20.500.12556/DiRROS-21966 Atypical adsorption of hydrogen on native ultrathin aluminum oxide films We report on an unusual hydrogen adsorption mode on native ultrathin aluminum-oxide films. Based on systematic density-functional theory (DFT) calculations on a model oxide film of varying thickness—i.e., α–Al2O3(001) supported on Al(111)—we show that on ultrathin films, H preferentially adsorbs on surface Al ions instead of O ions, as one would expect from chemical intuition. The so-adsorbed H is in hydride form, and for ultrathin films, it gets the electron charge from Al atoms at the oxide/metal interface. In contrast, for thicker films, this electron transfer ceases, and the charge instead predominantly comes from the surface O ions, making H adsorbed at Al sites inferior to H adsorbed at O sites. We further show that H adsorbed at Al sites can lead to H2 formation, which we propose to be connected to the experimentally observed hydrogen evolution in pits formed during the pitting corrosion of aluminum, where the protective oxide film has considerably degraded and is very thin hidrid ultra tenki filmi vodik true false true Elsevier Nizozemska Angleški jezik Slovenski jezik © 2025 The Authors. Neznano 2025-04-15 11:06:51 2025-04-15 11:06:51 2025-10-24 03:50:16 0000-00-00 00:00:00 2025 0 0 12 str. Art. 105742 Vol. 58 2025 0000-00-00 Zaloznikova Objavljeno NiDoloceno 2024-08-27 2025-01-02 2025-01-15 544 2468-0230 10.1016/j.surfin.2025.105742 223117827 RAZ_Poberznik_Matic_2025.pdf RAZ_Poberznik_Matic_2025.pdf 1 8B58BD735613880DA69276967AB2327F efe6f8ca2597c4098d6690d35ef8937bc2a1cfde229a0e9cd39dcb70c65728c3 584f9a52-19d9-11f0-963a-001a4af901a5 https://dirros.openscience.si/Dokument.php?lang=slv&id=31689 Institut Jožef Stefan 0 0 0