0000000000240017
AUTHOR
Preben J. Møller
Experimental and theoretical evidence for substitutional molybdenum atoms in theTiO2(110)subsurface
Molybdenum was deposited at room temperature on the ${\mathrm{TiO}}_{2}(110)$ surface in the 0--1.3 equivalent monolayer (eqML) range and was then annealed at $400\phantom{\rule{0.2em}{0ex}}\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$ in order to reach a kind of equilibrium state. A threshold was found in the behavior of the deposit: below 0.2 eqML, substitutional molybdenum occurs in titanium sites located under the bridging oxygen atoms of the ${\mathrm{TiO}}_{2}(110)$ surface. In this position, molybdenum atoms are in a structural and chemical ${\mathrm{MoO}}_{2}$-like environment. Density-functional theory calculations show that this molybdenum site is actually the most stable one in …
A photoemission study of molybdenum hexacarbonyl adsorption and decomposition on TiO2(110) surface.
International audience; The adsorption and decomposition of molybdenum hexacarbonyl on (110) TiO2 surfaces were studied using both core levels and valence band photoemission spectroscopies. It was found that after an adsorption at 140 K, when going back to room temperature, only a small part of molybdenum compounds, previously present at low temperature, remained on the TiO2 surface. This indicates that the desorption temperature on such a surface is lower than the decomposition one. The use of photon irradiation to decompose the hexacarbonyl molecule was also studied. It was shown that during such a decomposition molecular fragments were chemisorbed on the surface allowing a higher amount …
Reactivity between molybdenum and TiO2(110) surfaces: evidence of a sub-monolayer mode and a multilayer mode
Small amounts of molybdenum (from 0.03 to 1.3 eqML) were deposited on non-stoichiometric TiO 2 (1 1 0) surface. The deposits were investigated by means of LEED and X-ray/UV photoemission using synchrotron radiation. For the smallest coverage (<0.2 eqML), deposition leads to oxidation of molybdenum into species close to Mo 4+ .In such a case, states appearing in TiO 2 band gap are mainly due to reduced titanium. For higher coverages, metallic behaviour of molybdenum is observed. This phenomenon was explained, thanks to first principle calculations, as a decrease of the Mo-O interactions for the benefit of the Mo-Mo interactions as the surface molybdenum atom density increases.
From tungsten hexacarbonyl adsorption on TiO2(1 1 0) surface to supported tungsten oxide phases.
Abstract Synchrotron-based photoemission spectroscopies were used to study the adsorption of tungsten hexacarbonyl on (1 1 0) TiO 2 surfaces: experiments using W4f and Ti2p intensities variations show that, at 140 K, the hexacarbonyl growth proceeds via a layer-by-layer mode. Moreover, it was evidenced using both core levels and valence band experiments that, after back to room temperature, W(CO) 6 desorbs without significant decomposition. However, low energy (500 eV) ion (Ar + ) irradiation can allow partial decomposition of tungsten hexacarbonyl molecules leading to sub-carbonyl tungsten molecules. The bonding of sub-carbonyl species to the TiO 2 surface was then stronger than the one of…
Titanium dioxide surface stoichiometry and ordering studied by resonant photoemission spectroscopy
Abstract The electronic structure of titanium dioxide surfaces having undergone different preparations leading to different stoichiometries and crystallinities has been studied using resonant photoemission spectroscopy. Valence band photoemission spectra through the Ti 3p–3d/4s absorption edge between 45 and 55 eV were measured and allowed a characterization of defects present at the surface as well as of the quality of the surface organization. Indeed, from the comparison of the resonance results obtained for each kind of surface with the LEED patterns on the one hand and the corresponding Ti 2p core level lines on the other hand, it was evidenced that the high binding energy part of the v…