Enhanced dispersion and the reactivity of atomically thin Rh layers supported by molybdenum oxide films

The behavior of rhodium layers deposited on oxidized, 0.15-20.0 ML thick Mo films formed on a nearly stoichiometric TiO2(110) single crystal was characterized by AES, TPD and work function (WF) measurements. The oxidation of 0.15-2.7 ML thick Mo deposits was performed via the redox reaction with the titania support at 1000 K. Molybdenum oxide supports of MoO3 and MoO2 surface composition were formed by the oxidation of 20 ML thick Mo multilayers by O2 at 650 K and 1000 K, respectively. Rh grows in a layer-by-layer fashion on a mixed titanium-molybdenum oxide produced in the reaction between titania and 0.15 ML Mo, corresponding to a considerably enhanced dispersion of rhodium as compared with that on the clean TiO2(110). The surface reactivity of Rh layers supported by molybdenum oxides as a function of pre-annealing temperature was followed by carbon monoxide adsorption-desorption cycles. The CO uptake of a 0.4 ML thick Rh film formed on the MoO3 support was strongly suppressed at 300 K, indicating the encapsulation of rhodium with MoOX species of low surface free energy. The CO adsorption capability of rhodium particles supported by both MoO3 and MoO2 layers was eliminated due to pre-annealing at 600 K, related to the extended decoration of metal particles by MoOX moiety. The encapsulation of the rhodium films proceeded above 600 K on both supports, and annealing to 1000 K resulted in nearly equal WF values, indicating the formation of MoOX overlayers of similar surface composition close to MoO2. AES depth profiles revealed that the 0.4 ML thick Rh deposits covered by MoOX at 1000 K preserved their island structure. © 2015 Elsevier B.V. All rights reserved