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Catalysis is an indispensable part of our society, massively involved in numerous energy and environmental applications. Although, noble metals (NMs)-based catalysts are routinely employed in catalysis, their limited resources and high cost hinder the widespread practical application. In this regard, the development of NMs-free metal oxides (MOs) with improved catalytic activity, selectivity and durability is currently one of the main research pillars in the area of heterogeneous catalysis. The present review, involving our recent efforts in the field, aims to provide the latest advances—mainly in the last 10 years—on the rational design of MOs, i.e., the general optimization framework followed to fine-tune non-precious metal oxide sites and their surrounding environment by means of appropriate synthetic and promotional/modification routes, exemplified by CuOx/CeO2 binary system. The fine-tuning of size, shape and electronic/chemical state (e.g., through advanced synthetic routes, special pretreatment protocols, alkali promotion, chemical/structural modification by reduced graphene oxide (rGO)) can exert a profound influence not only to the reactivity of metal sites in its own right, but also to metal-support interfacial activity, offering highly active and stable materials for real-life energy and environmental applications. The main implications of size-, shape- and electronic/chemical-adjustment on the catalytic performance of CuOx/CeO2 binary system during some of the most relevant applications in heterogeneous catalysis, such as CO oxidation, N2O decomposition, preferential oxidation of CO (CO-PROX), water gas shift reaction (WGSR), and CO2 hydrogenation to value-added products, are thoroughly discussed. It is clearly revealed that the rational design and tailoring of NMs-free metal oxides can lead to extremely active composites, with comparable or even superior reactivity than that of NMs-based catalysts. The obtained conclusions could provide rationales and design principles towards the development of cost-effective, highly active NMs-free MOs, paving also the way for the decrease of noble metals content in NMs-based catalysts.

Ceria has been widely studied either as catalyst itself or support of various active phases in many catalytic reactions, due to its unique redox and surface properties in conjunction to its lower cost, compared to noble metal-based catalytic systems. The rational design of catalytic materials, through appropriate tailoring of the particles’ shape and size, in order to acquire highly efficient nanocatalysts, is of major significance. Iron is considered to be one of the cheapest transition metals while its interaction with ceria support and their shape-dependent catalytic activity has not been fully investigated. In this work, we report on ceria nanostructures morphological effects (cubes, polyhedra, rods) on the textural, structural, surface, redox properties and, consequently, on the CO oxidation performance of the iron-ceria mixed oxides (Fe2O3/CeO2). A full characterization study involving N2 adsorption at –196 °C, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), temperature programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) was performed. The results clearly revealed the key role of support morphology on the physicochemical properties and the catalytic behavior of the iron-ceria binary system, with the rod-shaped sample exhibiting the highest catalytic performance, both in terms of conversion and specific activity, due to its improved reducibility and oxygen mobility, along with its abundance in Fe2+ species.

A direct quantitative correlation of surface-to-bulk (Os/Ob) reducible oxygen of ceria nanoparticles (NPs) with catalytic activity was revealed.

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