Monatomic Co, CoO$_2$, and CoO$_3$ Nanowires on Ir(100) and Pt(100) surfaces: Formation, Structure, and Energetics


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In this study we investigate the structural and chemical changes of monatomic CoO$_2$ chains grown self-organized on the Ir(100) surface [P. Ferstl et al., PRL 117, 2016, 046101] and on Pt(100) under reducing and oxidizing conditions. By a combination of quantitative low-energy electron diffraction, scanning tunnelling microscopy, and density functional theory we show that the cobalt oxide wires are completely reduced by H$_2$ at temperatures above 320 K and a 3x1 ordered Ir$_2$Co or Pt$_2$Co surface alloy is formed. Depending on temperature the surface alloy on Ir(100) is either hydrogen covered (T < 400 K) or clean and eventually undergoes an irreversible order-disorder transition at about 570 K. The Pt$_2$Co surface alloy disorders with the desorption of hydrogen, whereby Co submerges into subsurface sites. Vice versa, applying stronger oxidants than O$_2$ such as NO$_2$ leads to the formation of CoO3 chains on Ir(100) in a 3x1 superstructure. On Pt(100) such a CoO$_3$ phase could not be prepared so far, which however, is due to the UHV conditions of our experiments. As revealed by theory this phase will become stable in a regime of higher pressure. In general, the structures can be reversibly switched on both surfaces using the respective agents O$_2$, NO$_2$ and H$_2$.

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