RESUMEN
Intermetallic compounds in the Al-Pt system were systematically studied via hard X-ray photoelectron spectroscopy, focusing on the positions of Pt 4f and Al 2s core levels and valence band features. On one hand, with increasing Al content, the Pt 4f core levels shift towards higher binding energies (BE), revealing the influence of the atomic interactions (chemical bonding) on the electronic state of Pt. On the other hand, the charge transfer from Al to Pt increases with increasing Al content in Al-Pt compounds. These two facts cannot be combined using the standard "chemical shift" approach. Computational analysis reveals that higher negative effective charges of Pt atoms are accompanied by reduced occupancy of Pt 5d orbitals, leading to the limited availability of these electrons for the screening of the 4f core hole and this in turn explains the experimentally observed shift of 4f core levels to higher BE.
RESUMEN
Al-Pt compounds have been systematically studied as electrocatalysts for the oxygen evolution reaction (OER). Considering the harsh oxidative conditions of the OER, all Al-Pt compounds undergo modifications during electrochemical experiments. However, the degree of changes strongly depends on the composition and crystal structure of a compound. In contrast to Al-rich compounds (Al4Pt and Al21Pt8), which reveal strong leaching of aluminum, changes in other compounds (Al2Pt, Al3Pt2, rt-AlPt, Al3Pt5, and rt-AlPt3) take place only on the surface or in the near-surface region. Furthermore, surface modification leads to a change in the electronic structure of Pt, giving rise to the in situ formation of catalytically more active surfaces, which are composed of intermetallic compounds, Pt-rich AlxPt1-x phases and Pt oxides. Forming a compromise between sufficient OER activity and stability, Al2Pt and Al3Pt2 can be considered as precursors for OER electrocatalysts.
