Observation and Identification of an Atomic Oxygen Structure on Catalytic Gold Nanoparticles

Interactions between oxygen and gold surfaces are fundamentally important in diverse areas of science and technology. In this work, an oxygen dimer structure was observed and identified on gold nanoparticles in catalytic decomposition of hydrogen peroxide to oxygen and water. This structure, which is different from isolated atomic or molecular oxygen surface structures, was observed with in situ surface‐enhanced Raman spectroscopic measurements and identified with density functional theory calculations. The experimental measurements were performed using monodisperse 5, 50 and 400 nm gold particles supported on silica with liquid‐phase hydrogen and deuterium peroxides at multiple pH values. The calculations show that on surfaces with coordinatively unsaturated gold atoms, two oxygen atoms preferentially share a gold atom with a bond distance of 0.194–0.196 nm and additionally bind to two other surface gold atoms with a larger bond distance of 0.203–0.213 nm, forming an Au‐O‐Au‐O‐Au structure. The formation of this structure depends on reaction rates and conditions. Katalyse auf Gold: Eine Au‐O‐Au‐O‐Au‐Struktur wurde bei der katalytischen Zersetzung von Wasserstoffperoxid zu Sauerstoff und Wasser auf Gold‐Nanopartikeln beobachtet und identifiziert. Rechnungen bestätigen, dass auf Oberflächen mit koordinativ ungesättigten Goldatomen zwei Sauerstoffatome bevorzugt ein Goldatom teilen und zusätzlich in größerem Abstand an zwei weitere Oberflächengoldatome binden.