Platinum nanocrystals supported by silica, alumina and ceria: metal–support interaction due to high-temperature reduction in hydrogen

Regular Pt nanoparticles, obtained by epitaxial deposition on NaCl surfaces, were supported by thin films of silica, alumina and ceria and subjected to hydrogen reduction at temperatures up to 1073 K. The changes in morphology and composition were followed by (HR)TEM, electron diffraction and EELS, and the results were supported by theoretical calculations. The structural changes of the Pt particles upon reduction at 773 K and above are surprisingly similar despite the differing chemical properties of the three supports. Some platelet- and cube-like geometries exhibit double lattice periodicities in high resolution images and electron diffraction patterns. With increasing reduction larger aggregates of more complex appearance and structure are formed. Surface reconstruction under hydrogen and alloy formation are considered as responsible for this effect. Most likely, the first step is identical on all three systems and consists in the topotactic formation of Pt rich Pt3Me (Me=Si, Al, Ce) under the influence of hydrogen, followed by transformation into diverging structures of lower Pt content and different crystallography. Density functional calculations were performed for deriving energies of formation of PtMe and Pt3Me compounds.