Consiglio Nazionale delle Ricerche and SISSA Via Bonomea 265 1 34136 Trieste Italy

Departament de Química Física and Institut de Quimica Teòrica i Computacional Universitat de Barcelona c Martí i Franquès 1 08028 Barcelona Spain

Erlangen Catalysis Resource Center Friedrich Alexander Universität Erlangen Nürnberg Egerlandstraße 3 D 91058 Erlangen Germany

Institucio Catalana de Recerca i Estudis Avançats 08010 Barcelona Spain

Lehrstuhl für Physikalische Chemie 2 Friedrich Alexander Universität Erlangen Nürnberg Egerlandstraße 3 D 91058 Erlangen Germany

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