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The Mars–van Krevelen mechanism is the foundation for oxide-catalyzed oxidation reactions and relies on spatiotemporally separated redox steps. Herein, we demonstrate the tunability of this separation with peroxide species formed by excessively adsorbed oxygen, thereby modifying the catalytic activity and selectivity of the oxide. Using CuO as an example, we show that a surface layer of peroxide species acts as a promotor to significantly enhance CuO reducibility in favor of H 2 oxidation but conversely as an inhibitor to suppress CuO reduction against CO oxidation. Together with atomistic modeling, we identify that this opposite effect of the peroxide on the two oxidation reactions stems from its modification on coordinately unsaturated sites of the oxide surface. By differentiating the chemical functionality between lattice oxygen and peroxide, these results are closely relevant to a wide range of catalytic oxidation reactions using excessively adsorbed oxygen to activate lattice oxygen and tune the activity and selectivity of redox sites.

The temperature dependence of phase composition and lattice parameters, for TiAlxN thin film coating, are experimentally investigated by in-situ synchrotron radiation X-ray diffraction (SR-XRD), at temperatures between 25 °C and 700 °C. Mechanical properties, such as: Young's modulus (E), hardness (H) and plastic deformation index (PDI) – were experimentally determined by nanoindentation, at 25 °C. Crystalline structural analysis, of SR-XRD results, indicates the major phases are TiN and AlN; with Ti2O and TiO2 phases also present above 600 °C. The lattice constants increased with an increase in temperature. Atomic and phase compositions, at 25 °C, were also verified by X-ray photoelectron spectroscopy (XPS). Field emission scanning electron microscopy (FESEM) images display an increase in surface roughness and reduction in grain size, with increasing Aluminium percentage (Al%). Nanoindentation analysis showed a maximum hardness of 25.1 ± 1.5 GPa (sample containing 12% Al), which was subsequently reduced upon addition of more Aluminium. Finite element modelling (FEM), including von Mises stress distribution, indicates lower mechanical integrity, for samples with high Al% content.

Ce/Ti mixed metal oxide thin films have well known optoelectrical properties amongst several other physio-chemical properties. Changes in the structural and mechanical properties of magnetron sputtered Ce/Ti oxide thin films on Si (100) wafers with different Ce:Ti ratios are investigated experimentally and by modelling. X-ray Photoemission Spectroscopy (XPS) and X-ray diffraction (XRD) confirm the primary phases as trigonal Ce2O3 and rutile form of TiO2 with SiO2 present in all prepared materials. FESEM imaging delivers information based on the variation of grain size, the mixed Ce/Ti oxides providing much smaller grain sizes in the thin film/substrate composite. Nanoindentation analysis concludes that the pure cerium oxide film has the highest hardness value (20.1 GPa), while the addition of excess titanium oxide decreases the hardness of the film coatings. High temperature in-situ XRD (up to 1000 degrees C) results indicate high thermal phase stability for all materials studied. The film with Ce:Ti = 68%:32% has a new additional minor oxide phase above 800 degrees C. Contact angle experiments suggest that the chemical composition of the surface is insignificant affecting the water contact angle. Results show a narrow band of 87.7-95.7 degrees contact angle. The finite element modelling (FEM) modelling of Ce/Ti thin film coatings based on Si(100); Si(110); silica and steel substrates shows a variation in stress concentration.