Comment on "Interaction of hydrogen with RuO2(110) surfaces: activity differences between various oxygen species".
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Biomedical subjects
Publications and source records attributed to A P Seitsonen.
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The reduction mechanism of the RuO(2)(110) surface by molecular hydrogen exposure is unraveled to an unprecedented level by a combination of temperature programmed reaction, scanning tunneling microscopy, high-resolution core level shift spectroscopy, and density functional theory calculations. We demonstrate that even at room temperature hydrogen exposure to the RuO(2)(110) surface leads to the formation of water. In a two-step process, hydrogen saturates first the bridging oxygen atoms to form (O(br)-H) species and subsequently part of these O(br)-H groups move to the undercoordinated Ru atoms where they form adsorbed water. This latter process is driven by thermodynamics leaving vacancies in the bridging O rows.
The visualization of surface reactions on the atomic scale provides direct insight into the microscopic reaction steps taking place in a catalytic reaction at a (model) catalyst's surface. Employing the technique of scanning tunneling microscopy (STM), we investigated the CO oxidation reaction over the RuO2(110) and RuO2(100) surfaces. For both surfaces the protruding bridging O atoms are imaged in STM as bright features. The reaction mechanism is identical on both orientations of RuO2. CO molecules adsorb on the undercoordinated surface Ru atoms from where they recombine with undercoordinated O atoms to form CO2 at the oxide surface. In contrast to the RuO2(110) surface, the RuO2(100) surface stabilizes also a catalytically inactive c(2 x 2) surface phase onto which CO is not able to adsorb above 100 K. We argue that this inactive RuO2(100)-c(2 x 2) phase may play an important role in the deactivation of RuO2 catalysts in the electrochemical Cl2 evolution and other heterogeneous reactions.
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Exposing water to a (2 x 2)-O precovered Pt(111) surface at 100 K and subsequently annealing at 155 K led to the formation of a well-ordered (square root 3 x square root 3)R30 degrees overlayer. The structure of this overlayer is determined by DFT and full dynamical LEED calculations. There are two O containing groups per (square root 3 x square root 3)R30 degrees unit cell and both occupy near on-top positions with a Pt-O bond length of (2.11 +/- 0.04) A. DFT calculations determined the hydrogen positions of the OH species and clearly indicate hydrogen bonds between the neighboring adsorbed OH groups whose interaction is mainly of electrostatic nature. A theoretical comparison with H(2)O shows the hybridization of OH on Pt(111) to be sp(3).