The metal-support interaction plays a critical role in heterogeneous catalysis. Under reducing conditions, oxidic supports may interact with supported metal particles, by either forming an oxide overlayer or an alloy. The structure of both the support and the nanoparticle, as well as of the interface itself, changes in response to varying environmental conditions. Here, we present a fullyab initioapproach to predict the structures and energetics of such systems for a range of transition metals (Me = Cu, Ru, Pd, Ag, Rh, Os, Ir, Pt, Au) supported on titania surfaces as a function of gas atmosphere composition. The competing formation of a monolayer comprising fully oxidized titania (TiO₂), its reduced forms (Ti₂O₃, TiO), and the Ti-Me surface alloy, is investigated. The stability of each of these phases is found to be very sensitive to the environmental conditions and the supported metal. Encapsulation of metal, also known as classical strong metal-support interaction (SMSI), was predicted by thermodynamic driving force analysis. We show that a simple parameter, the Ti-Me alloy formation energy, is a good descriptor for the strength of the interaction between metal substrates and reduced titania monolayers and has predictive power towards the conditions under which an overlayer is stable. The presented thermochemical data and phase diagram analysis can be used to identify the structure and stability of supported metal catalysts under realistic conditions.

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Catalytic systems based on supported noble metals are extensively studied because of their widespread application. Discussions remain about the nature of the active species, whether they are atomically dispersed or nanoparticles, and their reactivity. In this work, combining in situ/operando spectroscopy with theoretical modeling, we propose a phase diagram of atomically dispersed platinum on ceria, demonstrating that it reversibly changes from PtIVO2 to PtIIO as a function of temperature and oxygen partial pressure. The phase diagram helps identify the stability domain of each species, while spectroscopies provide a quantitative evaluation depending on the reaction conditions. Finally, our results show that high-temperature activation in the presence of steam of supported atomically dispersed platinum enhances the activity toward low-temperature carbon monoxide oxidation because it promotes aggregation into nanoparticles. This work highlights the structure-activity relationship in supported metal catalysts and proposes a suitable approach to determine the amount of each species before the investigation of the reaction mechanism.

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Heterogeneous catalysts play a pivotal role in the chemical industry. The strong metal-support interaction (SMSI), which affects the catalytic activity, is a phenomenon researched for decades. However, detailed mechanistic understanding on real catalytic systems is lacking. Here, this surface phenomenon was studied on an actual platinum-titania catalyst by state-of-the-art in situ electron microscopy, in situ X-ray photoemission spectroscopy and in situ X-ray diffraction, aided by density functional theory calculations, providing a novel real time view on how the phenomenon occurs. The migration of reduced titanium oxide, limited in thickness, and the formation of an alloy are competing mechanisms during high temperature reduction. Subsequent exposure to oxygen segregates the titanium from the alloy, and a thicker titania overlayer forms. This role of oxygen in the formation process and stabilization of the overlayer was not recognized before. It provides new application potential in catalysis and materials science.

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Process capability indices (PCIs) are widely used to assess whether an in-control process meets manufacturing specifications. In most applications of classical PCIs, the process characteristic is assumed normally distributed. However, the normal distribution has been found inappropriate in various applications. In the literature, the percentile-based PCIs are widely used to deal with the nonnormal process. One problem associated with the percentile-based PCIs is that they do not provide a quantitative interpretation to the process capability. In this study, new PCIs that have a consistent quantification to the process capability for both normal and nonnormal processes are proposed. The proposed PCIs are generalizations of the classical normal PCIs in the sense that they are the same as the classical PCIs when the process characteristic follows a normal distribution, and they offer the same interpretation to the process capability as the classical PCIs when the process characteristic is nonnormal. We then discuss nonparametric and parametric estimation of the proposed PCIs. The nonparametric estimator is based on the kernel density estimation and confidence limits are obtained by the nonparametric bootstrap, while the parametric estimator is based on the maximum likelihood estimation and confidence limits are constructed by the method of generalized pivots. The proposed methodologies are demonstrated using a real example from a manufacturing factory.@en

Through the combination of density functional theory calculations and ab initio atomistic thermodynamics modeling, we demonstrate that atomically dispersed platinum species on ceria can adopt a range of local coordination configurations and oxidation states that depend on the surface structure and environmental conditions. Unsaturated oxygen atoms on ceria surfaces play the leading role in stabilization of PtO_x species. Any mono-dispersed Pt⁰ species are thermodynamically unstable compared to bulk platinum, and oxidation of Pt⁰ to Pt²⁺ or Pt⁴⁺ is necessary to stabilize mono-dispersed platinum atoms. Reduction to Pt⁰ leads to sintering. Both Pt²⁺ and Pt⁴⁺ prefer to form the square-planar [PtO₄] configuration. The two most stable Pt²⁺ species on the (223) and (112) surfaces are thermodynamically favorable between 300 and 1200 K. The most stable Pt⁴⁺ species on the (100) surface tends to desorb from the surface as gas phase above 950 K. The resulting phase diagrams of the atomically dispersed platinum in PtO_x clusters on various ceria surfaces under a range of experimentally relevant conditions can be used to predict dynamic restructuring of atomically dispersed platinum catalysts and design new catalysts with engineered properties.

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Ostwald ripening is a leading cause of the degradation of platinum group catalysts at high temperature in an oxidizing atmosphere. Recent experiments suggested that volatile species can be trapped on ceria, forming atomically dispersed active catalytic sites instead of large nanoparticles. Here we present a comparative density functional theory study of the interaction of PtO₂(g), the most likely volatile species responsible for the process of Ostwald ripening, with various surfaces. Defect-free CeO₂(111) and Al₂O₃(100) surfaces have a very small binding energy towards PtO₂(g) compared to the platinum surface, indicative of particle growth. However, the stepped edge of the CeO₂(111) surface effectively traps the mobile species, generating atomically dispersed catalysts. Such trapped single-atom platinum-on-ceria catalysts are predicted to have a square-planar [PtO₄] structure, with the platinum atom strongly binding to the surface, preventing platinum atoms from aggregating into larger nanoparticles. These results provide an atomic insight into the single atom trapping and suggest a route for the development of sinter-resistant catalysts.

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